A Mossbauer Spectroscopy and Magnetometry Study of Magnetic Multilayers and Oxides - John Bland

A Mssbauer Spectroscopy and Magnetometry o Study of Magnetic Multilayers and Oxides
John Bland, M.Phys. (Hons)
Submitted in partial fullment of the requirements of the degree of Doctor of Philosophy Oliver Lodge Laboratory, Department of Physics, University of Liverpool September 2002
Abstract
A study of the magnetic properties of thin lms, multilayers and oxides has been performed using Mssbauer spectroscopy and SQUID magnetometry. The systems o studied are DyFe2 , HoFe2 and YFe2 cubic Laves Phase thin lms, DyFe2 /Dy and DyFe2 /YFe2 multilayers; Ce/Fe and U/Fe multilayers; and iron oxide powders and thin lms. CEMS results at room temperature show a low symmetry magnetic easy axis for all of the Laves Phase samples studied. Analysis of the dipolar and contact hyperne elds show that this axis is close to the [ 241] and [ 351] directions but cannot be fully determined. The spin moments lie out of plane in all samples by approximately 22 , indicating a signicant magneto-elastic anisotropy. 2.5 kG inplane applied eld measurements indicate a much larger magnitude of magnetocrystalline anisotropy in the DyFe2 system than in the YFe2 system. In the DyFe2 /YFe2 multilayer samples the anisotropy is dominated by the dysprosium single-ion anisotropy, propagated through the antiferromagnetic coupling with the iron moments and then through the YFe2 layers by the strong iron-iron exchange coupling. The DyFe2 (50 )/YFe2 (50 ) sample shows average hyperne elds conA A sistent with the DyFe2 and YFe2 thin lm results, whilst samples with thinner layers show an enhanced hyperne eld of up to 17%. The DyFe2 /Dy multilayers have identical zero eld properties to the DyFe2 thin lm system down to a DyFe2 thickness of 50 . In all samples studied under applied eld the hyperne elds A were reduced from their zero eld values. SQUID magnetometry results from the Ce/Fe multilayers show that most of the samples exhibit antiferromagnetic coupling, with a TN ranging between 125 K and 190 K, dependent upon both cerium and iron layer thicknesses. The exchange coupling constant, J(z), has been calculated for antiferromagnetically coupled samples and shows an oscillatory z dependence. CEMS results from the U/Fe multilayers shows that each iron layer is composed of BCC iron, a poorly-crystalline iron layer with a reduced hyperne eld of up to 3%, and a doublet from a paramagnetic UFe2 layer. The relative thicknesses of these layers scale nonlinearly with the thickness of the deposited iron layer below 60 . Above this thickness the disordered A iron and UFe2 layers reach maximum thicknesses of 20 and 18 respectively. A A Where the uranium layer has poor crystalline growth this is propagated into the iron layer and increases these thicknesses. Room temperature Mssbauer spectroscopy results from a selection of printer o toner powders were used to produce the ratio of magnetite to maghemite in the powders. CEMS results on magnetite thin lms showed good crystal growth on a Pt(111) substrate, with some iron forming a non-magnetic layer diused in the platinum. Magnetite deposited on Al2 O3 (0001) substrates showed good crystal growth when using an oxygen plasma source, but that from a normal sputtering source showed a distribution of hyperne elds and a paramagnetic contribution from iron substituting for aluminium in the substrate.
Acknowledgements
First and foremost I oer my sincerest gratitude to my supervisor, Dr Mike Thomas, who has supported me thoughout my thesis with his patience and knowledge whilst allowing me the room to work in my own way. I attribute the level of my Masters degree to his encouragement and eort and without him this thesis, too, would not have been completed or written. One simply could not wish for a better or friendlier supervisor. In the various laboratories and workshops I have been aided for many years in running the equipment by Keith Williams, a ne technician who kept me in sample holders and liquid helium against all odds. The smooth running of the Mssbauer laboratory is much more a testament to his eorts than my o own. Simon Case and Gaby Milford helped tutor me in the more esoteric methods necessary to run Mssbauer spectrometers and how to analyse the o data from them. Dr Jon Go gave useful guidance in the use of the SQUID magnetometer along with Pascale Deen, and her ingenious sample holder construction. As well as keeping me stocked with general supplies, Peter Davenport has also inadvertently, and without fail, provided something much greater in all the years Ive known him: a friendly smile and a hello every time we met. Drs Ward and Wells have provided me with all of the Laves Phase MBE samples covered in this thesis as well as many others, with consistent quality. Professor Bowden has oered much advice and insight throughout my work on Laves Phase systems. Drs F. Schedin, P. Morrel and G. Thornton provided me with the magnetite thin lms I studied. In my daily work I have been blessed with a friendly and cheerful group of fellow students. Pascale Deen, as well as SQUID information, has provided good arguments about Physics theory and helped me regain some sort of tness: healthy body, healthy mind. Adina Toader often made sure none of us starved and Simon Lee made sure none of us went thirsty (or sober). Tarek (Taz) Nouar kept us entertained with his huge repertoire of anecdotes and stories. Mark Gallagher amused us with his dry wit and a great nononsense Christmas shindig (and did a good job of trying to kill me with snakebite and black). Stuart Medway was a good companion on an otherwise exhausting and disappointing experiment in Grenoble and although he did once explain the dierence between League and Union rugby I must confess to have forgotten every word since. Matt Ball has had the good grace to pester me much less than average with computer questions and pulls a good A pint in the Cambridge. Jonathan Pearce helped me get on the road to L TEX and provided an experienced ear for my doubts about writing a thesis. Peter Normile has fascinated me with his ability to break computer systems but has i
also given me detailed discussions on physics theory and some good laughs. In many ways I have learnt much from and because of him! Angela Beesely has impressed me with her willingness to learn how to use both the computer systems I set up and the ner points of running the Mssbauer lab, which I o now consider to be in her capable hands. She also kept me on my theoretical toes with her Mssbauer questions. o Beyond Physics (which sometimes seemed to be nothing more than a distant dream) Andrew Herring has been a companiable housemate for many years as well as a colleague and possesses the greatest quality in a housemate: not driving me up the wall too often! Simon Lee has been an invaluable help in taking over the computer systems from me and sometimes managed to counter my introversion with the occasional sneaky one up the Cambridge (this being an approximation that only holds for large values of one). His willingness to help people and make sure everyone has a good time is only matched by his willingness to bare his behind at all and sundry. Thanks also go to the other (million or so) residents at 8, Church Road, for living without their front room for a month. Gillian Howden has brightened many a dull lunchtime. Kira Brown, as well as essentially teaching me everything I know about unix, has often had to bear the brunt of my frustration and rages against the world and recalcitrant spectrometers with equanimity and friendship. She also (eventually!) sourced me a quality workstation which much of the work has been done on. I am also indebted to the many countless contributors to the Open Source programming community for providing the numerous tools and systems I have used to produce both my results and this thesis. The entirety of my thesis has been completed using such technologies and I consider it to have been an enormous benet. Thanks chaps, keep up the good work. The Department of Physics has provided the support and equipment I have needed to produce and complete my thesis and the EPSRC has funded my studies. Finally, I thank my parents for supporting me throughout all my studies at University, moving my vast collections of stu across most of Liverpool and for providing a home in which to complete my writing up.
ii
Contents
1 Introduction 1.1 Thesis Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Mssbauer Spectroscopy o 2.1 The Mssbauer Eect . . . . . . . . . . . . . . . . . . . . o 2.1.1 Recoil and Line Broadening . . . . . . . . . . . . 2.1.2 Recoil-Free Events . . . . . . . . . . . . . . . . . 2.1.3 Resolution . . . . . . . . . . . . . . . . . . . . . . 2.2 Mssbauer Spectroscopy . . . . . . . . . . . . . . . . . . o 2.3 Hyperne Interactions . . . . . . . . . . . . . . . . . . . 2.3.1 Center Shift . . . . . . . . . . . . . . . . . . . . . 2.3.2 Electric Quadrupole Splitting . . . . . . . . . . . 2.3.3 Magnetic Hyperne Splitting . . . . . . . . . . . 2.3.4 Combined Magnetic and Quadrupole Interactions 2.3.5 Spectrum Line Intensities . . . . . . . . . . . . . 2.4 Relaxation Phenomena . . . . . . . . . . . . . . . . . . . 2.5 Conversion Electron Mssbauer Spectroscopy . . . . . . . o 2.5.1 CEMS Decay Scheme . . . . . . . . . . . . . . . . 2.5.2 Depth Dependence . . . . . . . . . . . . . . . . . 3 Magnetometry 3.1 Magnetic Measurements . . . . . . . . . . 3.1.1 Magnetic Moments . . . . . . . . . 3.1.2 Magnetisation . . . . . . . . . . . . 3.1.3 Magnetic Response . . . . . . . . . 3.1.4 Background Contributions . . . . . 3.2 Hysteresis . . . . . . . . . . . . . . . . . . 3.2.1 Diamagnetism and Paramagnetism 3.2.2 Ferromagnetism . . . . . . . . . . . 3.2.3 Remanence . . . . . . . . . . . . . 3.2.4 Coercivity . . . . . . . . . . . . . . iii 1 1 4 4 4 6 7 7 8 9 10 11 14 15 17 19 19 19 22 22 23 24 25 25 26 26 27 28 30
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
3.3 3.4 3.5
Antiferromagnetism . . . . . . . . . . . . . . . . . . . . . . . . Temperature Dependence . . . . . . . . . . . . . . . . . . . . SQUID Magnetometry . . . . . . . . . . . . . . . . . . . . . . 3.5.1 Electron-pair Waves . . . . . . . . . . . . . . . . . . . 3.5.2 Josephson Tunnelling . . . . . . . . . . . . . . . . . . . 3.5.3 Superconducting Quantum Interference Device (SQUID) 3.5.4 SQUID Magnetometer . . . . . . . . . . . . . . . . . .
31 31 35 35 38 39 41 43 43 43 44 46 48 48 48 49 49 49 50 52 52 53 53 53 53 54 55 55 56 56 58 58 60 62 63 63 63 67
4 Experimental Techniques 4.1 Mssbauer Spectrometers . . . . . . o 4.1.1 Gamma-ray Source . . . . . . 4.1.2 Basic Mssbauer Spectrometer o 4.1.3 CEMS . . . . . . . . . . . . . 4.2 Data Analysis . . . . . . . . . . . . . 4.2.1 2 Minimisation . . . . . . . . 4.2.2 Fitting Routines . . . . . . . 4.2.3 Calibration . . . . . . . . . . 4.3 SQUID Magnetometer . . . . . . . . 4.3.1 Magnetometer Overview . . . 4.3.2 RSO Measurements . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
5 Magnetic Interactions 5.1 Magnetic Anisotropy . . . . . . . . . . . . 5.2 Magnetocrystalline Anisotropy . . . . . . . 5.2.1 Uniaxial Anisotropy . . . . . . . . 5.2.2 Interface and Volume Anisotropy . 5.2.3 Single-ion Anisotropy . . . . . . . . 5.2.4 Shape Anisotropy . . . . . . . . . . 5.2.5 Exchange Interaction and Exchange 5.3 Magnetostriction . . . . . . . . . . . . . . 5.3.1 Magneto-elastic Anisotropy . . . . 5.4 The RKKY Interaction . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Anisotropy . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
6 RFe2 Laves Phase Thin Films 6.1 Introduction to Rare Earth/Iron Laves Phase Systems 6.1.1 Bulk Properties . . . . . . . . . . . . . . . . . . 6.1.2 Thin Films and Multilayers . . . . . . . . . . . 6.1.3 Sample Construction . . . . . . . . . . . . . . . 6.2 RFe2 Thin Films . . . . . . . . . . . . . . . . . . . . . 6.2.1 Determining the Magnetic Easy Axis . . . . . . 6.2.2 DyFe2 . . . . . . . . . . . . . . . . . . . . . . . iv
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
6.3 6.4
6.2.3 YFe2 . . . . . . . 6.2.4 HoFe2 . . . . . . DyFe2 /Dy Multilayers . DyFe2 /YFe2 Multilayers 6.4.1 Introduction . . . 6.4.2 Results . . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
71 74 74 77 77 78 83 84 85 93 95 97 98 107 107 108 108 109 111 111 112 119 122
7 RE/Fe & A/Fe Magnetic Multilayers 7.1 Ce/Fe Multilayers . . . . . . . . . . . . . . . . 7.1.1 Temperature vs Magnetisation Scans . 7.1.2 Estimation of Coupling Constant, J(z) 7.1.3 Hysteresis Loops . . . . . . . . . . . . 7.2 U/Fe Multilayers . . . . . . . . . . . . . . . . 7.2.1 CEMS Results . . . . . . . . . . . . . . 8 Magnetic Iron Oxides 8.1 Introduction to Magnetite . . . . 8.2 Printer Toner Powders . . . . . . 8.2.1 Introduction . . . . . . . . 8.2.2 Results . . . . . . . . . . . 8.3 Single Crystal Fe3 O4 Thin Films . 8.3.1 Introduction . . . . . . . . 8.3.2 Results . . . . . . . . . . . 9 Concluding Remarks A Publications
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
List of Figures
2.1 Recoil in a free nucleus during gamma ray emission. . . . . . . 2.2 Gamma ray energy distributions for emission and absorption in free atoms. The overlap is shown shaded and not to scale as it is extremely small. . . . . . . . . . . . . . . . . . . . . . 2.3 Example Mssbauer spectrum showing the simplest case of o emitter and absorber nuclei in the same environment. The uncertainty in the energy of the excited state, , is shown exaggerated. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4 The eect on the nuclear energy levels for a 3/2 1/2 transition, such as in 57 Fe or 119 Sn, for an asymmetric charge distribution. The magnitude of quadrupole splitting, is shown. . 2.5 The eect of magnetic splitting on nuclear energy levels in the absence of quadrupole splitting. The magnitude of splitting is proportional to the total magnetic eld at the nucleus. . . . . 2.6 The eect of a rst-order quadrupole perturbation on a magnetic hyperne spectrum for a 3/2 1/2 transition. Lines 2,3,4,5 are shifted relative to lines 1,6. . . . . . . . . . . . . . 2.7 Decay scheme of 57 Fe following excitation of the 14.41 keV state. 2.8 Probability of a 7.3keV K-conversion electron reaching the absorber surface in metallic iron. . . . . . . . . . . . . . . . . . . 3.1 5
12
13
15 20 21
3.2
3.3
Eect of moment alignment on magnetisation: (a) Single magnetic moment, m, (b) two identical moments aligned parallel and (c) antiparallel to each other. . . . . . . . . . . . . . . . . 24 Typical eect on the magnetisation, M , of an applied magnetic eld, H, on (a) a paramagnetic system and (b) a diamagnetic system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 Schematic of a magnetisation hysteresis loop in a ferromagnetic material showing the saturation magnetisation, Ms , coercive eld, Hc , and remanent magnetisation, Mr . Virgin curves are shown dashed for nucleation (1) and pinning (2) type magnets. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 vi
3.4 3.5
The process of magnetisation in a demagnetised ferromagnet. Shape of hysteresis loop as a function of H , the angle between anisotropy axis and applied eld H, for: (a) H = 0 , (b) 45 and (c) 90 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6 Rotation of sublattice magnetisation under an applied eld, H, perpendicular to the spin axis. . . . . . . . . . . . . . . . 3.7 Variation of reciprocal susceptibility with temperature for: (a) antiferromagnetic, (b) paramagnetic and (c) diamagnetic ordering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.8 Variation of saturation magnetisation below, and reciprocal susceptibility above Tc for: (a) ferromagnetic and (b) ferrimagnetic ordering. . . . . . . . . . . . . . . . . . . . . . . . 3.9 Superconductor enclosing a non-superconducting region. . . 3.10 Superconducting quantum interference device (SQUID) as a simple magnetometer. . . . . . . . . . . . . . . . . . . . . . 3.11 Critical measuring current, Ic , as a function of applied magnetic eld. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 Decay scheme for a 57 Co source leading to gamma-ray emission. Internal conversion accounts for the remaining 91% of 14.41 keV events. . . . . . . . . . . . . . . . . . . . . . . . . Mssbauer spectrometer schematic. . . . . . . . . . . . . . . o CEMS detector used at Liverpool University. . . . . . . . . . Illustration of an RSO measurement with a small amplitude. (a) shows the ideal SQUID response for a dipole and (b) shows the movement of the sample within the SQUID pickup coils.
. 29
. 30 . 32
. 33
. 34 . 37 . 40 . 42
4.2 4.3 4.4
. 44 . 45 . 47
. 51
5.1
Variation of the indirect exchange coupling constant, j, of a free electron gas in the neighbourhood of a point magnetic moment at the origin r = 0. . . . . . . . . . . . . . . . . . . . 57 The atomic positions in the C15 MgCu2 Cubic Laves Phase unit cell. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Schematic of the Laves Phase sample construction. . . . . . Comparison of spectra of DyFe2 , YFe2 and HoFe2 thin lms at room temperature under zero applied eld. . . . . . . . . 750 DyFe2 thin lm under 0 kOe and 2.5 kOe in plane apA plied magnetic elds. . . . . . . . . . . . . . . . . . . . . . . Spectra for 1000 YFe2 thin lm under 0 kOe and 2.5 kOe in A plane applied elds. . . . . . . . . . . . . . . . . . . . . . . . Spectra for DyFe2 (x)/Dy(y ) z , multilayers. . . . . . . . A A vii . 61 . 64 . 68 . 69 . 73 . 76
6.1 6.2 6.3 6.4 6.5 6.6
6.7 6.8 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8
Exchange coupling between iron sublattices in DyFe2 /YFe2 multilayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78 Spectra for DyFe2 (x )/YFe2 (y ) z , multilayers. . . . . . . . 79 A A Normalised magnetisation vs temperature scans for Ce(20 )/Fe(x ) A A multilayers. Cerium layer thickness is constant. . . . . . . . . 86 Normalised magnetisation vs temperature curves for Ce(27 )/Fe(x ) A A multilayers. Cerium layer thickness is constant. . . . . . . . . 88 Normalised magnetisation vs temperature scans for Ce(x )/Fe(10 ) A A multilayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 Normalised magnetisation vs temperature scans for Ce(x )/Fe(15 ) A A multilayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 Normalised magnetisation vs temperature scans for Ce(x )/Fe(20 ) A A multilayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 Percentage change in resistance under an applied eld for the Ce(20 )/Fe(17 ) 60 sample. . . . . . . . . . . . . . . . . . . 92 A A Exploded view of a Ce/Fe multilayer showing the antiferromagnetic coupling between the iron layers. . . . . . . . . . . . 93 Variation of antiferromagnetic coupling constant, J(z), with cerium layer thickness, z. The dashed line, representing a theoretical picture of oscillatory coupling, is added to guide the eye. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 Hysteresis loops taken at room temperature for all measured Ce/Fe samples. The magnetisation is normalised relative to the iron layers volume only. The hysteresis loop for the 20/10 sample is shown truncated in the main plot for clarity, but is compared to the other loops in the inset. . . . . . . . . . . . . 96 CEMS spectra for U/Fe multilayers: [U(40)/Fe(60)]10 , [U(80)/Fe(60)]20 , [U(101)/Fe(60)]20 and [U(42)/Fe(113)]21 . The spectra are unaected by the uranium layer thicknesses. . . . . . . . . . . . 100 CEMS spectra for U/Fe multilayers: [U(28)/Fe(30)]31 , [U(28)/Fe(43)]31 and [U(22)/Fe(180)]5 . Increasing crystallinity is observed within the iron layers as the thickness increases. . . . . . . . . . . . . 102 DCEMS spectra recorded from the [U(28)/Fe(43)]31 sample. Spectrum (a) is obtained from the top 5 bilayers in the sample, whilst spectrum (b) was recorded from the remaining layers underneath. . . . . . . . . . . . . . . . . . . . . . . . . 104 X-ray reectivity scans for a) [U(42)/Fe(113)]21 and b) [U(22)/Fe(180)]5 samples. Sharp peaks indicate well dened interfaces. . . . . . 106 Room temperature Mssbauer spectra for all toner samples. . 115 o viii
7.9
7.10
7.11
7.12
7.13 8.1
8.2 8.3 8.4
77K Mssbauer spectra for all toner samples. . . . . . . . . . . 116 o Fe3 O4 thin lms on (a) platinum and (b) sapphire substrates. Sample (b) was grown using an oxygen plasma source. . . . . 117 Fe3 O4 thin lm on a sapphire substrate, grown with a standard sputtering source. (a) shows the tted spectrum and (b) shows the hyperne eld distribution. . . . . . . . . . . . . . . . . . 118
ix
List of Tables
2.1 Relative probabilities for a dipole 3/2 1/2 transition. C 2 and are the angular independent and dependent terms arbitrarily normalised. Relative intensities for = 90 and = 0 are shown with arbitrary normalisation. . . . . . . . . . . . . . . . 16 Variation of susceptibility, , and permeability, , with material and magnetic ordering. . . . . . . . . . . . . . . . . . . . . 25 Final t parameters for 750 DyFe2 sample assuming [ A 241] or [ 351] easy axis in zero applied eld. . . . . . . . . . . . . . . Final t parameters for the 750 DyFe2 sample in 0 kOe or A 2.5 kOe in plane applied eld. No particular easy axis is applied to the tting parameters. The average angle is relative to the sample plane. . . . . . . . . . . . . . . . . . . . . . . Final t parameters for 1000 YFe2 sample assuming [ A 241] or [ 351] easy axis in zero applied eld. . . . . . . . . . . . . . . Final t parameters for the 1000 YFe2 sample in 0 kOe or A 2.5 kOe in plane applied eld. No particular easy axis is applied to the tting parameters. The average angle is relative to the sample plane. . . . . . . . . . . . . . . . . . . . . . . Final t parameters for the DyFe2 (x )/Dy(y ) z samples A A and a 750 DyFe2 thin lm sample. The average angle is A relative to the sample plane. . . . . . . . . . . . . . . . . . . Fit parameters for DyFe2 (x )/YFe2 (y ) z multilayers. The A A average angle is relative to the sample plane. . . . . . . . . . . 67
3.1 6.1 6.2
. 70 . 72
6.3 6.4
. 72
6.5
. 75 . 80
6.6 7.1
7.2
Sample thicknesses, areas and volumes. denotes a sample from which magnetometry data has been taken but whose area was not measured. . . . . . . . . . . . . . . . . . . . . . . . . 84 Hyperne values for all U/Fe multilayers studied. . . . . . . . 99
7.3
Calculated thickness of iron layers in a fully crystalline (FE), paramagnetic (PM) or reduced crystallinity (RC) state for all U/Fe samples studied. . . . . . . . . . . . . . . . . . . . . . . 103 Final room temperature t parameters for all toner powder samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 Calculated Fe2+ :Fe3+ and N1 :N2 ratios for the room temperature spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 Best t parameters for magnetite thin lm samples. The magnetic hyperne eld for the Fe3 O4 /Al2 O3 B sample is a distribution, shown in Figure 8.4(b). . . . . . . . . . . . . . . . . . 112
8.1 8.2 8.3
xi
Only in silence the word, only in dark the light, only in dying life : bright the hawks ight on the empty sky. Ursula Le Guin
xii
or Only in recoil-free the event, only in resonance the line, only in decay emission : bright the peaks height on the empty channel.
xiii
Chapter 1 Introduction
A eck, a ight in feather til, In hanging air to drift and fall, Alight in spot of light and gentle Rests a time to states unveil. Magnetic materials have been an important part of the technological advances of the past century. Most notable in recording media such as tapes and discs they also have crucial roles in many other areas; motors, actuators, sensors and a variety of industrial processes. The key to the rapid enhancement of magnetic devices is the ability to tailor materials with specic magnetic properties. Of particular current interest are magnetic multilayers, on which much research has already been done.1, 2 These can display many novel properties compared to bulk systems due to their construction. Interfacial and geometrical elements combine to produce these novel properties and can be adjusted by varying layer thicknesses and the composition of the layers. Fully understanding the mechanisms involved in the interactions between the layers and the eects of layer construction is vital to engineering new technologies from these materials.
1.1
Thesis Outline
The aims of this thesis are to investigate the structure and magnetic interactions in multilayer systems and how these aect their magnetic properties, to understand the mechanisms at work in nanoscale structures such as thin lms and how these aect bulk properties, and to contrast the dierent properties of iron as a magnetic constituent in intermetallics, multilayers and oxides. The main investigatory technique used in this thesis is 57 Fe Mssbauer o spectroscopy. Mssbauer spectroscopy is an isotope specic technique which o 1
CHAPTER 1. INTRODUCTION
can provide information about magnetic ordering via the hyperne eld, moment orientation, charge states and the local environment of the Mssbauer o isotope. Atoms in sites which dier in their electronic or magnetic environment can be distinguished. Chapter 2 covers the theory of the Mssbauer eect, its physical basis and o how it can be utilised as a spectroscopic technique. The various hyperne interactions which aect the shape of the resultant spectrum are explained and illustrated. Most Mssbauer data in this thesis have been obtained using o Conversion Electron Mssbauer Spectroscopy, a surface sensitive technique. o The dierences between this and the more common Transmission Mssbauer o Spectroscopy technique and CEMS depth dependence are explained. SQUID magnetometry has been used as the primary technique for examining the Ce/Fe multilayers. The physics of SQUIDs is given in Chapter 3. This is combined with an overview of magnetometry in general. Although magnetometry data were only used for a small part of the data presented in this thesis they are included to provide a resource for the basic principles of magnetism which are used in the explanation of much of the Mssbauer data o as well. Chapter 4 gives information about the actual equipment used to facilitate the theoretical techniques outlined in the above chapters, along with an overview of the analysis routines used for analysing the Mssbauer results. o As magnetic interactions, such as magnetic anisotropy, play an important role in the behaviour of many of the systems studied, Chapter 5 comprises a brief account of these topics. Chapter 6 is the rst chapter of experimental results. The crystal structure of Rare Earth/Iron cubic Laves Phase systems is discussed with respect to bulk systems. The eects, such as strain, of growing these systems as thin lms with Molecular Beam Epitaxy, are then applied to the bulk system. Results and analysis of the CEMS data obtained from thin lm samples are presented rst. These are then extended to multilayer samples of DyFe2 and a non-magnetic Dy spacer layer, or DyFe2 /YFe2 multilayers of varying layer thicknesses. Applied eld measurements were made on all samples apart from the DyFe2 /Dy system, to give information on the magnetic anisotropy. Chapter 7 presents results from two contrasting multilayer systems; Lanthanide/Iron and Actinide/Iron. SQUID magnetometry results from Ce/Fe multilayers are presented complementary to Mssbauer Spectroscopy results o 3 obtained by S. Case. The variation in the coupling type, and strength, of the iron layers across the cerium layers is examined. CEMS data and analysis from a series of U/Fe multilayers with dierent uranium and iron thicknesses are then presented. The moment orientations and crystalline nature of the iron layers is discussed. The data are compared to x-ray reectivity data
CHAPTER 1. INTRODUCTION
taken by A. Herring of the Liverpool University Condensed Matter Physics group. Chapter 8 is an investigation of iron oxide systems, with particular reference to magnetite. The crystalline and magnetic structure of magnetite is outlined. A commercial study for Laporte is given, where the ratios of iron oxides was determined in printer toner powders. The behaviour of magnetite in bulk systems is then compared to thin lm systems, with a Mssbauer o study of magnetite thin lms on dierent substrates. The crystalline growth and composition of the layers is discussed. Finally, Chapter 9 presents the conclusions produced from the analysis and suggestions for future work on the samples studied.
Chapter 2 Mssbauer Spectroscopy o

Alone, to give and lose, Far partner, never seen. Others, to join and help, Give all, take everything. Nuclei in atoms undergo a variety of energy level transitions, often associated with the emission or absorption of a gamma ray. In a free atom the nucleus recoils, due to conservation of momentum, resulting in the emitted gamma ray being of lower energy than the nuclear transition energy. The same is observed in absorption where the absorbing nucleus recoils, meaning the energy of the resonantly absorbed photon has to be greater than that of the transition. Thus, in these circumstances, resonant emission or absorption doesnt occur. In 1957 Rudolph Mssbauer discovered the phenomenon of Recoil-Free o Nuclear Resonance Fluorescence;4 a phenomenon later to become commonly known as the Mssbauer eect. o
2.1
2.1.1
The Mssbauer Eect o

Recoil and Line Broadening
The two main obstacles in the path of achieving nuclear resonant emission and absorption are the recoil energy shift and the thermal Doppler shift. Figure 2.1 shows an isolated atom in the gas phase undergoing a nuclear transition from an excited state, Ee , to the ground state, Eg .
Heisenberg Natural Linewidth and random thermal motion leads to line broadening and thus an overlap of the two energies in this simple regime but the eect is extremely small.
CHAPTER 2. MOSSBAUER SPECTROSCOPY
Recoil ER
Vx
Vx
Figure 2.1: Recoil in a free nucleus during gamma ray emission.
The recoil kinetic energy of the free nucleus, ER , is proportional to the mass of the nucleus, M , and the energy of the emitted gamma ray, E , and is given by 2 E ER = (2.1) 2M c2 The gamma ray energy will also be broadened into a distribution by the Doppler-eect energy, ED = M v Vx , which is proportional to the initial velocity, Vx , from the random thermal motion of the atom, and v from the recoil of the nucleus. This can be expressed as E D = E 2E k M c2 (2.2)
where E k is the mean kinetic energy per translational degree of freedom of a free atom.5 Heisenberg Natural Linewidth also broadens the lineshape. The uncertainty in the mean lifetime of the excited state, t, is related to the uncertainty in the energy of the excited state, E, by the Heisenberg uncertainty principle Et (2.3) Typical values of the linewidth broadening due to this are of the order of 106 times less than that due to ER and E D for isolated atoms and can be neglected in this case. The same equations apply for absorption. This leads to a distribution of emitted and absorbed gamma ray energies as shown in Figure 2.2. The resonance overlap is extremely small and so practically useless as the basis of a technique.
2E D
ER
Figure 2.2: Gamma ray energy distributions for emission and absorption in free atoms. The overlap is shown shaded and not to scale as it is extremely small.
2.1.2
Recoil-Free Events
The Mssbauer eect occurs when atoms are in a solid lattice or matrix. o The chemical binding energies in solids (1-10 eV) are much greater than free atom recoil energies, ER . The mass, M , recoiling then becomes eectively that of the entire crystal, which can be of the order of 1015 greater than a single atom. It can be seen from equations 2.1 and 2.2 that ER and ED will now be negligible in this case. However, although the nucleus is bound within the lattice it is still free to vibrate. The recoil energy can still be transferred to the lattice as a quantised lattice vibration, or phonon. If the recoil energy is less than the lowest quantised vibrational mode then a recoil-free event will occur. The probability of such an event is governed by the recoil-free factor, f , which is given as 2 E x2 f = exp (2.4) c2 where x2 is the mean square vibrational amplitude of the emitting or absorbing nucleus.5 It can be seen that f decreases exponentially with the square of the gamma ray energy; this is why the Mssbauer eect is only o detected in isotopes with a very low lying excited state. The other dependent factor, x2 , is a function of both the binding strength and temperature.
P E
2E D
ER
The optimum f factor, and hence the best signal/noise ratio, is obtained for isotopes with very low lying excited states at temperatures well below their Debye Temperature, D . A good example is 57 Fe, with a Mssbauer gamma o ray energy of 14.41 keV and a D of 470 K, allowing strong signals to be recorded at room temperature.
2.1.3
Resolution
Earlier the Heisenberg Natural Linewidth (HNL) was ignored as being totally negligible compared to ER . However, in recoil-free events ER is 0 and hence the HNL becomes the major limit on the resolution of the gamma ray energies. This spread in energies of width s is 4.67 109 eV in 57 Fe. Compared to the Mssbauer gamma ray energy of 14.41 keV for this isotope this gives a o resolution of 1 in 1012 . This is an incredibly high level of energy resolution and is of the order of nuclear hyperne interactions. Hence, the Mssbauer o eect can be used to probe the electronic environment of a sample via the hyperne interactions.
2.2
Mssbauer Spectroscopy o
The technique of Mssbauer spectroscopy involves using the gamma rays o emitted from the nuclei of a radioactive source to probe those in the sample o to be studied. The source contains the parent nucleus of the Mssbauer isotope, embedded in a rigid matrix to ensure a high f factor. The gamma rays emitted from this are passed through the material being investigated and those transmitted through the absorber are detected and counted. If the nuclei in the source and absorber are in the exact same environment (ie the energy of the nuclear transition is equal in both nuclei) the gamma rays will be resonantly absorbed and an absorption peak will be observed. In order to probe the energy levels in nuclei in dierent environments we must scan the energy of the Mssbauer gamma ray. This is achieved o by moving the source relative to the absorber. The Doppler eect produces an energy shift in the gamma ray energy allowing us to match the resonant energy level(s) in the absorber. The simplest case is shown in Fig 2.3. The spectrum recorded is a plot of transmission intensity versus source velocity in mm/s. The x-axis, through the
The radioactive source can be replaced by a synchrotron x-ray radiation source, which has certain advantages, particularly in time-dependent eects, but this is beyond the scope of the subject of this thesis.
Emitter Nucleus
Absorber Nucleus
counts
detector velocity
Figure 2.3: Example Mssbauer spectrum showing the simplest case of emito ter and absorber nuclei in the same environment. The uncertainty in the energy of the excited state, , is shown exaggerated.
Doppler eect on the gamma ray energy, is eectively an energy scale. The lineshape of the recorded peak in a thin sample is theoretically a Lorentzian, with a FWHM of twice the uncertainty in the energy of the excited state, .
2.3
Hyperne Interactions
The interaction between a nucleus and its surrounding environment is known as a hyperne interaction. These interactions are very small compared to the energy levels of the nucleus itself but the extreme energy resolution of the Mssbauer eect enables these interactions to be observed. The hyperne o interactions may shift energy levels or lift their degeneracy. Both of these variations will aect the shape of a Mssbauer spectrum. o The nuclear Hamiltonian can be expressed as H = H0 + E0 + M1 + E2 + . . . (2.5)
where H0 represents all of the terms of the Hamiltonian other than the hyperne interactions. E0 refers to the electric monopole interactions, M1 the magnetic dipole interactions and E2 the electric quadrupole interactions. These eects will be discussed in turn with reference to their physical causes and their eects on the Mssbauer spectrum lineshapes and positions. o
2.3.1
Center Shift
The Center Shift (CS) of a Mssbauer spectrum, which sets the centroid of o the spectrum, is composed of two factors: the Chemical Isomer Shift, , and the Second Order Doppler Eect (SODS), meaning that CS = + SODS Chemical Isomer Shift () The Isomer Shift arises due to the non-zero volume of the nucleus and the electron charge density due to s-electrons within it leading to an electric monopole (Coulomb) interaction which alters the nuclear energy levels. The volume of the nucleus in its ground and excited states are dierent and the selectron densities are aected by the chemical environment. This relationship between s-electron density and nuclear radius is given by 2 2 2 = Ze2 {|s (0)E |2 |s (0)A |2 }{ Re Rg } 3 (2.6)
2 2 where Rg and Re are the mean square radii of the ground and excited nuclear states, |s (0)E |2 and |s (0)A |2 are the electron densities at the emitting and absorbing nuclei and Z is the atomic number.5 Any dierence in the s-electron environment between emitter and absorber thus produces a shift in the resonance energy of the transition. This shift cannot be measured directly and so a suitable reference is necessary, such as a specic source or an absorber. In all of the results presented in this thesis isomer shifts are quoted relative to -Fe at room temperature (any isomer shifts quoted from other work which use a dierent calibration material are quoted relative to -Fe in this thesis for consistency). The Isomer Shift is good for probing the valency state of the Mssbauer o atom. As the wavefunctions of the s-electrons penetrate into outer shells changes in these shells will directly alter the s-electron charge density at the nucleus. For example, Fe2+ and Fe3+ have electron congurations of (3d)6 and (3d)5 respectively. The ferrous ions have less s-electron density at the nucleus due to the greater screening of the d-electrons. This produces a positive Isomer Shift greater in ferrous iron than in ferric.
Second Order Doppler Shift (SODS) The Second Order Doppler Shift (SODS) is a temperature-dependent eect on the center shift of a Mssbauer spectrum. Above 0 K atoms in a lattice o oscillate about their mean position. The frequency of this oscillation is of the
10
order of 1012 Hz meaning that the average displacement during the lifetime of a Mssbauer event is zero. However, the second term in the Doppler shift o depends on v 2 leading to the mean square displacement being non-zero. This energy shift is given by E v2 = 2 (2.7) E 2c For 57 Fe in the high temperature limit this gives a change of +0.07 mms1 for a decrease of 100 K.5
2.3.2
Electric Quadrupole Splitting
A nucleus that has a spin quantum number I > 1/2 has a non-spherical charge distribution. The magnitude of the charge deformation, Q, is given by eQ = r2 3 cos2 1 d (2.8)
where e is the charge on the proton, is the charge density in a volume element d at a distance r from the center of the nucleus and making an angle to the nuclear spin quantisation axis. The sign of Q indicates the shape of the deformation. Negative Q is due to the nucleus being attened along the spin axis, an elongated nucleus giving positive Q.5 An asymmetric charge distribution around the nucleus causes an asymmetric electric eld at the nucleus, characterised by a tensor quantity called the Electric Field Gradient (EFG) E. The electric quadrupole interaction between these two quantities gives rise to a splitting in the nuclear energy levels. The interaction between nuclear moment and EFG is expressed by the Hamiltonian 1 HEq = eQ E (2.9) 6 where E may be written as 2V Eij = = Vij , xi xj {xi , xj } = {x, y, z} (2.10)
where V is the electrostatic potential. There are two contributions to the EFG i) lattice contributions from charges on distant ions and ii) valence contributions due to incompletely lled electron shells. If a suitable coordinate system is chosen the EFG can be represented by three principal axes, Vxx , Vyy and Vzz . If an asymmetry
CHAPTER 2. MOSSBAUER SPECTROSCOPY parameter is dened using these axes as = Vxx Vyy Vzz
11
(2.11)
where |Vzz | |Vyy | |Vxx | so that 0 1, the EFG can be specied by two parameters: Vzz and . The Hamiltonian for the quadrupole interaction can be rewritten as HEq = 2 e2 qQ 2 2 3Iz I(I + 1) + I+ + I 4I(2I 1) 2 (2.12)
where I+ and I are shift operators and Iz is a spin operator.5 The excited state of 57 Fe has a spin I = 3/2. The EFG has no eect on the I = 1/2 ground state but does remove degeneracy in the excited state, splitting it into two sub-states mI = 1/2 and mI = 3/2 where the mI = 3/2 states are higher in energy for positive Vzz . The energy eigenvalues for I = 3/2 have exact solutions given by EEq e2 qQ = 3m2 I(I + 1) I 4I(2I 1) 2 1+ 3
1 2
(2.13)
whilst the energies for higher spin states require analytical methods to calculate the energies. The now non-degenerate excited states give rise to a doublet in the Mssbauer spectrum as illustrated in Figure 2.4. The separation between o the lines, , is known as the quadrupole splitting and is given by e2 qQ = 2 2 1+ 3
1 2
(2.14)
with the line intensities being equal for polycrystalline samples. Texture or orientation eects can lead to asymmetric doublets. As the nuclear quadrupole moment is xed the magnitude and sign of gives information about the sign of the EFG and magnitude of .
2.3.3
Magnetic Hyperne Splitting
Magnetic hyperne splitting is caused by the dipole interaction between the nuclear spin moment and a magnetic eld ie Zeeman splitting. The eective magnetic eld experienced by the nucleus is a combination of elds from the atom itself, from the lattice through crystal eld eects and from external
12
mI
3 2
I
3 2
1 2
1 2
1 2
Figure 2.4: The eect on the nuclear energy levels for a 3/2 1/2 transition, such as in 57 Fe or 119 Sn, for an asymmetric charge distribution. The magnitude of quadrupole splitting, is shown.
applied elds. This can be considered for now as a single eld, H, whose direction species the principal z axis. The Hamiltonian for the magnetic hyperne dipole interaction is given as H = .H = gN I.H (2.15)
where N is the nuclear Bohr magneton, is the nuclear magnetic moment, I is the nuclear spin and g is the nuclear g-factor.5 This Hamiltonian yields eigenvalues of EM = gN HmI (2.16)
where mI is the magnetic quantum number representing the z component of I (ie mI = I, I 1, . . . , I). The magnetic eld splits the nuclear level of spin I into (2I + 1) equispaced non-degenerate substates. This and the selection rule of mI = 0, 1 produces splitting and a resultant spectrum as shown in Figure 2.5 for a 3/2 1/2 transition. This splitting is a combination of a constant nuclear term and a variable magnetic term, inuenced by the electronic structure. The magnetic eld at
13
mI
3 2
1 2
3 2
1 2 3 2
1 2
Figure 2.5: The eect of magnetic splitting on nuclear energy levels in the absence of quadrupole splitting. The magnitude of splitting is proportional to the total magnetic eld at the nucleus.
the nucleus has several terms associated with it. A general expression is 4 H = H0 DM + M + HS + HL + HD 3 (2.17)
where H0 is the value of magnetic eld at the nucleus due to an external magnetic eld, DM is the demagnetising eld, 4/3M is the Lorentz eld, HS is the Fermi contact term, HL is the orbital magnetic term and HD is the dipolar term. The demagnetising eld and Lorentz eld are usually negligible compared to the other terms. HS is produced by the polarisation of electrons whose wavefunctions overlap the nucleus, ie s-electrons. This polarisation is due to unpaired electrons in the d or f orbitals and gives an imbalance in spin density at the nucleus from the dierence in interaction between the unpaired electron with s-electrons of parallel or antiparallel spin to its own. This can be expressed formally as 8 H S = 0 B {|s (0)|2 |s (0)|2 } (2.18) 3
1 2
1 2
14
HL arises from the net orbital moment at the nucleus caused by the orbital motion of electrons in unlled shells and given by HL = 20 B 3 r L 4 (2.19)
In transition metals L is usually quenched by interactions with the crystal eld, but it can be substantial in Rare Earth ions. HD arises from the dipolar interaction between the nucleus and the spin moment of 3d or 4f electrons and can be expressed as HD = 2B S r3 3 cos2 1 (2.20)
In transition metal compounds with cubic symmetry this has zero magnitude but can be substantial in Rare Earths.
2.3.4
Combined Magnetic and Quadrupole Interactions
When dealing with quadrupole or magnetic splitting separately with chemical isomer shifts the recorded spectrum has uniform shifts of resonance lines with no change in their relative separations. However, both the quadrupolar and magnetic interactions depend upon angle and so when they are both present the interpretation of the spectrum can be complex. The situation can be simplied a great deal if two assumptions are made 1. the electric eld gradient is axially symmetric with its principal axis, Vzz , at an angle to the magnetic axis 2. the strength of the quadrupole interaction is much less than the magnetic interaction, ie e2 qQ H. The solution to the Hamiltonian can then be solved by treating the quadrupole interaction as a perturbation so that the resultant energy levels are given by E = qN HmI + (1)|mI |+ 2
1
e2 qQ 4
3 cos2 1 2
(2.21)
giving a spectrum as in Figure 2.6.5 For most 57 Fe spectra the result is a shift in the relative position of lines 1,6 with lines 2,3,4,5. For a positive quadrupole splitting lines 1,6 are shifted positively relative to lines 2,3,4,5 and vice versa. The line separations are equal when there is no quadrupole eect or when cos = 1/ 3.
15
mI
3 2
3 2
1 2 1 2 3 2
1 2
Magnetic
Magnetic + Quadrupole
Figure 2.6: The eect of a rst-order quadrupole perturbation on a magnetic hyperne spectrum for a 3/2 1/2 transition. Lines 2,3,4,5 are shifted relative to lines 1,6.
2.3.5
Spectrum Line Intensities
The hyperne interactions thus far have given the relative energies of the various transitions taking place but have not given information on the relative intensities of these transitions in the recorded spectrum. The intensities arise from the coupling of two angular momentum states, which can be expressed as the product of both an angular dependent term and an angular independent term by A(L, ) = C 2 (J)(J, ) (2.22) where C 2 (J) is the transition probability of the -ray transition between two nuclear sub-levels, and (J, ) is the angular dependence of the radiation probability at an angle to the quantisation axis. The angular independent term is given by the square of the appropriate
1 2 3 4 5
1 2 1 2
CHAPTER 2. MOSSBAUER SPECTROSCOPY m2 +3/2 +1/2 1/2 3/2 +3/2 +1/2 1/2 3/2 m1 +1/2 +1/2 +1/2 +1/2 1/2 1/2 1/2 1/2 m +1 0 1 2 +2 +1 0 1 C 1 2/3 1/3 0 0 1/3 2/3 1 C2 3 2 1 0 0 1 2 3 = 90 1 + cos2 2 sin2 1 + cos2 0 0 2 1 + cos 2 sin2 1 + cos2 3 4 1 0 0 1 4 3 = 0 6 0 2 0 0 2 0 6
16
Table 2.1: Relative probabilities for a dipole 3/2 1/2 transition. C 2 and are the angular independent and dependent terms arbitrarily normalised. Relative intensities for = 90 and = 0 are shown with arbitrary normalisation.
Clebsch-Gordan coecient C 2 (J) = I1 J m1 m|I2 m2

2
(2.23)
where J is the vector sum J = I 1 +I 2 and m is the vector sum m = m1 m2 .5 J is the multipolarity of the radiation, J = 1 being dipolar and J = 2 being quadrupolar. As the multipolarity of the radiation increases the transition probability decreases. In 57 Fe the 14.41 keV transition is primarily dipolar and values for this transition are given in Table 2.1. In a magnetic spectrum the intensities of the outer, middle and inner lines are in a ratio derived from the product C 2 (J)(J, ). Using the values from Table 2.1 gives 3 1 + cos2 : 4 sin2 : 1 + cos2 (2.24)
from which it can be seen that the outer and inner lines are always in the ratio of 3:1 whilst the middle line varies between 0 4 with angle. In polycrystalline samples there is no angular dependence and thus the intensity depends only on C 2 (J), giving a sextet of 3:2:1:1:2:3. Non-magnetic spectra with quadrupole splitting have several degenerate
CHAPTER 2. MOSSBAUER SPECTROSCOPY transitions and the intensity of the two lines are in the ratio 3 1 + cos2 : 2 + 3 sin2
17
(2.25)
2.4
Relaxation Phenomena
There are many contributions to the hyperne eld at the nucleus as seen in Equation 2.17 but the major contributor for transition metals such as 57 Fe, when in zero applied eld, is HS . This arises from the polarising eect of unpaired electron spins with the direction of the eld being related to that of the electron spins. However, this direction is not invariant and can ip after a period of time. This is the relaxation phenomenon. The eects upon the Mssbauer lineshape depend upon the relative time scales of measurement o and the relaxation mechanism, there being three time scales to consider: the lifetime of the Mssbauer event, the Larmor precession time and the o relaxation time. The lifetime of the Mssbauer event, m , which is also the limiting time o scale of the measurement technique, is determined by the Heisenberg uncertainty relationship as shown in Equation 2.3. For 57 Fe this is of the order of 107 s. The second time scale to consider is the minimum time required for the nucleus to detect the hyperne eld. This is usually assumed to be equal to the Larmor precession time, l , which can be considered as the time taken for a nuclear spin state, I, to split into (2I + 1) substates under the inuence of a hyperne eld. l is proportional to the magnitude of the hyperne eld (and hence related to the nuclear energy levels as in Equation 2.16) with the following relation 2 l = (2.26) gn B where g is the gyromagnetic constant and n is the nuclear Bohr magneton. In iron oxides the hyperne eld is 400 500 kG giving l of the order of 108 s. This means that m l and hence the hyperne elds are detectable by the technique. The nal time scale is the relaxation time, r , associated with the time dependent uctuations of the electron spin. For the hyperne eld to be observed it must remain constant at the nucleus for at least one Larmor precession period. There are three regimes which are important when considering the eect of relaxation on the Mssbauer lineshape: o 1. If r l then the hyperne eld is static during a single Larmor
18
precession period. The spectral lines are narrow and Lorentzian in shape. 2. If r l then the nucleus experiences a time averaged hyperne eld. The magnitude is less than the value obtained for a static eld as the interaction will have changed many times during a single precession period and tends to zero as r decreases. Narrow Lorentzian lines are still observed. 3. If r l then resonance between the relaxation and the precession occurs leading to complex spectra and broadened lineshapes. As l is proportional to the energy dierence between the spectral lines l for the outer lines will be less than for the inner lines, causing the inner lines of a sextet to broaden and disappear before the outer ones.6 The two main mechanisms involved in the spin relaxation are Spin-Spin and Spin-Lattice relaxation. Spin-Spin Relaxation This involves energy transfer between interacting spins via dipole and exchange interactions. The relaxation rate depends heavily on the concentration of paramagnetic ions in the sample. This mechanism is largely temperature independent. The relaxation rate can be expressed as R | i|H|f |2 (2.27)
where i and f are the initial and nal spin states, H is the Hamiltonian of the mechanism and is a phase factor. Spin-Lattice Relaxation This mechanism involves energy transfer between the electron spin and lattice phonons mostly via the spin-orbit interaction but also weakly through dipolar interactions. The relaxation rate is of the same form as Equation 2.27 but with now involving the population of phonon modes. This leads to the spinlattice contribution to relaxation being strongly temperature dependent.
19
2.5
Conversion Electron Mssbauer Spectroo scopy
Standard Transmission Mssbauer Spectroscopy (TMS) records the absorpo tion of gamma rays in the beam transmitted through the absorber. If the absorber is too thick or on an opaque substrate so that the beam cannot pass through or the signal is too small, then a reective technique must be used, such as Conversion Electron Mssbauer Spectroscopy (CEMS). o
2.5.1
CEMS Decay Scheme
A nucleus that is promoted to an excited state by gamma ray absorption can de-excite by a number of mechanisms. These fall into two categories 1. Radiative: by the emission of a gamma ray with a probability of N () 2. Non-Radiative: by internal conversion and the ejection of an atomic electron with a probability of N (e) The ratio of these two process is given by the internal conversion coecient, , given by N (e) (2.28) = N () which for 57 Fe is 8.21, ie internal conversion is 8.21 times more probable than photon emission.7 The conversion electron is ejected from the atom with an energy Ec = E Eb where E is the energy of the transition and Eb is the binding energy of the electron. In 57 Fe the internal conversion can occur from K, L and M shells, in order of probability. This ejection leaves a hole which can be lled by an electron from an outer shell. This releases energy in the form of an X-ray or an Auger electron, with the process continuing in this manner until all of the energy has been dissipated. The principal decay scheme is shown in Figure 2.7. To exploit the decay of the resonantly excited nucleus the conversion and Auger electrons need to be detected. This is achieved by placing the sample inside a gas-ow proportional counter as shown in Section 4.1.3.
2.5.2
Depth Dependence
The conversion and Auger electrons produced by the resonant event have a nite range in the material of the absorber due to interactions with other
20
Figure 2.7: Decay scheme of
57
Fe following excitation of the 14.41 keV state.
charged particles. The range is dependent on both the mean free path of the electron in the absorber and the initial kinetic energy of the electron. This is illustrated in Figure 2.8. The dependence is essentially an inverse exponential one with the majority of the signal coming from the uppermost 1000 . A This depth dependency is a double-edged sword in that the quite shallow detection depth may prevent the probing of deeper structures and that surfaces have to be kept relatively clean but it also prevents such things as buer and seed layers in multilayer samples contaminating the signal. In the samples studied in this thesis using CEMS the whole of the thin lm or multilayer is 2000 or less and deposited onto thick, opaque substrates A
21
Figure 2.8: Probability of a 7.3keV K-conversion electron reaching the absorber surface in metallic iron.
making this technique a practical solution. The depth dependency can also be combined with the selection of electron energies to obtain separate spectra for dierent depths into the sample. This is known as Dierential CEMS or DCEMS.
Chapter 3 Magnetometry
Random grains to clasp, Regimented lines to wear, Snare in serpents grasp, Shake their secrets bare. Mssbauer Spectroscopy, as outlined in Chapter 2, is an eective probe of o magnetic ordering in materials. In particular it can distinguish dierent contributions to magnetic structure arising from dierent ions and dierent sites as in the Fe2+ and Fe3+ ions on A and B sites in Fe3 O4 (see Chapter 8). It cannot, however, provide a complete description of the magnetism alone. For example, Mssbauer Spectroscopy in zero applied eld cannot distinguish o between ferromagnetic and antiferromagnetic ordering. It is sensitive only to the particular Mssbauer isotope being probed and the spectra take a o relatively long time to accumulate. Magnetometry can produce results on the total moment of the system and its variation with applied eld and temperature relatively quickly and easily, providing complementary data to the Mssbauer spectrum as well as other techniques. o
3.1
Magnetic Measurements
The principle aim of magnetometry is to measure the magnetisation (either intrinsic or induced by an applied eld) of a material. This can be achieved in a number of ways utilising various magnetic phenomena. The various types of magnetometer fall within two categories: 1. Measuring the force acting on a sample in an inhomogeneous magnetic eld
22
CHAPTER 3. MAGNETOMETRY Magnetic balance Magnetic pendulum 2. Measuring the magnetic eld produced by a sample. Vibrating Sample Magnetometer (VSM) Superconducting Quantum Interference Device (SQUID)
23
Magnetometry data in this thesis has been recorded using a SQUID, the theoretical principles of which are outlined in Section 3.5 and the physical details in Section 4.3.
3.1.1
Magnetic Moments
A magnet in a eld has a potential energy, Ep , relative to the parallel position given by Ep = m H (3.1) where H is the applied eld and m is the magnetic moment.8 From this the units of magnetic moment can be seen to be J/T (emu in cgs notation, where emu is an acronym for ElectroMagnetic Unit). The origin of atomic magnetic moments is the incomplete cancellation of electronic magnetic moments. Electron spin and orbital motion both have magnetic moments associated with them but in most atoms the electronic moments are oriented so that they cancel giving no net atomic magnetic moment, leading to diamagnetism. If the cancellation of electronic moments is incomplete then the atom has a net magnetic moment. These magnetic atoms can display para-, ferro-, antiferro- or ferrimagnetic ordering depending upon the strength and type of magnetic interactions and external parameters such as temperature. The magnetic moments of atoms, molecules or formula units are often quoted in terms of the Bohr magneton , which is equal to the magnetic moment due to electron spin B = eh = 9.27 1024 J/T 4m
eg the atomic moment is 2.22 B/atom for metallic iron and 10.34 B/atom for metallic holmium.
Derived from three fundamental constants; electronic charge e, electronic mass m and Plancks constant h, the Bohr magneton is a natural unit of magnetic moment in the same way that e is a natural unit of electric charge.
CHAPTER 3. MAGNETOMETRY
24
Figure 3.1: Eect of moment alignment on magnetisation: (a) Single magnetic moment, m, (b) two identical moments aligned parallel and (c) antiparallel to each other.
3.1.2
Magnetisation
The output from a magnetometer, a single value of magnetic moment for the sample, is a combination of the magnetic moments on the atoms within the sample, the type and level of magnetic ordering and the physical dimensions of the sample itself. The moment is also aected by external parameters such as temperature and applied magnetic eld. The Intensity of Magnetisation , M , is a measure of the magnetisation of a body. It is dened as the magnetic moment per unit volume or M= m V (3.2)
with units of A/m (emu/cm3 in cgs notation).8 A sample contains many atoms and their arrangement aects the magnetisation. In Figure 3.1(a) a magnetic moment m is contained in unit volume. This has a magnetisation of m A/m. Figure 3.1(b) shows two such units, with the moments aligned parallel. The vector sum of moments is 2m in this case, but as the both the moment and volume are doubled M remains the same. In Figure 3.1(c) the moments are aligned antiparallel. The vector sum of moments is now 0 and hence the magnetisation is 0 A/m. Scenarios (b) and (c) are a simple representation of ferro- and antiferromagnetic ordering. Hence we would expect a large magnetisation in a ferromagnetic material such as pure iron and a small magnetisation in an antiferromagnet such as -Fe2 O3 .
This is often shortened to simply Magnetisation.
CHAPTER 3. MAGNETOMETRY Material/Ordering Vacuum Diamagnetic Paramagnetic Antiferromagnetic Ferromagnetic Ferrimagnetic 0 Small Small Small Large Large =1 1 1 1 1 1
25
and and and and and
negative positive positive positive positive
Table 3.1: Variation of susceptibility, , and permeability, , with material and magnetic ordering.
3.1.3
Magnetic Response
The response of a material to a magnetic eld is quantied by two quantities: the susceptibility, , which is the variation of magnetisation, M , with applied eld, H, M = (3.3) H and the permeability, , the variation of magnetic induction, B = 0 (H +M ), with applied eld, B = (3.4) H Permeability is often quoted relative to 0 = 4 107 H/m, the permeability of a vacuum or (within a high degree of accuracy) air. The susceptibility and permeability of a material depends upon its magnetic characteristics. Table 3.1 gives an indication of how they vary with the type of material and magnetic ordering (if any) it displays.
3.1.4
Background Contributions
A single measurement of a samples magnetisation is relatively easy to obtain, especially with modern technology. Often it is simply a case of loading the sample into the magnetometer in the correct manner and performing a single measurement. This value is, however, the sum total of the sample, any substrate or backing and the sample mount. A sample substrate can produce a substantial contribution to the sample total. The samples studied in this thesis using
26
magnetometry have a single type of substrate, silicon, substantially greater in volume and mass than the sample itself. Fortunately the substrate is diamagnetic (see Section 3.2.1). Under zero applied eld this means it has no eect on the measurement of magnetisation. Under applied elds its contribution is linear and temperature independent. The diamagnetic contribution can be calculated from a knowledge of the volume and properties of the substrate and substracted as a constant linear term to produce the signal from the sample alone. The diamagnetic background can also be seen clearly at high elds where the sample has reached saturation: the sample saturates but the linear background from the substrate continues to increase with eld. The gradient of this background can be recorded and subtracted from the readings if the substrate properties are not known accurately.
3.2
Hysteresis
The response of a material to an applied eld and its magnetic hysteresis is an essential tool of magnetometry. Paramagnetic and diamagnetic materials can easily be recognised, soft and hard ferromagnetic materials give dierent types of hysteresis curves and from these curves values such as saturation magnetisation, remanent magnetisation and coercivity are readily observed. More detailed curves can give indications of the type of magnetic interactions within the sample. Hysteresis is a subject which covers a wide range of behaviour in materials, both in magnetism and other disciplines. The aim of this section is to cover the basic principles of the use of hysteresis as a probe of magnetism.
3.2.1
Diamagnetism and Paramagnetism
As explained in Section 3.1.2 the intensity of magnetisation depends upon both the magnetic moments in the sample and the way that they are oriented with respect to each other, known as the magnetic ordering. Diamagnetic materials, which have no atomic magnetic moments, have no magnetisation in zero eld. When a eld is applied a small, negative moment is induced on the diamagnetic atoms proportional to the applied eld strength. See Figure 3.2(b). As the eld is reduced the induced moment is reduced. In a paramagnet the atoms have a net magnetic moment but are oriented randomly throughout the sample due to thermal agitation, giving zero magnetisation. As a eld is applied the moments tend towards alignment along
27
Figure 3.2: Typical eect on the magnetisation, M , of an applied magnetic eld, H, on (a) a paramagnetic system and (b) a diamagnetic system.
the eld, giving a net magnetisation which increases with applied eld as the moments become more ordered. See Figure 3.2(a). As the eld is reduced the moments become disordered again by their thermal agitation. The gure shows the linear response of M vs H where H kT .
3.2.2
Ferromagnetism
The hysteresis curves for a ferromagnetic material are more complex than those for diamagnets or paramagnets. Figure 3.3 shows the main features of such a curve for a simple ferromagnet. In the virgin material (point 0) there is no magnetisation. The process of magnetisation, leading from point 0 to saturation at M = Ms , is outlined in Figure 3.4.8 Although the material is ordered ferromagnetically it consists of a number of ordered domains arranged randomly giving no net magnetisation. This is shown in Figure 3.4(a) with two domains whose individual saturation moments, Ms , lie antiparallel to each other. As the magnetic eld, H, is applied, (b), those domains which are more energetically favourable increase in size at the expense of those whose moment lies more antiparallel to H. There is now a net magnetisation, M . Eventually a eld is reached where all of the material is a single domain with a moment aligned parallel, or close to parallel, with H. The magnetisation is now M = Ms cos where is the angle between Ms along the easy magnetic axis
28
Figure 3.3: Schematic of a magnetisation hysteresis loop in a ferromagnetic material showing the saturation magnetisation, Ms , coercive eld, Hc , and remanent magnetisation, Mr . Virgin curves are shown dashed for nucleation (1) and pinning (2) type magnets.
and H. Finally Ms is rotated parallel to H and the ferromagnet is saturated with a magnetisation M = Ms . The process of domain wall motion aects the shape of the virgin curve. There are two qualitatively dierent modes of behaviour known as nucleation and pinning,9 shown in Figure 3.3 as curves 1 and 2 respectively. In a nucleation-type magnet saturation is reached quickly at a eld much lower than the coercive eld. This shows that the domain walls are easily moved and are not pinned signicantly. Once the domain structure has been removed the formation of reversed domains becomes dicult, giving high coercivity. In a pinning-type magnet elds close to the coercive eld are necessary to reach saturation magnetisation. Here the domain walls are substantally pinned and this mechanism also gives high coercivity.
3.2.3
Remanence
As the applied eld is reduced to 0 after the sample has reached saturation the sample can still possess a remanent magnetisation, Mr . The magnitude of this remanent magnetisation is a product of the saturation magnetisation,
29
Figure 3.4: The process of magnetisation in a demagnetised ferromagnet.
the number and orientation of easy axes and the type of anisotropy symmetry. If the axis of anisotropy or magnetic easy axis is perfectly aligned with the eld then Mr Ms , and if perpendicular Mr 0. = = At saturation the angular distribution of domain magnetisations is closely aligned to H. As the eld is removed they turn to the nearest easy magnetic axis. In a cubic crystal with a positive anisotropy constant, K1 , the easy directions are 100 . At remanence the domain magnetisations will lie along one of the three 100 directions. The maximum deviation from H occurs when H is along the 111 axis, giving a cone of distribution of 55 around the axis.10 Averaging the saturation magnetisation over this angle gives a remanent magnetisation of 0.832 Ms In a system with uniaxial anisotropy with positive K1 at remanence the magnetisation vectors cover a hemicircle in a two-dimensional system and a hemisphere in a three-dimensional system. These give Mr 0.637 and = 9 Mr = 0.5 respectively. These situations are for ideal cases and can be modied greatly by further interactions and sample characteristics.
30
Figure 3.5: Shape of hysteresis loop as a function of H , the angle between anisotropy axis and applied eld H, for: (a) H = 0 , (b) 45 and (c) 90 .
3.2.4
Coercivity
The coercive eld, Hc , is the eld at which the remanent magnetisation is reduced to zero. This can vary from a few A/m for soft magnets to 107 A/m for hard magnets. It is the point of magnetisation reversal in the sample, where the barrier between the two states of magnetisation is reduced to zero by the applied eld allowing the system to make a Barkhausen jump to a lower energy. It is a general indicator of the energy gradients in the sample which oppose large changes of magnetisation. The reversal of magnetisation can come about as a rotation of the magnetisation in a large volume or through the movement of domain walls under the pressure of the applied eld. In general materials with few or no domains have a high coercivity whilst those with many domains have a low coercivity. However, domain wall pinning by physical defects such as vacancies, dislocations and grain boundaries can increase the coercivity.
Named after H. Barkhausen who, in 1919, gave experimental evidence of spontaneous reconguration of domains as an applied eld continuously alters the systems energy balance. These jumps can be small, resulting from localised domain wall movement, or large when associated with the nucleation of domains with reverse magnetisation, for example. The Berkhausen eect gives ne structure to magnetisation curves.
31
The loop illustrated in Figure 3.3 is indicative of a simple bistable system. There are two energy minima: one with magnetisation in the positive direction, and another in the negative direction. The depth of these minima is inuenced by the material and its geometry and is a further parameter in the strength of the coercive eld. Another is the angle, H , between the anisotropy axis and the applied eld. Figure 3.5 shows how the shape of the hysteresis loop and the magnitude of Hc varies with H . This eect shows the importance of how samples with strong anisotropy are mounted in a magnetometer when comparing loops.
3.3
Antiferromagnetism
Below TN the two sublattices of an antiferromagnet spontaneously magnetise in the same way as a ferromagnet but the net magnetisation is zero due to the opposing orientation of the sublattices magnetisation. If an external eld, H, is applied a small net magnetisation can be detected. The resultant magnetisation depends upon the orientation of the eld with respect to the magnetisation or spin axis. If the eld is applied parallel to the spin axis the zero-eld value of magnetisation of one sublattice, A, is increased by MA whilst the other, B, is decreased by MB . The net magnetisation in the direction of the eld is then M = |MA | + |MB | (3.5) If the eld is applied perpendicular to the spin axis each sublattice magnetisation is turned from the spin axis by a small angle, , as shown in Figure 3.6. The spins reorient by angle given by 2 (HmA sin ) = H (3.6)
where HmA is the molecular eld given by HmA = 2AM where A is the exchange energy and the resultant magnetisation is then equal to M = 2MA sin This magnetisation is linear with applied eld with no hysteresis. (3.7)
3.4
Temperature Dependence
A hysteresis curve gives information about a magnetic system by varying the applied eld but important information can also be gleaned by varying the
32
Figure 3.6: Rotation of sublattice magnetisation under an applied eld, H, perpendicular to the spin axis.
temperature. As well as indicating transition temperatures, all of the main groups of magnetic ordering have characteristic temperature/magnetisation curves. These are summarised in Figures 3.7 and 3.8. At all temperatures a diamagnet displays only any magnetisation induced by the applied eld and a small, negative susceptibility. The curve shown for a paramagnet is for one obeying the Curie law, = C T (3.8)
and so intercepts the axis at T = 0. This is a subset of the Curie-Weiss law, = C T (3.9)
where is a specic temperature for a particular substance (equal to 0 for
33
Figure 3.7: Variation of reciprocal susceptibility with temperature for: (a) antiferromagnetic, (b) paramagnetic and (c) diamagnetic ordering.
paramagnets). Above TN and Tc both antiferromagnets and ferromagnets behave as paramagnets with 1/ linearly proportional to temperature. They can be distinguished by their intercept on the temperature axis, T = . Ferromagnetics have a large, positive , indicative of their strong interactions. For paramagnetics 0 and antiferromagnetics have a negative . = The net magnetic moment per atom can be calculated from the gradient of the straight line graph of 1/ versus temperature for a paramagnetic ion, rearranging Curies law to give = 3Ak Nx (3.10)
where A is the atomic mass, k is Boltzmanns constant, N is the number of atoms per unit volume and x is the gradient. Ferromagnets below Tc display spontaneous magnetisation. Their susceptibility above Tc in the paramagnetic region is given by the Curie-Weiss law10 =
J(J + 1)N g 2 m2 3k(T )
(3.11)
The slight curvature for the ferrimagnet is due to the diering Curie temperatures and interactions for the two types of magnetic atom.
34
Figure 3.8: Variation of saturation magnetisation below, and reciprocal susceptibility above Tc for: (a) ferromagnetic and (b) ferrimagnetic ordering.
where g is the gyromagnetic constant. In the ferromagnetic phase with T Tc the magnetisation M (T ) can be simplied to a power law, for example the magnetisation as a function of temperature can be given by M (T ) (Tc T ) (3.12)
where the term is typically in the region of 0.33 for magnetic ordering in three dimensions. The susceptibility of an antiferromagnet increases to a maximum at TN as temperature is reduced, then decreases again below TN . In the presence of crystal anisotropy in the system this change in susceptility depends on the orientation of the spin axes: decreases with temperature whilst is constant. These can be expressed as = C 2 (3.13)
where C is the Curie constant and is the total change in angle of the two sublattice magnetisations away from the spin axis, and = 2ng 2 B (J, a0 ) H 2kT + ng 2 B (J, a0 ) H (3.14)
35
where ng is the number of magnetic atoms per gramme, B is the derivative of the Brillouin function with respect to its argument a , evaluated at a0 , H is the magnetic moment per atom and is the molecular eld coecient.
3.5
SQUID Magnetometry
One of the most sensitive forms of magnetometry is SQUID magnetometry. This uses a combination of superconducting materials and Josephson junctions to measure magnetic elds with resolutions up to 1014 kG or greater.11
3.5.1
Electron-pair Waves
In superconductors the resistanceless current is carried by pairs of electrons, known as Cooper Pairs. Each pair can be treated as a single particle with a mass and charge twice that of a single electron, whose velocity is that of the center of mass of the pair. In a normal conductor the coherence length of the conduction electron wave is quite short due to scattering. Cooper pairs, however, are not scattered hence their wavefunctions are coherent over very long distances. Each pair can be represented by a wavefunction of the form12 P = ei(P .r)/ (3.15)
where P is the net momentum of the pair whose center of mass is at r. In a uniform current density all the electron wavelengths will be equal with the superposition of these coherent waves producing a single wave of the same wavelength, meaning all of the electron-pairs in a superconductor can be described by a single wavefunction P = ei(P
r)/
(3.16)
This electron-pair wave retains its phase coherence over long distances and it is this characteristic which leads to interference and diraction phenomena. As they are macroscopic manifestations of quantum interactions the phenomena are collectively termed Quantum Interference. Phase and Coherence An implication of this long range coherence is the ability to calculate phase and amplitude at any point on the waves path from the knowledge of its
36
phase and amplitude at any single point, combined with its wavelength and frequency. The wavefunction of the electron-pair wave in Equation 3.16 can be rewritten in the form of a one-dimensional wave as P = sin 2 x vt (3.17)
If we take the wave frequency, , as being related to the kinetic energy of the Cooper pair with a wavelength, , being related to the momentum of the pair by the relation = h/P then it is possible to evaluate the phase dierence between two points in a current carrying superconductor. If a resistanceless current ows between points X and Y on a superconductor there will be a phase dierence between these points that is constant in time. The phase dierence for such a plane wave is given by
Y
()XY = X Y = 2
X
x dl
(3.18)
where x is a unit vector in the direction of the wave propagation, and dl is an element of a line joining X to Y.12 The relation of v to the supercurrent density, Js , is Js = 1/2 ns .2e.v, where ns is the superelectron density, and 1/2 ns is the electron-pair density. The wavelength can therefore be written as = hns e 2mJs (3.19)
and hence the phase dierence between points X and Y can be written as ()XY Eect of a Magnetic Field The phase of the electron-pairs can be aected not only by the current density but also quite strongly by an applied magnetic eld. In the presence of a magnetic eld the momentum, p, of a particle with charge q in the presence of a magnetic eld becomes mv + qA where A is the magnetic vector potential. For electron-pairs in an applied eld their moment P is now equal to 2mv + 2eA.12 In an applied eld the phase dierence between points X and Y is now a combination of that due to the supercurrent and that due to the applied 2m = hns e
Y
J s dl
X
(3.20)
CHAPTER 3. MAGNETOMETRY eld, ie ()XY = [()XY ]i + [()XY ]B where [()XY ]i = and [()XY ]B = The Fluxoid 4e h 4m hns e
Y
37
(3.21) (3.22)
J s dl
X Y
A dl
X
(3.23)
One eect of the long range phase coherence is the quantisation of magnetic ux in a superconducting ring. This can either be a ring, or a superconductor surrounding a nonsuperconducting region. Such an arrangement can be seen in Figure 3.9 where region N has a ux density B within it due to supercurrents owing around it in the superconducting region S.
Figure 3.9: Superconductor enclosing a non-superconducting region.
In the closed path XYZ encircling the nonsuperconducting region there will be a phase dierence of the electron-pair wave between any two points, such as X and Y, on the curve due to the eld and the circulating current as given by Equation 3.21. The total phase change around the path XYZX can be written as = 4m hns e J s dl + 4m h B dS
S
(3.24)
38
where S is the area enclosed by XYZX.12 If the superelectrons are represented by a single wave then at any point on XYZX it can only have one value of phase and amplitude. Due to the long range coherence the phase is single valued meaning around the circumference of the ring must equal 2n where n is any integer.13 Rewriting Equation 3.24 using this condition we have a denition for = m ns e2 J s dl + m 2e B dS = n
S
h 2e
(3.25)
with the central part of this equation named the uxoid by F. and H. London. Due to the wave only having a single value the uxoid can only exist in quantised units. This quantum is termed the uxon, 0 , given by 0 = h = 2.07 1015 Wb 2e (3.26)
3.5.2
Josephson Tunnelling
If two superconducting regions are kept totally isolated from each other the phases of the electron-pairs in the two regions will be unrelated. If the two regions are brought together then as they come close electron-pairs will be able to tunnel across the gap and the two electron-pair waves will become coupled. As the separation decreases the strength of the coupling increases. The tunnelling of the electron-pairs across the gap carries with it a superconducting current as predicted by B.D. Josephson14 and is called Josephson Tunnelling with the junction between the two superconductors called a Josephson Junction. Like a superconductor this gap has a critical current. If a supercurrent, is , ows across a gap between regions with a phase dierence, , it is related to the critical current, ic , by is = ic sin (3.27)
so that the maximum current ows across the gap when there is a phase dierence of /2, where is = ic . The Josephson Tunnelling Junction is a special case of a more general type of weak link between two superconductors. Other forms include constrictions and point contacts but the general form is of a region between two superconductors which has a much lower critical current and through which a magnetic eld can penetrate.
39
3.5.3
Superconducting Quantum Interference Device (SQUID)
A Superconducting Quantum Interference Device (SQUID) uses the properties of electron-pair wave coherence and Josephson Junctions to detect very small magnetic elds. The central element of a SQUID is a ring of superconducting material with one or more weak links. An example is shown in Figure 3.10, with weak-links at points W and X whose critical current, ic , is much less than the critical current of the main ring. This produces a very low current density making the momentum of the electron-pairs small. The wavelength of the electron-pairs is thus very long leading to little dierence in phase between any parts of the ring. If a magnetic eld, Ba , is applied perpendicular to the plane of the ring, a phase dierence is produced in the electron-pair wave along the path XYW and WZX. A small current, i, is also induced to ow around the ring, producing a phase dierence across the weak links. Normally the induced current would be of sucient magnitude to cancel the ux in the hole of the ring but the critical current of the weak-links prevents this. The quantum condition that the phase change around the closed path must equal n2 can still be met by large phase dierences across the weaklinks produced by even a small current. An applied magnetic eld produces a phase change around a ring, as shown in Equation 3.23, which in this case is equal to (B) = 2 a 0 (3.28)
where a is the ux produced in the ring by the applied magnetic eld.12 a may not necessarily equal an integral number of uxons so to ensure the total phase change is a multiple of 2 a small current ows around the ring, producing a phase dierence of 2(i) across the two weak-links, giving a total phase change of (B) + 2(i) = n2 (3.29)
The phase dierence due to the circulating current can either add to or subtract from that produced by the applied magnetic eld but it is more energetically favourable to subtract: in this case a small anti-clockwise current, i .12 Substituting values from Equations 3.27 and 3.28, the magnitude of the
40
Figure 3.10: Superconducting quantum interference device (SQUID) as a simple magnetometer.
circulating current, i , can be obtained |i | = ic sin a 0 (3.30)
As the ux in the ring is increased from 0 to 1/20 the magnitude of i increases to a maximum. As the ux is increased greater than 1/20 it is now energetically favourable for a current, i+ , to ow in a clockwise direction,
41
decreasing in magnitude to 0 as the ux reaches 0 . The circulating current has a periodic dependence on the magnitude of the applied eld, with a period of variation of 0 , a very small amount of magnetic ux. Detecting this circulating current enables the use of a SQUID as a magnetometer.
3.5.4
SQUID Magnetometer
The circulating current produced by a ux change in the SQUID can be detected by the use of a measuring current, I, as shown in Figure 3.10. This current divides equally between both weak-links if the ring is symmetrical. Whilst the current through the weak-links is small there will be no voltage detected across the ring. As I is increased it reaches a critical measuring current, Ic , at which voltages begin to be detected. The magnitude of the critical measuring current is dependent upon the critical current of the weak-links and the limit of the phase change around the ring being an integral multiple of 2. For the whole ring to be superconducting the following condition must be met a = n 2 (3.31) 0 where and are the phase changes produced by currents across the weaklinks and 2 a/0 is the phase change due to the applied magnetic eld. When the measuring current is applied and are no longer equal, although their sum must remain constant. The phase changes can be written as + + 2 a 0 a 0
= n = n
(3.32) (3.33)
where is related to the measuring current I. Using the relation between current and phase in Equation 3.27 and rearranging to eliminate i we obtain an expression for I, I = 2ic cos a sin 0 (3.34)
As sin cannot be greater than unity we can obtain the critical measuring
42
Figure 3.11: Critical measuring current, Ic , as a function of applied magnetic eld.
current, Ic from Equation 3.34 as Ic = 2ic cos a 0 (3.35)
which gives a periodic dependence on the magnitude of the magnetic eld, with a maximum when this eld is an integer number of uxons and a minimum at half integer values as shown in Figure 3.11.
Chapter 4 Experimental Techniques

Hunt with eyes of falling light, A single jewel on the shore, Reveals itself with rising light, Hidden in its shell no more. Cupped the shell to ears so tight, Now to hear these secrets roar. This chapter outlines the equipment used to obtain the data for this thesis using the phenomena covered in Chapters 2 and 3.
4.1
Mssbauer Spectrometers o
This section covers a generic Mssbauer spectrometer and the specic equipo ment used in the Mssbauer laboratory in the University of Liverpool for the o room temperature spectrometer and an electromagnet CEMS spectrometer.
4.1.1
57
Gamma-ray Source
Fe Mssbauer spectroscopy uses a 57 Co source. The decay scheme of this o isotope is shown in Figure 4.1. The half-life of 57 Co is 271.7 days and decays by electron capture to the I = 5/2 excited state of 57 Fe. This excited state decays to the I = 3/2 excited state (14.41 keV) or to the I = 1/2 ground state by gamma-ray emission. The 14.41 keV state decays in turn to the ground state by gamma-ray emmission or internal conversion. The ratio of these two decay rates are given by Equation 2.28, where = 8.21 for 57 Fe. The half-life of the 14.41 keV excited state is 97.8 ns, giving a Mssbauer gammao mm/s. The linewidth of a resonant emission and ray with a linewidth of 0.097 absorption event is thus 0.194 mm/s in perfect conditions.7 43
CHAPTER 4. EXPERIMENTAL TECHNIQUES
44
Figure 4.1: Decay scheme for a 57 Co source leading to gamma-ray emission. Internal conversion accounts for the remaining 91% of 14.41 keV events.
The sources used in this thesis are fabricated by diusing 57 Co atoms in a rhodium foil matrix: the rhodium matrix provides a solid environment for the 57 Co atoms with a high recoil-free fraction and a cubic, non-magnetic site environment to produce mono-energetic gamma-rays. The initial source activities are 100 mCi with a linewidth of 0.22 mm/s measured with a thin absorber.
4.1.2
Basic Mssbauer Spectrometer o
Figure 4.2 shows a schematic diagram of a simple Mssbauer spectrometer. o The source velocity is controlled by a transducer which is oscillated with constant acceleration. A waveform generator sends a reference waveform (triangular in the spectrometers at Liverpool) to the drive amplier, via a Digital to Analogue Converter. This signal is sent to the vibrator where it is converted to a mechanical oscillation of the drive shaft and source. A small
45
Figure 4.2: Mssbauer spectrometer schematic. o
coil within the vibrator provides a feedback signal to correct any deviations from the reference waveform. The detector is a proportional counter containing a 90% argon and 10% methane gas mixture. It uses an applied bias voltage of 2.0 to 2.5 keV and has a 65% detection eciency for 14.41 keV gamma-rays. The pulse magnitude from the detector is directly proportional to the gamma-ray energy and is sorted by a single channel analyser after amplication. This allows the selection of the Mssbauer gamma-ray from any other radiation emitted o from the source. The detector counts and source velocity are synchronised by a microprocessor system. The counts accumulate in 576 channels for one complete cycle, which contain two complete spectra: one for positive acceleration and one for negative acceleration of the source. As the acceleration is constant the time interval is equal for all velocity intervals, hence each channel records for the same amount of time. During analysis the full spectrum is folded around a center point to produce a single spectrum. This increases the number of counts (and hence gives better statistics) and attens the background prole produced by the dierence in intensity of the source radiation as the source
CHAPTER 4. EXPERIMENTAL TECHNIQUES moves relative to the absorber and detector.
46
4.1.3
CEMS
Conversion Electron Mssbauer Spectroscopy utilises the emission of convero sion electrons from the decay of the 14.41 keV state in the absorber to record the spectrum. This is useful for samples with thick substrates which would block transmission of gamma-rays or for studies of the surfaces of samples rather than the bulk. As the ratio of conversion electrons to gamma-rays emitted by the 14.41 keV Mssbauer event in 57 Fe is 8.21 the counting eo ciency of CEMS is much greater than the transmission method. A schematic diagram of the CEMS spectrometer as used in this thesis is shown in Figure 4.3.15 As the emitted electrons are of a low energy they would be attenuated by a detector window hence the sample is inserted directly into the detector. The source irradiates the sample through the window. An anode wire is maintained at a high voltage ( 800 V) directly in front of the sample. Electrons emitted from the sample are accelerated towards the anode, ionising atoms in the counting gas, producing an avalanche eect which amplies the signal from the original emitted electron. This electronic pulse is detected and recorded as for Transmisson Mssbauer Spectroscopy. o The counting gas, a 90% helium and 10% methane mix, is constantly replenished by a small ow from a cannister. This ushes out any contaminants from the atmosphere, such as oxygen, which would reduce the counting eciency. The methane acts as a quenching gas, preventing helium ions reaching the cathode whilst maintaining a high gain. The counting gas mixture of helium/methane has negligible reaction with the incident 14.41 keV gammarays - making it transparent to the incident radiation - but when electrons are emitted from the sample the normal proportional counter eect described above takes place. The perspex window attenuates the 6.3 keV x-rays from the source which would otherwise produce a large background signal from non-resonantly emitted electrons, but only attenuates the 14.41 keV gammaray by a small amount. Measurements with this system are restricted to room temperature due to the bulk of the detector itself and the condensation of the methane gas at low temperatures. A magnetic eld of up to 2.5 kOe can be applied in the plane of the sample. This is supplied by placing the CEMS detector between the soft iron poles of an electromagnet. Fields greater than 2.5 kOe are prohibited due to the curved trajectory of the emitted electrons in a magnetic eld producing a reduced counting eciency. Samples are mounted upon the aluminium faceplate of the sample mount
47
Figure 4.3: CEMS detector used at Liverpool University.
using a thin layer of vacuum grease. The samples are then covered with a sample shroud constructed from aluminium foil to present a smooth, continuous face to the anode wire. This surface is cleaner than the sample mount which can become coated with contaminants stuck to the vacuum grease and prevents electric elds building at sharp corners or edges on the sample which may produce electron discharges towards the anode and hence increase the background noise.
48
4.2
Data Analysis
Although simple analysis can be performed by eye on Mssbauer spectra (eg o seeing whether a sample is magnetised or not) to determine the hyperne parameters computer analysis is necessary. The raw data is collected by a data acquisition computer system and transferred to a Sun Solaris system for analysis. The spectrum is folded and a theoretical spectrum is calculated according to specied hyperne parameters and compared to the data. The parameters can then be varied to obtain the lowest 2 value and give the best t. As there are a number of minima of 2 that can be obtained from various points in parameter space the resulting ts must then be checked for consistent parameters to ensure a t that is physically valid.
4.2.1
2 Minimisation
2 is a measure of the deviation of the theoretical spectrum and the experimental spectrum, giving a best t when it is at a minimum. The analysis programs vary the parameters of the theoretical spectrum to nd a minimum in 2 according to the following formula: 1 = N n
2 N
i=1
Ei Ti Ei
(4.1)
where N is the number of channels (576 in this case) and n is the number of parameters that are free to vary. Ei and Ti are the number of counts in the ith channel of the experimental and theoretical spectra respectively.
4.2.2
Fitting Routines
The core program of the main tting routines as used at Liverpool is called fcfcore which contains code to read and write the data les, vary the parameters and perform 2 minimisation (using NAG routine E04FCF). The physics which determines the line positions and intensities is contained in separate subroutines, making it easy to alter and add new types of tting routines. For most spectra a general purpose subroutine called FFitA is used. This can produce multiple singlets, doublets or sextets using Lorentzian lineshapes. To reduce the computing time necessary for tting it uses the approximations described in Section 2.3.4.
49
For spectra with distributions of hyperne eld or quadrupole splitting values a program called NORMOS/DIST is used. This is an extension to the NORMOS/SITE tting package. This uses the VA02A routine for 2 minimisation. The routines can t with multiple hyperne eld or quadrupole splitting distribution blocks as well as multiple crystalline sites.
4.2.3
Calibration
To analyse the recorded spectra the spectrometer needs to be calibrated. The three main calibration parameters are the velocity scale, the center point of the spectrum and the alinearity of the velocity/time prole of the oscillation compared to a standard reference. The calibration is performed using a spectrum recorded from an -iron foil at room temperature and tted with the FCal subroutine. The velocity scale is calibrated using the well dened line positions of the sextet from -iron, which occur at 5.312 mm/s, 3.076 mm/s and 0.840 mm/s.16 The center of this -iron spectrum at room temperature is taken as the reference point (0.0 mm/s) for isomer shift values of sample spectra.
4.3
SQUID Magnetometer
The magnetometry data for this thesis have been taken using a Quantum Design Magnetic Property Measurement System (MPMS) XL SQUID magnetometer.
4.3.1
Magnetometer Overview
The MPMS system comprises of two main sections: the dewar, probe and SQUID assembly, and the electronic control system. The probe system is modular allowing the addition of extra component options (such as the RSO option, see Section 4.3.2). The probe contains a high precision temperature control system, allowing measurements between 1.9 K and 400 K with an accuracy of 0.01 K, and superconducting electromagnet, giving a eld of up to 50 kG with an accuracy of up to 0.1 G. The dewar consists of an inner liquid helium reservoir and outer liquid nitrogen jacket, to reduce excessive liquid helium boil o. The liquid helium is used both for maintaining the electromagnet in a superconducting state and for cooling the sample space.
50
Samples are mounted within a plastic straw and connected to one end of a sample rod which is inserted into the dewar/probe. The other end is attached to a stepper motor which is used to position the sample within the center of the SQUID pickup coils. The pickup coils are congured as highly balanced second-derivative coils, approximately 3 cm long. The coils reject the applied eld from the superconducting magnet to a resolution of 0.1%.
4.3.2
RSO Measurements
The data were taken using the Reciprocating Sample Option (RSO). Unlike DC measurements where the sample is moved through the coils in discrete steps the RSO measurements are performed using a servo motor which rapidly oscillates the sample, see Figure 4.4. These measurements have a sensitivity of 5 109 EMU.17 A shaft encoder on the servo motor records the position of the sample synchronous with the SQUID signal. The data received is tted to an ideal dipole moment response. To ensure this assumption is applicable samples need to be small: the calibration sample is a cylinder of 3 mm diameter and 3 mm height. Samples of this size or smaller match an ideal point dipole to an accuracy of approximately 0.1%.17 RSO measurements can be made in one of two congurations: Center or Maximum slope. Center scans use large oscillations (2 to 3 cm) around the center point of the pickup coils. These scans take a long time but the sample always remains properly located and a large number of measurements are recorded. These give the most accurate readings. The Maximum Slope method oscillates the sample over a small region (2 mm) at the most linear part of the SQUID response (as shown in Figure 4.4). The smaller amplitude makes measurements quicker and prevents the sample being subjected to signicant magnetic eld variation, however it also makes the measurement less accurate and susceptible to drift in the sample position. All measurements taken in this thesis using the MPMS XL SQUID were performed in Center mode with an amplitude of 3 cm.
51
Figure 4.4: Illustration of an RSO measurement with a small amplitude. (a) shows the ideal SQUID response for a dipole and (b) shows the movement of the sample within the SQUID pickup coils.
Chapter 5 Magnetic Interactions

Hawk alone in wait, hunkered down to grasp with talons bare, talons barbed, tight within its perch, in branch embed and feeling naught from wind and squall, none to break its steadfast gaze upon its prey; a sparkling shoal. Scale and movement mirrored, facing all towards the stream, its ow and whirl portrayed in their gently twisting dance. This chapter gives an overview of some of the more important magnetic interactions that occur within the thin lm systems studied in this thesis. Of particular importance is the magnetic anisotropy of a system, as this can change considerably when going from bulk to thin lm and multilayer systems. The RKKY interaction can also greatly inuence the magnetic ordering in some systems as distances between magnetic entities are varied.
5.1
Magnetic Anisotropy
Magnetic anisotropy is the dependence of the internal energy of a system on the direction of the spontaneous magnetisation. An energy term of this kind is called magnetic anisotropy energy. In general most kinds of magnetic anisotropy are related to the crystal symmetry of a material and this is known as magnetocrystalline anisotropy. Anisotropy can also be related to mechanical stress in the system and this is known as magnetostrictive anisotropy.
52
CHAPTER 5. MAGNETIC INTERACTIONS
53
5.2
5.2.1
Magnetocrystalline Anisotropy
Uniaxial Anisotropy
The simplest form of crystal anistropy is uniaxial anisotropy. For cubic crystals the anisotropy energy can be expressed in terms of the direction cosines (1 , 2 , 3 ) of the internal magnetisation with respect to the three cube edges. Due to the high symmetry of the cubic crystal this can be expressed in a simple manner as a polynomial series in the direction cosines. This can be simplied further10 to
2 2 2 2 2 2 2 2 2 Ea = K1 1 2 + 2 3 + 3 1 + K2 1 2 3 +
(5.1)
When K1 > 0 the rst term of Equation 5.1 becomes a minimum for 100 directions, whilst for K1 < 0 it is a minimum for 111 directions.
5.2.2
Interface and Volume Anisotropy
It has been shown18 that in multilayers the eective magnetic anisotropy energy, Kef , can be phenomenologically split into two components: a volume contribution, KV , and an interface contribution, KS , which are related to Kef by 2KS Kef = KV + (5.2) t where t is the thickness of the magnetic layer. The relation is a weighted average of the magnetic anisotropy energy of the interface atoms and the inner volume atoms in the layer. The factor of 2 arises from the layer being bounded by two interfaces. In bulk systems the magnetocrystalline anisotropy of a system is dominated by the volume term. In thin lms and multilayers, however, the surface term can become more signicant as t becomes small ( 2KS/KV ). In most cases the anisotropy in thin magnetic layers is dominated by the dipolar shape anisotropy, favouring inplane moment alignment.
5.2.3
Single-ion Anisotropy
Single-ion anisotropy (often referred to simply as magnetocrystalline anisotropy) is determined by the interaction between the orbital state of a magnetic ion and the surrounding crystalline eld which is very strong. The anisotropy is a product of the quenching of the orbital moment by the crystalline eld.
54
This eld has the symmetry of the crystal lattice. Hence the orbital moments can be strongly coupled to the lattice. This interaction is transferred to the spin moments via the spin-orbit coupling, giving a weaker d-electron coupling of the spins to the crystal lattice. When an external eld is applied the orbital moments may remain coupled to the lattice whilst the spins are more free to turn. The magnetic energy depends upon the orientation of the magnetisation relative to the crystal axes. In a magnetic layer, the single-ion anisotropy is present throughout the layer volume, and so contributes to KV . Whether this is in addition to or subtraction from KV depends upon the crystal orientation of the layer. In transition metals this contribution is generally much smaller than the shape anisotropy but can be comparable in magnitude in rare earth metals, hence the large interest in rare earth materials in thin lm systems to tailor moment orientation such as Perpendicular magnetic Anisotropy. The single-ion anisotropy can also contribute to the surface anisotropy via Nel interface anisotropy,19 where the reduced symmetry at the interface e strongly modies the anisotropy at the interface compared to the rest of the layer. This can be in addition to or subtraction from the interface anisotropy depending upon the crystal properties of the layer and the sample construction.
5.2.4
Shape Anisotropy
The magnetic dipolar anisotropy, or shape anisotropy, is mediated by the dipolar interaction. This interaction is long range and so its contribution is dependent upon the shape of the sample. Hence shape anisotropy becomes important in thin lms and often produces inplane alignment of moments. In a thin lm considered as a magnetic continuum the dipolar anisotropy energy per unit volume is given by20 1 2 E = 0 Ms cos2 2 (5.3)
where Ms is the saturation magnetisation, assumed to be uniform throughout the layer. The magnetisation subtends an angle, , to the plane normal. The dipolar anisotropy energy is thus minimised for an angle of 90 ie moments lying in the plane of the layer.
55
5.2.5
Exchange Interaction and Exchange Anisotropy
The origin of the interaction which lines up the spins in a magnetic system is the exchange interaction. When spin magnetic moments of adjacent atoms i and j make an angle ij , the exchange energy, wij , between the two moments can be expressed as10 wij = 2JS 2 cos ij (5.4) where J is the exchange integral and S is the total spin quantum number of each atom. For positive values of J this gives a minimum when ij = 0 ie the spins are aligned parallel to each other. Although the exchange interaction produces strong interactions between neighbouring magnetic atoms it can also be mediated by various mechanisms, producing long range eects. As the exchange energy for neighbouring atoms is dependent only upon the angle between them it does not give rise to anisotropy. In multilayers where magnetic layers are separated by a non-magnetic layer, there can be an exchange coupling between the two magnetic layers mediated by, for example, the RKKY interaction (see Section 5.4). The exchange coupling is composed of two terms: an isotropic exchange coupling and an anisotropic Dzialoshinski-Moriya exchange coupling. The total exchange interaction energy is given by21 EEX = 2J(z)M 1 M 2 (5.5)
where J(z) is the exchange coupling constant, M 1 and M 2 are the magnetisation of the adjacent magnetic layers and z is the non-magnetic layer thickness. This product is a maximum for ferromagnetically aligned layers. The anisotropic exchange energy is given by21 EDM = J DM (z) (M 1 M 2 ) (5.6)
where J DM is the Dzialoshinski-Moriya exchange constant. The cross product gives a resultant that is perpendicular to the direction of the layer magnetisation. This is at a maximum when the two layer magnetisations are at right angles to each other. This can favour inplane moment alignment for positive J DM and out of plane alignment for negative J DM .
5.3
Magnetostriction
Magnetostriction is the change in length in a given direction of a magnetic material when it is magnetised along that direction. Similarly strain in a
CHAPTER 5. MAGNETIC INTERACTIONS ferromagnet can alter the direction of the magnetisation.
56
5.3.1
Magneto-elastic Anisotropy
The magneto-elastic eect arises from the spin-orbit interaction. The spin moments are coupled to the lattice via the orbital electrons. If the lattice is changed by strain the distances between the magnetic atoms is altered and hence the interaction energies are changed. This produces magneto-elastic anisotropy. Magnetostriction constants, hkl , are dened for various crystal directions. For an elastically isotropic medium, with isotropic magnetostriction, the magneto-elastic energy per unit volume is given by8 3 E = cos2 2 (5.7)
where is the stress and is the angle between the magnetisation and stress directions. For positive , as in metallic iron, the easy magnetic direction will be along a direction of tensile stress, or perpendicular to a compressive stress. Strain in thin lms and multilayers can be produced by the growth conditions, such as lattice mismatch between layers or thermal stress caused by dierences in thermal expansion coecients of adjacent layers.
5.4
The RKKY Interaction
Indirect exchange couples moments over relatively large distances. It is the dominant exchange interaction in metals where there is little or no direct overlap between neighbouring magnetic electrons. It therefore acts through an intermediary which in metals are the conduction electrons (itinerant electrons). This type of exchange was rst proposed by Ruderman and Kittel22 and later extended by Kasuya and Yosida to give the theory now generally know as the RKKY interaction. The interaction is characterised by a coupling coecient, j, given by23 j (Rl Rl ) = 9 j2
F
F (2kF |Rl Rl |)
(5.8)
where kF is the radius of the conduction electron Fermi surface, Rl is the
57
Figure 5.1: Variation of the indirect exchange coupling constant, j, of a free electron gas in the neighbourhood of a point magnetic moment at the origin r = 0.
lattice position of the point moment, F (x) =
is the Fermi energy and (5.9)
x cos x sin x x4
The RKKY exchange coecient, j, oscillates from positive to negative as the separation of the ions changes and has the damped oscillatory nature shown in Figure 5.1. Therefore, depending upon the separation between a pair of ions their magnetic coupling can be ferromagnetic or antiferromagnetic. A magnetic ion induces a spin polarisation in the conduction electrons in its neighbourhood. This spin polarisation in the itinerant electrons is felt by the moments of other magnetic ions within range, leading to an indirect coupling. In rare-earth metals, whose magnetic electrons in the 4f shell are shielded by the 5s and 5p electrons, direct exchange is rather weak and insignicant and indirect exchange via the conduction electrons gives rise to magnetic order in these materials.
Chapter 6 Binary Laves Phase Multilayers and Thin Films

Strong and closed, Locking selsh and within, Weak and opened, Reaching shared and calling, Face out and unite, Free yet in nature chained, Let loose in ight, Power set on wings claimed. This chapter presents CEMS measurements of Rare Earth/Iron Laves Phase thin lms and multilayers. The rst section gives an outline of the characteristics of these systems and their potential uses. Then the results are displayed and discussed from the viewpoint of a Mssbauer spectroscopy study of the o magnetic anisotropy in thin lm samples. We are attempting to determine the magnetic easy axis through analysis of accurate line positions which are sensitive to the dipolar magnetic hyperne eld. The latter sections observe the eects of multilayers of dierent Laves Phase materials on the anisotropy and hyperne elds.
6.1
Introduction to Rare Earth/Iron Laves Phase Systems
The Lanthanides are the group of elements with atomic numbers between 57 and 71. They are often accompanied by yttrium as it has similar chemical characteristics and are termed Rare Earths due to the diculty with which 58
CHAPTER 6. RFE2 LAVES PHASE THIN FILMS
59
they are chemically isolated. This diculty arises from the typical atomic conguration of a rare earth,13 [Xe]4f n 5d(1 or 0) 6s2 . The 4f shell is partially lled whilst the outer valence electrons are much the same in nature throughout the series, giving similar chemical characteristics to all fteen elements. The partially lled 4f shells in rare earths lead to magnetic properties in a similar manner to the partially lled 3d shell in transition elements. In an intermetallic of a rare earth and a transition element the spatial extent of the 4f wavefunction is highly localised giving very weak interactions between rare earth atoms. In such compounds where the transition element carries no magnetic moment this gives rise to low ordering temperatures,24 eg Tc = 26.5 K for DyNi2 . Any interactions must take place indirectly through such mechanisms as spin polarization of the s-conduction electrons.24 The localised 4f moments are aected by the polarisation produced by 4f moments elsewhere in the lattice and can orient themselves accordingly. This polarization is not uniform in space and has an oscillitatory form as given by the RKKY interaction (see Section 5.4). The transition element, however, has much stronger and more long range interatomic interactions due the large spatial extent of the 3d electron wavefunctions. The wavefunctions of neighbouring atoms overlap producing 3delectron energy bands rather than levels. The strong exchange interactions between the 3d electrons can produce unequal numbers of spin-up and spindown electrons. Relative dierences in the density of states of 3d electrons produces a net moment given by m=
E
(N (E) N (E) )
(6.1)
where N (E) and N (E) are the density of states of the spin-up and spindown electrons respectively. Chemical substitution can alter the number of 3d electrons producing changes in the 3d magnetic moment.24 The magnetic interaction between the rare earth and transition element has a strength intermediate between that of the two cases discussed above. The rare earth and transition element sublattices couple antiparallel in the case of a heavy rare earth (eg Holmium) and parallel in the case of a light rare earth (eg Praseodymium). The 3d moments align antiferromagnetically with the spin-moment of the rare earth and the dierence in coupling between the light and heavy rare earth cases is attributed to the total angular momentum of a rare earth being J = L S for light rare earths and J = L + S for heavy rare earths.24 Another way in which the rare earth and transition element dier is in the strength and types of magnetic anisotropy they display. Dipolar interactions
60
are proportional to the square of the moment, the pair energy of a magnetic dipole interaction given by10 3M 2 l= 40 r3 (6.2)
where M is the magnetic moment and r the distance between the atoms. As the magnetic moment of a rare earth is typically an order of magnitude greater than a transition element a large anisotropy could be expected due to dipolar interactions. However, there is only appreciable ordering of rare earth magnetic moments at low temperatures and so at room temperature or above the dipolar interactions are small and of comparable magnitude to those for a transition element.24 The dominant contribution to anisotropy in these intermetallics is due to the eects of the crystal eld on the rare earths 4f wavefunction. Rare earths have very strong single-ion magnetocrystalline anisotropy (see Section 5.2), essentially the interaction between orbital state and the crystal eld. In bulk materials rare earth metals require applied elds of hundreds of kOe to overcome the anisotropic forces, compared to a few kOe for a transition element such as metallic Iron. Intermetallics of rare earths and transition elements can combine the quite dierent natures of the two types of material via the antiferromagnetic coupling between the 3d moment and 4f spin-moment. The rare earth can provide strong magnetocrystalline anisotropy, a large magnetic moment per atom and a large degree of magnetostriction (see Section 5.3), and this is combined with the strong magnetic exchange coupling of the 3d moments. Using particular elements and compositions we can engineer magnetic systems with specic properties for applications such as permanent magnets and recording media and readheads. The similar chemical properties but varying magnetic properties of the rare earths across the entire series also oers benets for research as often the same compositions of intermetallic can be produced with all the rare earths but with widely varying physical properties allowing the investigation of fundamental properties such as spin and angular momentum under dierent conditions.
6.1.1
Bulk Properties
The bulk properties of RFe2 systems have been studied extensively for many years.25, 26, 27, 28 They show ferro- or ferrimagnetic structures in binary compounds. Their crystal structure is the cubic Laves Phase MgCu2 type, shown in Figure 6.1, and the iron atoms occupy corner-sharing tetrahedral networks
61
R Fe
Figure 6.1: The atomic positions in the C15 MgCu2 Cubic Laves Phase unit cell.
with a ( point symmetry and a threefold axis lying along one of the 111 3m) directions. This direction is the principal axis of the electric eld gradient, Vzz . The rare earth atoms have a cubic ( 43m) site symmetry. In the high temperature paramagnetic state the four iron sites are equivalent, giving a single Mssbauer spectrum. In the magnetically ordered state o the number of sites which are magnetically equivalent or inequivalent depends upon the angle between the magnetisation and the axes of local symmetry along the 4 111 directions. If the magnetisation is parallel to the [100] direction (as in DyFe2 or HoFe2 ) this makes an equivalent angle to all iron sites of 54.7 . Again a single Mssbauer spectrum is observed.27 o If the magnetisation is parallel to the [111] direction (as in YFe2 ) there are two inequivalent types of iron site; one at an angle of 0 to the magnetisation and the remaining three at an angle of 70.5 . The hyperne interactions are dierent at the two sites due to the total hyperne splitting at the nucleus being a function of the angle between the hyperne eld and the principal axis of the quadrupole interaction, Vzz , (Equation 2.21) and the angular dependence of dipolar elds on this same angle (Equation 2.20). Hence in a Mssbauer spectrum we would expect two components in a ratio of 3:1 and o this is observed.27 If the magnetisation is along an arbitrary direction then all the iron sites may be inequivalent, giving a Mssbauer spectrum with four components of o equal intensity.
62
6.1.2
Thin Films and Multilayers
The RFe2 family of intermetallics have shown potential uses in a number of nano-scale applications such as magnetic media readheads and nanosensors and so their behaviour in thin lms and other low-dimensional systems has become of great interest to fundamental and applied research. Going from bulk to a thin lm increases the eect of otherwise negligible eects such as shape anisotropy, strain and interface eects. Previous work29 on expitaxial Laves Phase DyFe2 thin lm samples highlighted the importance of expitaxial strain in perturbing the magnetic behaviour seen in bulk samples. In pure rare earths the anisotropy energy is roughly an order of magnitude greater than the magnetoelastic energy. RFe2 systems, however, show giant magnetostriction at room temperature. The magnetoelastic energies in these samples can be large enough to strongly inuence the overall anisotropy energy and hence the magnetic easy axis. In an unstressed sample the dominant inuence on the direction of the easy axis is the magnetocrystalline anisotropy energy, Emc , given by30
2 2 2 2 2 2 2 2 2 Emc = K1 x y + x z + y z + K2 x y z
(6.3)
where i are the cosines of the magnetisation direction and K1 and K2 are the anisotropy constants. The direction of magnetisation is mainly related to the magnitude and sign of the anisotropy constants (eg in DyFe2 K1 is positive and K2 is negative, and |K2 |/K1 < 9 leading to a magnetisation along the [100] direction, see Section 5.2.1). In the samples studied in this chapter there are strains caused by a dierence in thermal contraction between lm and substrate as the sample cools from the deposition temperature.30 It is now necessary to take into account the magnetoelastic energy, Eme , given by
2 2 2 Eme = b0 (xx + yy + zz ) + b1 x xx + y yy + z zz +b2 (x y xy + x z xz + y z yz )
(6.4)
where ij is the strain tensor and b0 , b1 and b2 are the magnetoelastic coecients, and the elastic energy, Eel , given by Eel = 1 C11 2 + 2 + 2 + C12 (xx yy + yy zz + xx zz ) xx yy zz 2 1 (6.5) + C44 2 + 2 + 2 xy yz xz 2
where C11 , C12 and C44 are the cubic elastic constants.30
63
The main strain in the samples is a negative shear30 of xy = 0.55%. This simplies Equation 6.4 to Eme = b2 xy x y . The total energy, Etot , is thus Etot = Emc + b2 xy x y + M 2 (x + y )2 (6.6) where M 2 (x + y )2 is the shape anisotropy as a function of the magnetisation, M .30 The magnetic easy axis will orient so as to minimise the energies of the competing magnetocrystalline and magnetoelastic energies and the shape anisotropy. The shape anisotropy favours an in plane alignment. DyFe2 in bulk has an easy axis along the [001] direction, which lies in plane for thin lm samples so we would expect these samples to show the same easy axis in the absence of signicant magnetoelastic anisotropy. However, results from other studies do not show an in plane magnetisation.29, 30
6.1.3
Sample Construction
All of the samples studied in this chapter have been prepared using Molecular Beam Epitaxy (MBE) by Dr R.C.C. Ward and Dr M.R. Wells, Clarendon Laboratory, Oxford University. An outgassed (11 sapphire substrate is 20) 11 placed into an MBE chamber at 4 10 Torr and 500 of Niobium is A is then deposited followed deposited as a buer. A thin Fe seed layer of 15 A by an 800 YFe2 seed layer. This provides basis for growth of good quality A lms and multilayers. The sample growth direction is (110), perpendicular to the plane of the sample. A generic schematic of the samples is shown in Figure 6.2.
6.2
RFe2 Thin Films
This section presents analysis of data from a CEMS study of the easy axis direction in thin lms (500 1000 ) of rare earth/iron intermetallics. CEMS A A was used as all samples have a thick Sapphire substrate which is opaque to the 14.41 keV Mssbauer gamma ray. All measurements are taken at room o temperature in either 0 kOe or 2.5 kOe in plane applied magnetic eld. The samples are not 57 Fe enriched.
6.2.1
Determining the Magnetic Easy Axis
A particularly important parameter to extract from the spectra is the direction of the magnetic easy axis. This is well known in bulk RFe2 intermetallics24 but has been shown to not be along any expected high-symmetry
64
(110)
Film or Multilayer
800A YFe2 Seed 15A Fe Seed 500A Nb Buffer Al2O3 Substrate
Figure 6.2: Schematic of the Laves Phase sample construction.
axis in thin lms at room temperature.29, 30 Mssbauer spectroscopy is paro ticularly sensitive to the orientation of magnetic moments at a particular site, either through the angular dependency of the dipolar hyperne eld (Equation 2.20) or from the relative line intensities (Equation 2.24). The latter is often much more pronounced and so easy to obtain reliable information from. Previous work on single-crystal RFe2 thin lms by V. Oderno et al 29 showed that the easy direction was 100 at 4.2 K but was a direction of low symmetry at room temperature. Their best ts were for those assuming an easy magnetic axis of 241 , with [ 142], [ 241], [ 124] and [124] being the most likely as they were closest to the angle displayed by their Mssbauer spectra. o Subsequent experiments by Mougin et al 30 again showed the dierence in easy axis at 4.2 K and room temperature. Their analysis indicated an easy axis along 351 directions, with the most likely being [ 351]. Consequently
65
our analysis starts with the assumption of a 241 or 351 easy axis at room temperature. However, the proposed easy axes of 241 or 351 both have a high level of degeneracy in a cubic system, corresponding to 24 dierent directions. These samples are conceived as single-crystal, thus a given axis such as [ 351] denotes a unique axis in the sample. However, there will be magnetic domains in which the magnetisation direction, while linked to an equivalent direction of 351 , does not dene a unique direction in the sample. Thus the Mssbauer spectrum will display the relative directions of Vzz and H o through line positions but will not give reliable information through relative line intensities as these can be aected by dierent magnetic domain patterns which can be aected by sample history. In the absence of a training eld there are still physical characteristics which favour particular directions. The shape anisotropy of the sample will favour moments that are more in plane and this is corroborated by the average angle obtained from the line intensities of 21 to the sample plane (for DyFe2 ). This does, however, still leave at least four non-equivalent directions and with no direct evidence of their relative populations.29 In interpreting the line positions of the Mssbauer spectra with high o accuracy it is necessary to consider the dipole contribution to the total eld at the iron nuclei. The dipolar hyperne eld is determined by the local environment of the nucleus: the interaction between the hyperne eld and EFG vectors at that site. As a localised interaction it is invarient with respect to the domain or sample orientation and so it is not subject to any averaging eects across the sample volume. The dipolar eld inuences the relative line positions both by its contribution to the magnitude of the total hyperne eld detected at the nucleus and also to its direction. This aects the quadrupolar hyperne interaction (explained in Section 2.3.4) as the dipolar eld tips the spins away from the primary EFG axis, Vzz , which for RFe2 Laves Phase samples is one of the 111 directions. The dipolar hyperne eld can be calculated using a matrix form devised by G.J. Bowden et al 31 of HD = D
111
(6.7)
where is the direction of the magnetic easy axis and D 111 is a set of matrices for each inequivalent iron site. These are shown in Equation 6.9. This can be used to evaluate the direction of the dipolar eld at each site. For example to calculate HD for the [111] Fe site assuming an easy axis of
CHAPTER 6. RFE2 LAVES PHASE THIN FILMS [ 351] we would use 0 1/2 = Dzz 1/2
1/2
66
HD
0
1/2
3 3 1/2 5 = D 1 zz 0 1 1
1/2
(6.8)
where Dzz is the magnitude of the dipolar eld, estimated as 16 kG in DyFe2 and 5 kG in YFe2 .27 1/2 1/2 1/2 0 0 1/2 D = 1/2 0 0 = 1/2 [111] 1/2 1/2 1/2 1/2 0 0 1/2 1/2 0 1/2 1/2 D = 1/2 0 0 = 1/2 [111] 1/2 1/2 1/2 1/2 0 1/2 1/2 0 1/2 1/2 0
D[111]
D [ 111]
(6.9)
The Fermi contact eld, H S (Equation 2.18), is much larger ( 215 kG in DyFe2 ) and lies along the magnetic easy axis, [ 351] in this case. Vector adding H D and H S gives the total hyperne eld at the site, H. The relative magnitude of the quadrupolar interaction can then be calculated using the angle, , between the resultant total hyperne eld, H, and the direction of Vzz for that site using = eqQ 2 1 3 cos2 1 2 (6.10)
where 1/2 (3 cos2 1) can be evaluated and the value of (eqQ/2) is determined through least squares analysis of the spectrum. The initial magnitudes of H S and H D are estimates taken from bulk systems. After the spectrum is tted according to the values obtained as in the above method and the best t is obtained, the tting parameters can be analysed. Taking a pair of total hyperne eld values and the known angle between H S and H D a simultaneous equation can be used to extract HS and HD . These derived values can then be used to calculate a new set of initial t parameters and the whole process is repeated in an interative fashion until stable values are obtained.
Any other terms are taken as having negligible eect on the total eld and its direc-
tion.
CHAPTER 6. RFE2 LAVES PHASE THIN FILMS [ 241] [ 351] HS = 205 2 kG HS = 205 5 kG HD = 15 4 kG HD = 17 7 kG 2 = 2.05 2 = 2.06 IS QS Field IS QS Field mm/s) mm/s) mm/s) mm/s) ( ( (kG) ( ( (kG) 0.1 0.0604 198.8 0.1 0.0935 199.7 0.1 0.1387 182.5 0.1 0.1432 182.5 0.1 +0.2191 209.1 0.1 +0.2167 208.8 0.1 +0.0644 205.7 0.1 +0.0949 204.8
67
Site [111] [11 1] [111] [1 11]
Table 6.1: Final t parameters for 750 DyFe2 sample assuming [241] or A [351] easy axis in zero applied eld.
6.2.2
DyFe2
In common with all the samples studied in this chapter at room temperature the 750 DyFe2 sample needs a minimum of four components to be tted A properly. Figure 6.3 shows the spectra for all of the thin lm samples studied in zero applied eld. Four inequivalent iron sites conrm the easy axis is not along any of the high symmetry directions expected in bulk systems. The best t parameters for the DyFe2 samples in zero applied eld are shown in Table 6.1 for ts assuming [ 241] or [ 351] easy axis directions with values calculated according to the dipole hyperne eld analysis in Section 6.2.1. The isomer shift values (IS) are xed to be equal for all components but free to vary as a whole. The IS value of 0.1 mm/s is consistent with those reported for bulk samples.32 The quadrupole splitting is xed and its value is calculated using the analysis outlined in Section 6.2.1. The hyperne elds are initially xed according to the values calculated from H S and H D and then allowed to vary. The theoretical values do not give satisfactory ts and are allowed to freely vary (with the quadrupole splitting remaining constant). Iteratively varying HS and HD to account for the dierence is prohibitively time consuming as it is not an automated process: there is no way to automatically transfer the parameters from the dipolar eld analysis into the Mssbauer tting routines. The spread in o values is from the dierent angle that the axis of symmetry at each iron site makes with the magnetic easy axis, and hence the dipolar eld contribution is dierent.
68
DyFe2(750A)
1.5 1.0 0.5 0.0
YFe2(1000A)
1.5 Percent Emission 1.0 0.5 0.0
0.6 0.4 0.2 0.0
HoFe2(500A)
2 0 2 Velocity (mm/s)
Figure 6.3: Comparison of spectra of DyFe2 , YFe2 and HoFe2 thin lms at room temperature under zero applied eld.
69
Figure 6.4: 750 DyFe2 thin lm under 0 kOe and 2.5 kOe in plane applied A magnetic elds.
The values of HS and HD (Table 6.1) obtained are consistent with those found for bulk samples.27 There is no signicant dierence between the ts for [ 241] and [ 351] easy axes either in the quality of the tting of theory to the spectrum or in the comparison of the derived hyperne eld values with those from other studies. A spectrum was recorded under an in plane applied eld, (H0 in Equation 2.17) of 2.5 kOe. This spectrum is compared to the zero applied eld spectrum in Figure 6.4 and the t parameters compared in Table 6.2. The tting parameters do not have any particular easy axis applied. The Isomer Shifts and relative line intensities are xed to be equal for all sites but free to vary. The change in average angle of the spin moments under applied eld is 0.2 . The two spectra were not recorded sequentially and thus this change in angle is well within the experimental error of the relative angular positioning of the source and sample, taken to be 2 .
CHAPTER 6. RFE2 LAVES PHASE THIN FILMS 0 kOe = 2.53 QS Field Angle IS (mm/s) (kG) ( ) (mm/s) 0.24 186.6 23.3 0.09 +0.12 200.6 23.3 0.09 +0.22 209.2 23.3 0.09 0.01 200.2 23.3 0.09
2
70
Site 1 2 3 4
IS (mm/s) 0.10 0.10 0.10 0.10
2.5 kOe 2 = 1.91 QS Field Angle (mm/s) (kG) ( ) 0.32 185.2 23.1 +0.19 197.0 23.1 +0.16 208.6 23.1 0.01 197.1 23.1
Table 6.2: Final t parameters for the 750 DyFe2 sample in 0 kOe or 2.5 kOe A in plane applied eld. No particular easy axis is applied to the tting parameters. The average angle is relative to the sample plane.
The change in the average hyperne eld due to the applied eld is 2.35 kG. The negative change in the hyperne eld indicates the iron moments being parallel to H0 : the hyperne eld lies antiparallel to the magnetic moment. It was expected that the hyperne elds would increase as the dysprosium moments, being signicantly larger than the iron moments, would tend to align parallel with an applied eld. Through the antiferromagnetic coupling the iron moments would then be lying antiparallel to the applied eld. To explain this there are competing eects in the sample under an applied eld from the sample and the seed layer. Although the signal from the seed layer underneath the 750 sample layer produces at most a 15% background A contribution to the spectrum (using the theory outlined in Section 2.5.2), the seed layer can inuence the moment orientation of the sample layer. In this bilayer arrangement a magnetic exchange-spring can be produced, where the moments in the soft magnetic seed layer twist at their free end whilst being pinned by the hard magnetic sample layer. The onset of this exchange spring under an applied eld is governed by a critical bending eld BB . For a bilayer this is related to the exchange eld, BEX , by the relation 2 (6.11) BB = BEX 2N where N is the number of monolayers in the soft magnetic layer.33 The exchange spring also penetrates into the hard magnetic layer, with the extent determined by the strength of the applied eld and the axial anisotropy of
Individual components cannot be compared due to the amount of overlap between all four components.
71
the hard magnetic layer. Using the conditions cited in Reference 33 for DyFe2 /YFe2 , an iron-iron exchange eld BEX = 6000 kOe and N = 114 gives a bending eld BB = 0.7 kOe. Our applied eld of 2.5 kOe is thus sucient to produce an exchange spring. The applied eld should, however, be far too small to overcome the single ion anisotropy of the DyFe2 thin lm (elds an order of magnitude greater than used in these measurements were used in Reference 33 without overcoming the anisotropy of the hard magnetic pinning layer). Whilst a small portion at the interface with the YFe2 seed layer would be rotated somewhat along the applied eld direction it is expected that the majority of the upper sample layer (also from which the majority of the CEMS signal is obtained) would be unperturbed. A sample oriented with the Dy moments antiparallel to the applied eld would give the observed results. The arrangement of the sample within the spectrometer was not recorded, however, so this is currently conjecture. DyFe2 , in bulk, has an easy axis that lies along one of the 100 directions. As the sample geometry includes the [001] direction in the plane of the sample, also favoured by the shape anisotropy of a thin lm, the magneto-elastic energy must be substantial to produce an easy axis so far out of plane. This direction is seemingly unperturbed by the application of a 2.5 kOe eld, also trying to force the moments into the plane of the sample. Without higher eld or temperature measurements (both of which are impossible with the CEMS equipment) an absolute value of Eme cannot be calculated but the data point to it being of at least the same order as the magnetocrystalline and shape anisotropy energies combined.
6.2.3
YFe2
A 1000 YFe2 sample was also studied in the the same way as that outlined A for the DyFe2 sample. The zero applied eld spectrum is compared to other thin lm samples in Figure 6.3. The Isomer Shifts of each site are xed to be equal but free to vary as a whole, as are the relative line intensities. The Isomer Shift values are the same as for DyFe2 which is expected as rare earths are chemically very similar. The results from applying a 2.5 kOe in plane magnetic eld are shown in comparison to zero eld in Table 6.4 and Figure 6.5. The most noticeable dierence is in the angle of the iron moments to the incident gamma ray (from the relative line intensities), the moments have been forced more in plane by 10.8 to lie at an angle of 14 to the sample plane. There is no error on the change in angle as the spectra were recorded sequentially.
CHAPTER 6. RFE2 LAVES PHASE THIN FILMS [ 241] [ 351] HS = 187 2 kG HS = 189 4 kG HD = 9 4 kG HD = 8 6 kG 2 = 2 = IS QS Field IS QS Field mm/s) mm/s) mm/s) mm/s) ( ( (kG) ( ( (kG) 0.10 0.48 184.8 0.10 0.66 185.4 0.10 0.93 172.3 0.10 0.96 173.2 0.10 +0.73 187.0 0.10 +0.72 185.1 0.10 +0.13 188.5 0.10 +0.26 189.0
72
Site [111] [11 1] [111] [1 11]
Table 6.3: Final t parameters for 1000 YFe2 sample assuming [241] or A [351] easy axis in zero applied eld. 0 kOe = 1.14 QS Field Angle IS mm/s) mm/s) ( (kG) () ( 0.31 178.8 24.8 0.09 0.03 179.4 24.8 0.09 +0.09 187.7 24.8 0.09 +0.22 183.5 24.8 0.09
2
Site 1 2 3 4
IS (mm/s) 0.10 0.10 0.10 0.10
2.5 kOe 2 = 1.19 QS Field Angle mm/s) ( (kG) ( ) +0.02 182.5 14.0 0.02 171.3 14.0 +0.13 184.4 14.0 0.08 180.2 14.0
Table 6.4: Final t parameters for the 1000 YFe2 sample in 0 kOe or 2.5 kOe A in plane applied eld. No particular easy axis is applied to the tting parameters. The average angle is relative to the sample plane.
As yttrium does not carry a magnetic moment in this system there is no single ion magnetocrystalline anisotropy, as in the DyFe2 sample, strongly locking the iron moments to a particular crystalline direction. The applied eld of 2.5 kOe is of the order necessary to overcome the exchange anisotropy between iron atoms, displacing the domain walls in the untrained sample producing a single domain sample. In this case the relative line intensities give a unique angle for the direction of the iron moments, recorded as 14 to the sample plane. This lies in between either the [ 241] or [ 351] directions, which make angles of 18 and 13.8 respectively to the sample plane for a sample normal direction of (110). Although the observed angle is much closer to the [ 351] direction it is also closer to the sample plane. With no
73
Figure 6.5: Spectra for 1000A YFe2 thin lm under 0 kOe and 2.5 kOe in plane applied elds.
magnetocrystalline anisotropy to overcome through coupling with the rare earth it would be expected that the iron moments would be more free to rotate in the direction of the applied eld, which is into the plane of the sample. The angle observed is one that balances the magneto-elastic and external eld energies in this sample and so is unlikely to be truly indicative of the magnetic easy axis in zero eld. Thus this result cannot be taken as absolute evidence of a [ 351] direction without other corroborating data. The iron moments would be expected to lie in plane, even under zero applied eld; the shape anisotropy favours in plane alignment, as does the applied eld. As this isnt the case the strain in the sample plane must be causing a magnetostrictive eect through the iron atoms dipolar interactions but of a much smaller magnitude than for the DyFe2 system as evidenced by the much larger change in moment alignment under applied eld. Magnetic rare earths display much stronger magnetostriction than transition elements.
74
The change in the average magnetic hyperne eld is 2.75 kG. This is slightly larger than the applied eld and signicantly larger than the change recorded in the DyFe2 sample. This is explained by the iron moments lying more parallel to the applied eld and the increased magnetisation of the sample as the separate domains rotate with the eld, increasing the magnetic eld within the sample. In the DyFe2 sample the domains were still pinned by the magnetic anisotropy of the dysprosium atoms and thus the change in magnetisation was negligible.
6.2.4
HoFe2
o As can be seen in Figure 6.3 the HoFe2 lm has a markedly dierent Mssbauer spectrum compared to YFe2 and DyFe2 . Unfortunately this may not be a pure HoFe2 spectrum as, due to the thinness of the sample layer, part of the spectrum will be recorded from the YFe2 seed layer. Using the CEMS theory outlined in Section 2.5.2 an upper limit can be placed on the relative spectral contributions from the two layers. For a 500 A sample layer the ratio of sample to seed layer is 55%:45%. Thus the spectrum is more akin to that from a HoFe2 /YFe2 bilayer. Hence we cannot analyse the spectrum to give any accurate information about a HoFe2 thin lm due to the overlap of the two sub-spectra and any possible interface eects. In the 750 DyFe2 thin lm this ratio is 85%:15% giving a more repreA sentative spectrum of the sample layer. In the YFe2 thin lm this eect does not apply as the sample and seed layer are the same material and continuous.
6.3
DyFe2/Dy Multilayers
A series of spectra from DyFe2 /Dy multilayers were obtained to investigate the eect of reduced thickness on DyFe2 thin lms between 50 and 200 . A A A limiting factor on examining such thin lms using Mssbauer spectroscopy o is that the signal to noise ratio will be far too large when there is so little iron to obtain a signal from, especially if the iron is non-enriched with the 57 Fe isotope. To counter this the signal from a number of such lms needs to be accumulated. To achieve this we used a number of DyFe2 lms in a multilayer, spaced by layers of dysprosium. Dysprosium is not magnetically ordered at room temperature, with a TN = 180 K, and provides good epitaxial growth conditions for the DyFe2 layers. The substrate, buer and seed are the same as for the previous thin lm samples.
CHAPTER 6. RFE2 LAVES PHASE THIN FILMS Sample DyFe2 (200 )/Dy(100 ) A A
5
75 Field Angle (kG) ( ) 200.0 22.6 186.0 22.6 210.0 22.6 205.0 22.6 200.1 21.4 186.5 21.4 210.5 21.4 206.0 21.4 197.5 20.6 186.4 20.6 209.0 20.6 205.0 20.6 198.0 21.1 186.0 21.1 209.0 21.1 205.0 21.1 200.0 23.3 187.4 23.3 209.0 23.3 202.2 23.3
Site 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4
DyFe2 (200 )/Dy(50 ) A A
DyFe2 (100 )/Dy(50 ) A A
DyFe2 (50 )/Dy(50 ) A A
12
DyFe2 (750 ) A
IS (mm/s) 0.12 0.11 0.10 0.10 0.11 0.08 0.11 0.10 0.12 0.07 0.10 0.10 0.12 0.09 0.09 0.09 0.12 0.10 0.11 0.08
QS (mm/s) 0.04 0.21 +0.21 +0.09 0.07 0.19 +0.21 +0.10 0.05 0.16 +0.19 +0.10 0.06 0.15 +0.19 +0.07 0.02 0.23 +0.20 +0.15
Table 6.5: Final t parameters for the DyFe2 (x A)/Dy(y ) z samples and A a 750 DyFe2 thin lm sample. The average angle is relative to the sample A plane.
The spectra are shown in Figure 6.6 and the tting parameters are given in Table 6.5. The spectra have been tted with four sextets of equal intensity, adopting a model of a low symmetry magnetic easy axis giving four inequivalent iron sites. No particular easy axis direction is assumed in the ts. The relative intensity of lines 2 and 5 to lines 1,3,4 and 6 has been xed to be equal for all four components but free to vary. All other parameters were free to vary individually. Comparison between the four dysprosium spaced samples shows little signicant variation in hyperne parameters. The isomer shift and quadrupole splitting values for all sites are identical for the four samples within a tting error of 0.05 mm/s. The average angle which the spin moments make
76
Figure 6.6: Spectra for DyFe2 (x)/Dy(y ) z , multilayers. A A
77
to the sample plane show no trend with thickness and at most vary by 2 , comparable to the nominal error on the source and sample positioning of 2 . There are small variations in the hyperne elds for particular sites but whether these are physical or artifacts of the overlapping nature of four components in a small area is hard to determine. The average hyperne eld is constant across all samples within 1 kG. The 750 DyFe2 sample was also tted with the same parameter restricA tions as the dysprosium spaced samples as a comparison with a thick lm. The results are also shown in Table 6.5. This spectrum was recorded on a dierent spectrometer to the dysprosium spaced samples so the margins of error when comparing the hyperne parameters and average moment angle are larger. Again there is no signicant variation to be seen. From these results we can conclude that the mechanisms which were present in the 750 sample are unaected by reducing the thickness of the A layer to at least 50 . A
6.4
DyFe2/YFe2 Multilayers
This section presents analysis of data from a CEMS study of DyFe2 /YFe2 multilayers. All spectra were recorded at room temperature under an in plane applied eld of 0 kOe or 0.25 kOe. The results are compared to the thin lm samples presented in Sections 6.2.2 and 6.2.3.
6.4.1
Introduction
There has been much interest recently in layered magnets34, 35 particularly those composed of a two-phase distribution of hard and soft magnetic materials. One potential application of such systems is in permanent magnets where the hard magnetic layers provide high anisotropy and coercive elds, whilst the soft magnetic layers can enhance the magnetic eld and reduce the rare earth content. These systems also have potential as GMR readheads with a reported R/R of 12% in an applied eld of 230 kOe.36 A series of DyFe2 (x )/YFe2 (y ) multilayers were investigated with varyA A ing DyFe2 and YFe2 layer thicknesses of 50 /50 , 40 /20 , 20 /40 and A A A A A A /20 . They have the same sample structure as for all the previous sam20 A A ples, shown in Figure 6.2. In these multilayers the soft magnetic YFe2 layers will be exchangecoupled to the DyFe2 layers through the strong ( 6000 kOe) iron-iron exchange coupling. This is illustrated in Figure 6.7. The strong single-ion
78
Figure 6.7: Exchange coupling between iron sublattices in DyFe2 /YFe2 multilayers.
anisotropy coupled antiferromagnetically through the dysprosium moments to the iron moments, as seen in the DyFe2 thin lm results in Section 6.2.2, will be transferred to the YFe2 layers by the strong iron-iron exchange coupling. Hence we expect the system as a whole to be dominated by the dysprosium moments. CEMS spectra were recorded at room temperature under in plane applied magnetic elds of 0 kOe and 2.5 kOe. The applied eld of 2.5 kOe will not be sucient to induce exchange springs in the YFe2 layers where the bending eld, BB , is of the order of 70 kOe,36 but there will be an exchange spring induced in the 800 YFe2 seed layer as discussed in Section 6.2.2. A
6.4.2
Results
The spectra are shown in Figure 6.8 and the tting parameters are shown in Table 6.6. The spectra have been tted with four components. Although the spectrum will be composed of subspectra from both the DyFe2 and YFe2 layers with four components each, eight components would be too many to realis-
79
Figure 6.8: Spectra for DyFe2 (x )/YFe2 (y ) z , multilayers. A A
CHAPTER 6. RFE2 LAVES PHASE THIN FILMS 0 kOe 2.5 kOe QS Field Angle IS QS Field Angle (mm/s) (kG) ( ) (mm/s) (mm/s) (kG) ( ) DyFe2 (50 )/YFe2 (50 ) 20 A A +0.15 206.1 23.0 0.10 +0.17 203.0 21.7 0.16 186.6 23.0 0.18 0.19 185.1 21.7 0.03 184.5 23.0 +0.01 0.03 183.6 21.7 +0.22 193.2 23.0 0.09 +0.09 190.2 21.7 DyFe2 (40 )/YFe2 (20 ) 16 A A +0.23 240.0 22.3 0.14 +0.25 236.8 19.6 0.21 218.6 22.3 0.27 0.13 216.6 19.6 0.06 216.1 22.3 0.00 0.06 211.6 19.6 +0.09 226.5 22.3 0.06 +0.00 223.0 19.6 DyFe2 (20 )/YFe2 (40 ) 16 A A 0.21 227.0 20.9 0.15 +0.11 227.5 17.6 0.19 214.0 20.9 0.14 0.27 205.0 17.6 0.05 214.1 20.9 0.07 0.11 210.0 17.6 +0.06 222.0 20.9 0.14 +0.04 216.0 17.6 DyFe2 (20 )/YFe2 (20 ) 25 A A +0.13 235.3 27.2 0.15 +0.20 233.0 24.3 0.25 214.7 27.2 0.15 0.14 211.9 24.3 +0.15 218.6 27.2 0.06 +0.07 213.0 24.3 +0.02 225.0 27.2 0.14 0.02 226.0 24.3
z
80
Site
IS (mm/s) 0.10 0.18 +0.02 0.10 0.14 0.23 +0.01 0.12 0.11 0.22 +0.02 0.15 0.13 0.14 0.07 0.16
1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4
Table 6.6: Fit parameters for DyFe2 (x )/YFe2 (y ) A A average angle is relative to the sample plane.
multilayers. The
tically t the spectrum. To maintain consistency with the previous results four components are used to t the spectra. The results for the DyFe2 (50 )/YFe2 (50 ) sample are consistent with A A the thin lm results in Sections 6.2.2 and 6.2.3. The average hyperne eld of 192.6 kG for the zero eld results match closely that of averaging the hyperne elds of the thin lm DyFe2 and YFe2 results, giving 190.8 kG. The small enhancement of 1.8 kG may be the onset of the hyperne eld enhancement seen in the other multilayer samples with thinner layers although slight differences in calibration and tting error could also account for this. The iron moments are 23.0 out of plane, again consistent with the values obtained
81
for all the other samples studied, where iron moments lie in the region of 20 to 25 out of plane. Under an applied eld the iron moments are forced only slightly in plane by 1.3 . This is greater than that seen in the DyFe2 thin lm where this change was 0.2 but also much less than that seen in YFe2 where the change was 10.8 . As the other results in this sample and the DyFe2 /Dy samples studied in Section 6.3 point to 50 DyFe2 layers having the same properties A thin lm the small increase in the average angle can be attributed as the 750 A to the YFe2 layers possessing an induced anisotropy through the various coupling mechanisms less than that of the dysprosium moments. Under the applied eld the average hyperne eld is reduced by 2.13 kG, consistent with that observed in the DyFe2 thin lm. Although the exact mechanism by which the hyperne elds are reduced rather than increased as expected is not currently explained (see the discussion in Section 6.2.2), we can expect that this eect would be seen in this sample as this layer thickness of 50 appears to not aect the DyFe2 layer properties. The YFe2 layer will A be strongly coupled to the DyFe2 layer and so will orient itself to the eld in the same manner, producing the same vector addition of hyperne eld and applied eld. The results for the DyFe2 (40 )/YFe2 (20 ) sample show a variation from A A the thin lm results. The hyperne elds have been enhanced by an average of 17% compared to the DyFe2 (50 )/YFe2 (50 ) sample, and 18% compared A A to the DyFe2 thin lm. The hyperne elds are reduced by an average of 3.30 kG under an applied eld of 2.5 kOe. The iron moments lie 22.3 out of plane, within the range seen for all of the Laves Phase samples studied, and are rotated by an average of 2.7 under the applied eld. The hyperne eld enhancement for the DyFe2 (20 )/YFe2 (40 ) sample A A is 14% compared to the DyFe2 (50 )/YFe2 (50 ) sample. The hyperne A A elds are reduced by an average of 4.65 kG under an applied eld of 2.5 kOe. The iron moments lie 20.9 out of plane and are rotated by an average of 3.3 under the applied eld. The DyFe2 (20 )/YFe2 (20 ) sample has a hyperne eld enhancement A A of 16% compared to the DyFe2 (50 )/YFe2 (50 ) sample. The hyperne A A elds are reduced by an average of 2.43 kG under an applied eld of 2.5 kOe. The iron moments lie 27.2 out of plane, greater than that seen for any other sample, and are rotated by an average of 2.9 under the applied eld. The biggest change in parameters with the applied eld occurs in the DyFe2 (20 )/YFe2 (40 ) sample, which has the largest proportion of soft A A magnetic material. All samples show a reduction in anisotropy compared to the DyFe2 thin lm sample, with iron moments being rotated in plane by an angle an order of magnitude greater than that for the thin lm sample.
82
A change in behaviour is occurring as the layer thicknesses are reduced below 50 . There is expected to be an interface roughness of 5 . This A A roughness becomes signicant in the thinner layers, particularly the 20 A layers where the roughness is 25% of the layer thickness. An increased out of plane moment alignment is also seen in the sample with the thinnest layers. There appears to be some form of interfacial eect occurring in the system, which becomes signicant as the layer thicknesses are reduced below 50 , A although the hyperne eld enhancement doesnt seem signicantly aected by the relative thicknesses of the DyFe2 or YFe2 layers.
Chapter 7 4f /3d and 5f /3d Magnetic Multilayers: Ce/Fe and U/Fe

Brothers stay in jealous guard Gifts to loose and render freed Hidden skill and talent barred, Save the younger of their creed. Easy nds what kin fears hard, Prot comes in more than greed. In crowd and mob of heavy men All ght stuck in seething mess, Weapons pressed too close again All actions met with no success. Lone and free to might unchain, Gains the more from giving less.
This chapter presents results on multilayers combining the eects of elements with delocalised f -shell electrons (4f in cerium, 5f in uranium) with the 3d electrons of iron. SQUID magnetometry results have been taken as a continuation of the Mssbauer spectroscopy work on Ce/Fe multilayers by o G.S. Case.3 The magnetometry data can indicate the presence and type of magnetic ordering across the layers (ferromagnetic, antiferromagnetic or uncoupled) and can then be compared with a study of GMR in these samples by A. Mohamed and M.F. Thomas.37 The data can also provide information on the magnetic moments of the samples, particularly to ascertain whether the cerium atoms possess a magnetic moment or not. CEMS spectra have been recorded at room temperature of U/Fe multilayers with various thicknesses of uranium and iron. These samples have been produced by UHV magnetron sputtering by A. Herring, Liverpool, working at the Clarendon Laboratory, Oxford University with Dr. R.C.C. Ward and Dr. M.R. Wells. The results are interpreted to provide information on the state of the iron layers: level of crystallinity, direction of the iron magnetic moments with respect to the sample plane, whether or not the iron is magnetically ordered and to detect any alloys/intermetallics or changes in 83
CHAPTER 7. RE/FE & A/FE MAGNETIC MULTILAYERS Sample Label
84
Area Ce volume Fe volume Total (mm2 ) (mm3 ) (mm3 ) (mm3 ) (104 ) (104 ) (104 ) 4.07 4.40 8.80 2.86 8.02 8.96 3.91 5.28 10.56 4.64 12.99 21.50 2.44 2.64 7.92 2.58 9.46 10.75 6.35 7.92 18.48 7.21 22.45 32.26
Ce(12 )/Fe(10 ) A A Ce(16 )/Fe(10 ) A A Ce(20 )/Fe(10 ) A A Ce(20 )/Fe(15 ) A A )/Fe(17 ) Ce(20 A A )/Fe(20 ) Ce(20 A A Ce(27 )/Fe(15 ) A A Ce(27 )/Fe(20 ) A A Ce(40 )/Fe(20 ) A A
60 60 60 60 60 60 60 60 60
12/10 16/10 20/10 20/15 20/17 20/20 27/15 27/20 40/20
Table 7.1: Sample thicknesses, areas and volumes. denotes a sample from which magnetometry data has been taken but whose area was not measured.
magnetism formed at the layer interfaces. These data are complementary to x-ray reectivity data obtained by A. Herring on the same samples.
7.1
Ce/Fe Multilayers
Multilayers containing cerium display many interesting properties,38 particularly as a result of its delocalised 4f electrons and their interactions with the 3d electrons of the transition metals. The hybridisation of the two shells is seen to induce a small magnetic moment on interface cerium atoms.39 The Ce/Fe multilayers studied in this section were fabricated by P. Boni and S. Tixier at the Laboratory for Neutron Scattering, Switzerland, using DC sputtering using a Leybold Z600 high vacuum system onto silicon substrates. These were characterised and studied using CEMS by G.S. Case,3 the results of which will be compared to the data acquired in this thesis. All of the samples studied are listed in Table 7.1, with the sample composition, label, and, where available, the sample area allowing the calculation of volumes for normalising the magnetisation to the sample size. All applied eld measurements were performed with the applied eld parallel to the plane of the sample.
CHAPTER 7. RE/FE & A/FE MAGNETIC MULTILAYERS
85
7.1.1
Temperature vs Magnetisation Scans
The variation with temperature of a samples magnetisation can give information upon the type and strength of magnetic ordering in the sample. All samples were eld cooled from room temperature to 1.8 K under an applied eld of 1000 Oe. The sample magnetisation was then measured under the same applied eld from 1.8 K to 400 K. As the sample size is not known for all of the samples the magnetisation cannot be compared quantitatively for these scans. As information can be obtained from the shape of the scans rather than the actual magnetisation the magnetisation vs temperature data has been normalised for each sample to its own magnetisation at 1.8 K. This allows groups of samples to be compared visually. Most of the datasets were obtained whilst the SQUID unit was experiencing considerable electronic noise problems. This has been reduced signicantly by smoothing the resultant data with a Gaussian convolution. Whilst the main shape of the scan becomes more visible the smoothing cannot totally remove large noise artifacts when they are over a large number of data points and so any ne structure in the scans obtained from the sample cannot be distinguished from that produced by the noise. The room temperature CEMS results obtained by G.S. Case3 show the iron to be composed of ordered bcc iron and an amount of paramagnetic amorphous iron which increases in proportion as the iron layer thickness decreases. In samples with iron layer thicknesses < 20 the amorphous/bcc A iron ratio increases and Perpendicular Magnetic Anisotropy increases, tipping the spins out of the plane of the sample. For the discussion of the magnetometry results the iron layers are taken to be ferromagnetically ordered in the iron layers, whilst the interlayer coupling can be antiferromagnetic, ferromagnetic or uncoupled depending upon the cerium layer thickness and the magnetisation of the iron layers. The results are plotted in sets for comparison, where either the cerium or iron layer thickness has been kept constant. The data is plotted as magnetisation, but as the eld, H, is constant the y-axis also corresponds to = M/H . Ce(20 )/Fe(x ) A A Figure 7.1 shows the scans for Ce(20 )/Fe(x ) multilayers. The sample A A with the thinnest iron layer, 20/10, shows either ferromagnetic or no interlayer coupling. There is a small reduction in magnetisation as the temperature increases, as expected in the ferromagnetic layers below Tc . This is illustrated in Figure 3.8(a). Although coupling will be seen in other sam-
86
Figure 7.1: Normalised magnetisation vs temperature scans )/Fe(x ) multilayers. Cerium layer thickness is constant. Ce(20 A A
for
ples with iron layers of this thickness, Mssbauer results3 show this to be o an anomalous sample, most probably because of the thinness of both the cerium and iron layers. The Mssbauer data for this sample shows iron moo ments lying 51 out of plane and with a hyperne eld 12% less than that of other samples with 10 iron layers. Hysteresis measurements also show this A anomalous behaviour (see Section 7.1.3). As the iron layer thickness is increased to 15 in the 20/15 sample we A see coupling between the iron layers. The data for this sample shows an antiferromagnetic temperature dependence around TN , as illustrated in Figure 3.7(a) (note the y-axis is 1/), with a TN = 152 10 K. The Mssbauer o data for this sample shows a 12% reduction in magnetic hyperne eld and spin moments lying 31 out of plane. This is one possible explanation for the small eect compared to the samples with thicker iron layers. The at value of M up to TN = 152 10 K corresponds to a system of
87
layers antiferromagnetically coupled and, due to small in plane anisotropy, spin opped with the antiferromagnetic axis normal to the applied eld. The M response is then due to the canting of the layer moments until their coupling to the applied eld overcomes the antiferromagnetic coupling at TN . The increase in M with temperature up to TN for the 20/17 and 20/20 samples is likely to arise from incomplete spin op of the antiferromagnetic system which allows some combination to the tot = + . At an iron layer thickness of 17 the characteristic change in tot for A an antiferromagnet is much more pronounced. The Mssbauer data show o this sample to have only a 9% reduction in hyperne eld and spin moments fully in plane. The increased in plane magnetisation in the iron layers may be giving an increased variation in tot compared to the 20/15 sample, assuming the same moment orientation. This sample has a TN = 160 5 K. As the iron layer thickness is increased further to 20 the eect becomes A stronger still. For this sample TN = 96 5 K. A larger change in between 1.8 K and TN is tending to give a lower TN , consistent with a less uniform alignment of spin moments to the eld producing a weaker coupling across the cerium layers (the 20/15 sample cannot be included in this comparison due to its undetermined moment orientation). From this set of results it can be seen that at this cerium layer thickness where the iron moments are not signicantly out of plane the coupling is antiferromagnetic. Ce(27 )/Fe(x ) A A A A Figure 7.2 shows the scans for Ce(27 )/Fe(x ) multilayers. This is another set of scans with a xed cerium layer thickness. Here, too, the coupling can be seen to be antiferromagnetic. The 27/15 sample shows a strong increase in tot with increasing temperature approaching TN , indicative of antiferromagnetic coupling with a mixture of parallel and perpendicular moment alignment. This sample has a TN = 125 5 K. Mssbauer data show this o sample to have a 20% reduction in hyperne eld and has moments lying 38 out of plane. The 27/20 also shows an antiferromagnetic coupling. The data shows a much atter curve below TN , indicating the sample has fully spin-opped moments. This sample has a TN = 145 5 K, 20 K higher than that of the 27/15 sample. At this cerium layer thickness of 27 the iron layers are coupled antiferA romagnetically.
88
Figure 7.2: Normalised magnetisation vs temperature curves for )/Fe(x ) multilayers. Cerium layer thickness is constant. Ce(27 A A
Ce(x )/Fe(10 ) A A Figure 7.3 shows the scans for Ce(x A)/Fe(10 A) multilayers. This set of . scans has a xed iron layer thickness of 10 A The 12/10 sample shows a ferromagnetic coupling between iron layers. The magnetisation slowly decreases before dropping o more sharply at a Tc = 2405 K. The magnetisation then drops linearly as for the samples with antiferromagnetically coupled iron layers in their paramagnetic region. The 16/10 sample shows an antiferromagnetic temperature dependence. The data for this sample was particularly poor so it is dicult to tell if there is an increase in approaching TN = 185 5 K or if it is merely an artifact. The data does, however, favour at least a at below TN as expected for such an antiferromagnet. The 20/10 sample, as discussed in Section 7.1.1, shows anomalous behaviour and will not be compared to the rest of the set. This set of data shows the type of interlayer coupling changing from
89
Figure 7.3: Normalised magnetisation )/Fe(10 ) multilayers. Ce(x A A
vs
temperature
scans
for
ferromagnetic at a cerium layer thickness of 12 to antiferromagnetic at A 16 . A Ce(x )/Fe(15 ) A A Figure 7.4 shows the scans for Ce(x )/Fe(15 ) multilayers. This set of A A scans has a xed iron layer thickness of 15 . A The 20/15 sample shows an antiferromagnetic coupling, with a TN = 157 5 K. The region below TN is relatively at (within equipment error), indicating moments perpendicular to the applied eld. The 27/15 sample also shows antiferromagnetic coupling, with a TN = 125 5 K, but with the temperature dependence of a mixed state of perpendicular and parallel moments. The TN for this sample is lower than that of the 20/15 sample with the more perpendicularly aligned moments. Mssbauer measurements show both samples have moments lying 32 out o
90
vs
temperature
scans
for
of plane, but the 27/15 sample has a lower hyperne eld compared to bcc iron than the 20/15 sample. The hyperne elds are reduced by 20% and 12% for the 27/15 and 20/15 samples respectively. This dierence in hyperne elds and perpendicular or parallel moment alignment does not coincide for all samples, however. It cannot be determined from these data alone whether the variation in moment alignment is due to the cerium layer thickness or merely a coincidence of the sample construction. Indeed the following Ce(x )/Fe(20 ) A A measurements show the opposite arrangement for cerium layer thicknesses of 20 and 27 . A A Ce(x )/Fe(20 ) A A Figure 7.5 shows the scans for Ce(x A)/Fe(20 A) multilayers. This set of scans has a xed iron layer thickness of 20 . A The 20/20 and 27/20 samples have already been discussed. Both samples
91
vs
temperature
scans
for
show antiferromagnetic coupling across the cerium layers. The 20/20 sample shows a mix of parallel and perpendicular moment alignment whilst the 27/20 sample shows perpendicular alignment. The 40/20 sample shows either weak ferromagnetic or no coupling of the iron layers. It shows a similar temperature dependence to the 20/10 layer, with a small decrease in magnetisation with temperature of the ferromagnetically ordered iron layers far below their TC point. The iron layers in this sample have spins at most 10 out of plane and only a 4% reduction in hyperne eld compared to bcc iron, according to the Mssbauer measurements. o This set of data shows antiferromagnetic coupling for 20 and 27 A A layers. cerium layers, and no or weak ferromagnetic coupling for 40 A
92
Figure 7.6: Percentage change in resistance under an applied eld for the Ce(20 )/Fe(17 ) 60 sample. A A
GMR Results GMR data was taken on some of the Ce/Fe samples studied in this thesis by A. Mohamed.37 All samples studied at room temperature showed no signicant change in resistance under an applied magnetic eld. One sample, Ce(20 )/Fe(17 ) 60 , was studied at 77 K and this data is A A plotted in Figure 7.6. A reduction in resistance from the zero eld state is seen as the eld is applied in the positive or negative direction. A quadratic t is included as a guide for the eye. This result is typical of the GMR eect in antiferromagnetically coupled multilayers.40 This correlates with the typical antiferromagnetic temperature dependence seen for this sample in Figure 7.1. The SQUID data shows the sample has a TN = 160 5 K, placing the 77 K GMR measurement within the antiferromagnetic region.
93
Figure 7.7: Exploded view of a Ce/Fe multilayer showing the antiferromagnetic coupling between the iron layers.
7.1.2
Estimation of Coupling Constant, J(z)
The magnetisation vs temperature scans can be used to estimate the strength of the exchange coupling between the iron layers when they are antiferromagnetically coupled. Figure 7.7 shows an exploded view of an Fe/Ce/Fe section of a multilayer in an applied eld. In this system there is an energy, WAF M , associated with the antiferromagnetic exchange coupling and an energy, WH , from the applied eld, H. These are related to the magnetisation of the iron layers by the following WAF M = 2J(z)M 1 M 2 WH = M 1 H M 2 H W = WAF M + WH
(7.1)
where M1 and M2 are the respective magnetisations of the two layers. In our systems we take the layer magnetisations to be equal, hence M1 = M2 = M . We can nd the minimum in energy with respect to the angle between the
94
Figure 7.8: Variation of antiferromagnetic coupling constant, J(z), with cerium layer thickness, z. The dashed line, representing a theoretical picture of oscillatory coupling, is added to guide the eye.
applied eld and the magnetisation, where W/ = 0. This yields the result J(z) = H 4M cos (7.2)
When the system is at TN the spins will be fully aligned with the applied eld and = 0, hence H J(z) = (7.3) 4M The magnetisation, M , can be read from the magnetisation vs temperature scans at the TN of each sample. As J(z) is a function of the distance, z, between the two iron layers we would expect the values obtained to vary with the cerium layer thickness. This is likely to be an oscillatory dependence on separation distance between the magnetic layers similar to the RKKY inter-
95
action between magnetic atoms that has been observed in many transition metal systems.41 The calculated J(z) values are plotted in Figure 7.8. The plot does show a variation with z although with so few points the actual dependence upon z cannot be calculated. The scans for the 40/20 sample appear to show either weak ferromagnetic or no coupling between the iron layers, hence it can be assumed that J(40 ) 0, showing a rapid reduction A in coupling strength with z consistent with the 1/z3 dependence of the oscillatory interaction. The ferromagnetically coupled 12/10 sample shows that J(12 ) is positive, although the magnitude cannot be determined. This too A is consistent with an oscillatory z dependence, as illustrated in Figure 5.1. This oscillatory dependence in coupling has been discussed theoretically as arising from RKKY or quantum well mechanisms. The reader is referred to References 41, 42, 43 for more detailed information. There is some verication of the results as both the 27/15 and 27/20 samples give consistent values of J within experimental error, as is expected for samples with the same non-magnetic layer thickness.
7.1.3
Hysteresis Loops
A series of hysteresis loops were taken from the Ce/Fe samples at room temperature. Only the data for those samples with known sample sizes are presented. All magnetisation results have been normalised to the total volume of the iron layers. These data are shown in Figure 7.9. The errors for the data points in each loop are shown only once for clarity. Saturation Magnetistion The room temperature hysteresis loops show the distinction between ferromagnetic, antiferromagnetic and weak ferromagnetic/uncoupled samples. The samples with a 15 iron layer thickness have the lowest volume A magnetisation. Both the 20/15 and 27/15 samples have saturation magnetisations which are consistent within experimental error, of 230 50 EMU/cm3 and 300 60 EMU/cm3 respectively This is as expected as both samples show antiferromagnetic iron layer coupling in the magnetisation vs temperature scans and have the same iron layer thickness. The 27/20 sample has a larger volume magnetisation than the samples with a 15 iron layer thickness, of 500 60 EMU/cm3 . As the layer coupling A is also antiferromagnetic in this case this is expected for a thicker magnetic layer. The 40/20 has the same iron layer thickness but has a much larger volume magnetisation than the 27/20 sample. The 40/20 sample has weakly
96
Figure 7.9: Hysteresis loops taken at room temperature for all measured Ce/Fe samples. The magnetisation is normalised relative to the iron layers volume only. The hysteresis loop for the 20/10 sample is shown truncated in the main plot for clarity, but is compared to the other loops in the inset.
ferromagnetic or uncoupled iron layers rather than the antiferromagnetically coupled layers in the 27/20 sample. The 16/10 and 20/10 samples show larger than expected magnetisations at room temperature, of 700160 EMU/cm3 and 2100500 EMU/cm3 respectively. These samples have the thinnest iron layers and so would be expected to have a lower TC than the thicker layers and hence have a lower magnetisation at room temperature. The saturation magnetisation values at room temperature reect strongly the rapidity of the decrease in M with temperature seen in Figures 7.1 to 7.5. Samples that show a relatively slow decrease in M with T , such as the 20/10 and 40/20 samples, show the greatest saturation magnetisation at room temperature.
97
The antiferromagnetically coupled samples 16/10, 20/15, 27/15 and 27/20 show much smaller saturation magnetisations at room temperature. This separation in behaviour is likely to arise from the fact that at room temperature the aligning inuence on the layers are either ferromagnetic in addition to the applied eld for ferromagnetic layers, solely from the applied eld for uncoupled layers and applied eld against antiferromagnetic alignment for the layers coupled antiferromagnetically below TN . Coercivity The temperature scans showed the 20/10 and 40/20 samples to be ferromagnetically coupled or uncoupled. Both of these samples have dierent loop shapes compared to all of the other, antiferromagnetically coupled layers. The hysteresis loops for both the 20/10 and 40/20 samples have a higher coercive eld than the coupled samples, of 154 10 Oe. The coercive eld gives the typical eld necessary to produce magnetisation reversal in the sample. Assuming a bistable system the uncoupled layers have to overcome a much larger energy gradient to change their magnetisation direction than the coupled layers. The more magnetically continuous coupled layers have a smaller gradient to overcome. The coercivity of the antiferromagnetically coupled samples seen in Figure 7.9 is exaggerated by the lack of resolution. The coercive eld for these samples is of the order of 100 Oe yet the step size in the loop is also 100 Oe. Whilst this is still less than the uncoupled layers it is most probably much smaller still.
7.2
U/Fe Multilayers
Some of the properties exhibited by Ce in multilayers can be expected in samples incorportating the Actinides, by using uranium. Uranium has some very interesting and potentially useful magnetic properties. Uranium can possess very large orbital magnetic moments which, through their coupling to the lattice, produce substantial magnetic anisotropy. This may allow perpendicular magnetic anisotropy, an important goal in magneto-optical devices. Also of interest for magneto-optical applications is the Kerr-eect, also of a large magnitude in some uranium compounds. Similar to the 4f electrons in cerium, uranium 5f electrons have a large spatial extent and can potentially hybridise with 3d electrons. These can produce polarisation eects across the multilayer interfaces, potentially of greater magnitude than in Ce/Fe multilayers.
98
In its elemental form uranium is not magnetic. When in close proximity the itinerant 5f electrons form wide bands through f -d hybridisation, producing no localised magnetic moment.44 To attain a magnetically ordered state the uranium atoms must be forced suciently apart to reduce the formation of 5f bands. Although unlikely to occur within the uranium layers of the U/Fe multilayer, interface eects such as strain or interdiusion of elements may produce magnetic uranium atoms within the immediate presence of the U/Fe interface.
7.2.1
CEMS Results
All of the 57 Fe Mssbauer results for the U/Fe multilayers were recorded using o CEMS at room temperature. Transmission mode Mssbauer spectroscopy is o prohibited by the attenuation of the Mssbauer gamma ray by the glass o substrates. The spectra were recorded with the sample plane normal to the incident gamma ray direction. The hyperne parameters from the least squares ts are given in Table 7.2. The parameters for the sextets are consistent with magnetically ordered bcc iron. In all iron layers there are two magnetic components: one having the values of crystalline bcc iron with a linewidth close to that of the calibration (indicating good crystalline growth) and hyperne elds close to those for bulk bcc iron and a second, broader component with a reduced hyperne eld. The hyperne parameters are unaected by the thickness of the uranium layer. Figure 7.10 shows four spectra, three with the same iron layer thickness but varying thicknesses of uranium. These three spectra are essentially identical in both hyperne parameters and the relative areas of each component. The fourth spectrum shows a sample with a much thicker iron layer and the relative amount of each component can be seen to have changed considerably. The rst component is attributed to a layer of crystalline bcc iron in the center of the iron layer. The linewidth is the same as a pure iron foil used for calibrating the spectrometer. The slightly reduced hyperne eld in the samples with iron layers < 60 arises from a reduction in Tc as A the strength of interactions between the iron layers is diminished by the interspacing of uranium layers and reduced coordination with neighbouring iron atoms. This eect is at its greatest in the sample with the thinnest iron layer, [U(28)/Fe(30)]31 , where there is a 3% reduction in hyperne eld. The eect decreases as the iron layer thickness is increased and the hyperne eld reaches a maximum for samples with an iron layer thickness 60 of A 329 kG, identical to that of pure bulk iron.
CHAPTER 7. RE/FE & A/FE MAGNETIC MULTILAYERS Sample U(28 )/Fe(30 ) A A IS (mm/s)
31
99 Area (%) 14 38 48 30 34 36 38 34 28 35 34 31 34 34 32 69 15 16 53 31 16
QS (mm/s) 0.05 0.02 0.71 +0.02 0.13 0.76 +0.00 0.07 0.73 +0.00 0.07 0.69 0.02 0.02 0.69 0.01 0.09 0.70 +0.00 0.12 0.89
(mm/s) 0.31 0.94 0.78 0.26 0.90 0.73 0.28 0.72 0.73 0.27 0.73 0.70 0.27 0.76 0.64 0.28 0.67 0.69 0.29 1.10 0.72
Field (kG) 320.7 288.0 0 325.3 288.0 0 328.9 304.6 0 327.8 304.0 0 328.3 300.0 0 329.0 302.0 0 328.8 299.0 0
U(28 )/Fe(43 ) A A
31
U(40 )/Fe(60 ) A A
10
U(80 )/Fe(60 ) A A
20
U(101 )/Fe(60 ) A A
20
U(42 )/Fe(113 ) A A
21
U(22 )/Fe(180 ) A A
+0.02 +0.05 0.15 +0.02 0.10 0.20 +0.01 +0.00 0.18 +0.01 +0.00 0.19 +0.02 +0.00 0.20 +0.01 0.01 0.19 +0.02 0.06 0.24
Table 7.2: Hyperne values for all U/Fe multilayers studied.
The second magnetic component has a much reduced hyperne eld of up to 13% and a very broad linewidth. This is a region of iron at the interfaces with much reduced crystallinity and subject to interface eects. Interdiusion of iron and uranium atoms, and assuming only the iron atoms carry a moment, gives fewer magnetic neighbours for each iron atom and hence a reduction in hyperne eld. The large linewidth is due to a distribution of iron sites with increasing hyperne eld as the concentration of iron atoms increases further into the iron layer. Thicker iron layers will have more pure iron sites and so the hyperne eld of the second component increases. The proportion of this region to the crystalline iron is very large in the sample with the thinnest layer (the iron layers are only just thick enough to begin
100
1.0 0.5
0.8 0.6 0.4 0.2
Percent Emission
0.6 0.4 0.2
3 2 1 0
6 5 4 3 2 1 0 1 2 Velocity (mm/s)
Figure 7.10: CEMS spectra for U/Fe multilayers: [U(40)/Fe(60)]10 , [U(80)/Fe(60)]20 , [U(101)/Fe(60)]20 and [U(42)/Fe(113)]21 . The spectra are unaected by the uranium layer thicknesses.
!
0.0
U 42 Fe 113

0.0
U 101 Fe 60
0.0
U 80 Fe 60
U 40 Fe 60
10
20
20
21
101
fully crystalline growth) but this proportion decreases with increasing iron layer thickness. This change in the proportion of crystalline iron to the distribution of magnetic iron sites is illustrated in Figure 7.11. The rst spectrum from the [U(28)/Fe(30)]31 sample shows the majority of the iron is the poorlycrystalline state or as part of the UFe2 intermetallic. As the iron thickness is increased to 43 the crystalline component can be seen to increase in A the iron layer is predominantly crystalline. intensity. At 180 A The paramagnetic doublet matches well the bulk hyperne parameters of the Laves Phase intermetallic UFe2 , with the same crystal structure as the Re/Fe2 samples studied in this thesis (Figure 6.1). The values reported in References 45 and 46 for room temperature measurements show that UFe2 is in a paramagnetic phase (Tc = 167 K) with an isomer shift of 0.21 mm/s and a quadrupole splitting of 0.45 mm/s (the sign of the quadrupole splitting is obtained from low temperature magnetically ordered spectra). The doublet has a much broader linewidth of 0.50 mm/s than that of magnetically split spectra. The broader linewidth and slightly larger quadrupole splitting observed in the UFe2 component within the U/Fe layers studied in this thesis can be explained by the decreased crystallinity compared to the bulk samples studied in Reference 45. The magnetron sputtering process may be forming UFe2 by co-evaporation at room temperature producing the formation of the intermetallic as the atoms of either element are driven into the surface of the newly formed thin lm. Other possible materials which could form such as UFe, U6 Fe and amorphous iron do not match all of the hyperne parameters consistently recorded for the doublet in all of the multilayer spectra. The current samples can only be recorded using CEMS and this restricts the readings to room temperature. Future work with samples on kapton backings will allow conrmation of the composition of the doublet as these will allow low temperature (below Tc ) measurements. Analysis of the intensity of each component can give an indication of the amount (roughly corresponding to layer thickness) of the total iron deposited which is in a particular state: crystalline iron, iron with reduced crystallinity or UFe2 intermetallic. These values are shown in Table 7.3. In the sample with the thinnest iron layer, [U(28)/Fe(30)]31 , the crystalline iron layer is very thin, only amounting to 34 monolayers (using an iron atom spacing of 2.5 . The amount of crystalline iron does not increase A linearly with the increase of iron layer thickness at rst. An increase of 13 A of crystalline iron. Similarly in the iron layer only gives an increase of 4 A the next increase of 17 in the total iron layer only gives a further 10 at A A most. Once the total iron layer is above 60 , however, the increase is more A
102
0.8 0.6 0.4 0.2
1.2 1.0
Percent Emission
0.8 0.6 0.4 0.2 0.0 0.8 0.6 0.4 0.2 0.0 10 8 6 4 2 0 2 Velocity (mm/s) 4 6 8 10
Figure 7.11: CEMS spectra for U/Fe multilayers: [U(28)/Fe(30)]31 , [U(28)/Fe(43)]31 and [U(22)/Fe(180)]5 . Increasing crystallinity is observed within the iron layers as the thickness increases.

U 22 Fe 180

0.0
U 28 Fe 43
U 28 Fe 30
31
31
CHAPTER 7. RE/FE & A/FE MAGNETIC MULTILAYERS Sample Fe Area (%) 14 30 38 35 34 69 53 Fe Layer () A 9 13 23 21 21 78 95 PM Area (%) 48 36 28 31 32 16 16 PM Layer () A 14 15 17 18 19 18 29 RC Area (%) 38 34 34 34 34 15 31 RC Layer () A 11 15 20 20 20 17 56
103
[U(28)/Fe(30)]31 [U(28)/Fe(43)]31 [U(40)/Fe(60)]10 [U(80)/Fe(60)]20 [U(101)/Fe(60)]20 [U(42)/Fe(113)]21 [U(22)/Fe(180)]5
Table 7.3: Calculated thickness of iron layers in a fully crystalline (FE), paramagnetic (PM) or reduced crystallinity (RC) state for all U/Fe samples studied.
linear. At low thicknesses the dierent iron layers appear to not be forming in a set ratio but in an equilibrium between each type of iron site. Apart from the sample with the very thickest iron layers ([U(22)/Fe(180)]5 , which will be discussed later) the amount of UFe2 and non-crystalline iron is relatively constant once there is sucient iron. Although smaller in the thinner iron layers, as there is less room for their growth, there appears to be a maximum of 18 of UFe2 and 20 for the diuse iron sites. It is A A not possible to determine from these spectra whether the UFe2 and diuse iron form one on top of the other or whether there is interdiusion of iron with both uranium and UFe2 . Normal CEMS spectra cannot give any information about the relative depths of particular iron sites and so the spectra presented so far cannot determine whether the paramagnetic doublet is from a thin layer on the surface of the sample or whether it is distributed throughout the sample thickness as in the proposed model of UFe2 forming at U/Fe interfaces. To test the model a DCEMS experiment was run on one sample, [U(28)/Fe(43)]31 , with one spectrum recorded from approximately 5 bilayers at the top of the sample, and one spectrum recorded from the remaining layers underneath. These spectra are shown in Figure 7.12. The rst conclusion to be drawn is that the paramagnetic doublet is present in both spectra with a substantial intensity. This iron site is thus distributed throughout the sample thickness and supports the model of UFe2 forming at the U/Fe interfaces. The relative intensity of the ordered iron
104
Figure 7.12: DCEMS spectra recorded from the [U(28)/Fe(43)]31 sample. Spectrum (a) is obtained from the top 5 bilayers in the sample, whilst spectrum (b) was recorded from the remaining layers underneath.
sites and the paramagnetic sites are slightly dierent in the two spectra. The ratio of UFe2 /Fe is 3:2 in the top layers and 2:3 in the lower layers. This may be due to slight dierences in growth conditions during sample growth or the central doublet in the top layers may have a small contribution from a surface iron oxide contaminant, such as FeO which is paramagnetic at room temperature.
105
The relative areas of the components in the spectrum from the sample with the thickest iron layer, [U(22)/Fe(180)]5 , give disproportionately large amounts of UFe2 and non-crystalline iron compared to the trends seen in the rest of the series. As the iron layer thickness is increased the relative areas of these two components should decrease compared to the crystalline iron. Although the iron layer is very thick the uranium layer is the thinnest of all the samples. At 22 the uranium layer is at the lower limit necessary to deposit A homogenous uranium lms and hence produce well dened layers. If the layer is not well dened this will be propagated into the iron layers deposited upon it, increasing the thickness of iron necessary to reach a state where fully crystalline growth can start. This explains the larger than expected thickness of the non-crystalline component. This badly dened uranium layer could also make it easier for iron atoms to penetrate during the sputtering process, increasing the probability of forming UFe2 . The multilayer thus consists of thick layers of crystalline iron between disproportionately large amounts of non-crystalline iron and UFe2 and inhomogenous layers of uranium. The lack of well dened interfaces is supported by specular x-ray reectivity measurements taken by A.Herring. In Figure 7.13 a reectivity scan of the [U(22)/Fe(180)]5 sample is compared with one from [U(42)/Fe(113)]21 , a sample which Mssbauer shows to have less interdiusion at the interfaces. o It can be seen that the reectivity scan from [U(42)/Fe(113)]21 has many sharp peaks. This is indicative of well dened interfaces.47 The scan from the [U(22)/Fe(180)]5 sample shows no sharp peaks, indicating either very diuse or very rough interfaces . All recorded spectra show that the iron spins are entirely within the plane of the sample, as expected from the shape anisotropy of a thin lm. There appears to be no appreciable perpendicular magnetic anisotropy of any form in the system as might be expected from the coupling of the uranium orbital moment to the lattice if it possessed a magnetic moment. It should be noted however that in the analogous Ce/Fe multilayers perpendicular magnetic anisotropy was only observed for iron layer thicknesses less than 15 .3 This A result gives no indication of there being any signicant magnetic moment on the uranium atoms at the U/Fe interfaces in the studied samples.
Specular reectivity alone cannot distinguish between roughness or diusion.47 Actinides in Laves Phase AFe2 intermetallics possess no, or very small, magnetic moments.
106
Figure 7.13: X-ray reectivity scans for a) [U(42)/Fe(113)]21 and b) [U(22)/Fe(180)]5 samples. Sharp peaks indicate well dened interfaces.
Chapter 8 Magnetic Iron Oxides

Over breathed, ever stirring, life from tired metal pry, roles juggled, never dropping, faster than the watching eye. The magnetic properties of iron oxides have had wide-ranging technological applications for many years, ranging from navigation with magnetite (or Lodestone) to modern high-density magnetic recording media and readhead devices. The two systems studied in this chapter concentrate on magnetite and maghemite (Fe3 O4 and -Fe2 O3 ). Mssbauer spectroscopy is particularly o adept at investigating these materials and obtaining information on oxidation states and sample compositions and has been used extensively for both technological and fundamental research.48 The rst section is a commercial study of the magnetite content in printer toner materials. The emphasis is on determining the ratio of magnetite to maghemite in the materials. The following section concerns the growth of thin lms of magnetite upon various substrates, using Mssbauer spectroo scopy to determine the growth quality and to conrm the growth of magnetite.
8.1
Introduction to Magnetite
Magnetite, Fe3 O4 is a member of the Spinel family of minerals, all of whose crystal structures are similar. Crystallographically magnetite takes a cubic inverse spinel form.49 The oxygen ions form a close-packed cubic lattice with the iron ions located at interstices between the oxygen ions. There are two dierent interstices that the metal ions can take, tetrahedral (A) sites and octohedral (B) sites. 107
CHAPTER 8. MAGNETIC IRON OXIDES Chemically magnetite/maghemite can be represented by the formula Fe3+ Fe2+ Fe3+ Fe3+ 1y 1y 1.67y
0.33y
108
O4
where y = 0 for pure magnetite and y = 1 for pure maghemite, and vacancies are represented by .50 Magnetite exhibits a variety of characteristics, dependent on its temperature. There are three regions of temperature where magnetite behaves dierently: 1. between 0 K and 119 K (the Verwey transition temperature, Tv ), 2. between 120 K and 840 K (the Curie temperature, Tc ), 3. above 840 K. In region 3 magnetite is paramagnetic with metallic-like conductivity. In region 2 the A sites are populated by Fe3+ ions and the B sites by Fe3+ and Fe2+ ions, with twice as many B sites populated as A sites. At these temperatures electron-hopping occurs between the B sites. This electron hopping occurs over a timescale of approximately 109 s. As the timescale of the Mssbauer event is 107 s the nuclei at each site display an average o charge state of 2.5+ during this time interval. Thus a Mssbauer spectrum o 3+ displays two distinct components: one from the Fe ions on the A sites and one from the Fe2.5+ average on the B sites. Below Tv the electron hopping process stops and the ions on the B sites have a xed charge. A Mssbauer spectrum now has three components: one o from Fe3+ ions on the A sites, one from Fe3+ ions on the B sites and one from the Fe2+ ions on the B sites.
8.2
8.2.1
Printer Toner Powders

Introduction
As part of a commercial collaboration with Laporte Pigments, Technical Center UK, we have investigated the magnetite content of printer and photocopier toners of both Laportes own materials and that of competing companies. Magnetite forms a pivotal role in laser printing technologies. The main component of toner is a resin which when heated (or forced under pressure into the paper) binds the toner to the paper. Approximately 10% of toner is the actual colourant, usually carbon. These colourants must be able to hold
CHAPTER 8. MAGNETIC IRON OXIDES
109
an electronic charge which allows them to be attracted to photoreceptors which then electrostatically transfer the toner to the charged paper. If the colourant is of a low charge it may not stick to the developer roll and so a small amount of magnetic material is added and the developer roll contains a small permanent magnet. The magnetic eld then helps hold the toner particles to the developer roll. Magnetite is the most common magnetic eld creating material used. The ability of the magnetite additive to increase the acceptance of toner onto the roll improves the reliability of the printer, reduces toner usage and the build up of machine dirt (which can have damaging eects on the printers internal mechanisms). Toners containing magnetic materials are also important components of Magnetic Ink Character Recognition (MICR) systems where characters are read directly from documents with magnetic sensors. Laporte asked us to evaluate the ratio of Fe3 O4 to Fe2 O3 in the toner samples, using spectra recorded at room temperature and 77 K.
8.2.2
Results
All of the room temperature spectra showed that the iron oxide content was not pure Fe3 O4 . In pure Fe3 O4 there is a distinctive ratio between the intensity of the two spectral components. This ratio, R, should equal 1:1.88 (A:B). In all cases for the toner samples R was greater than this. This indicated another iron oxide being present and comparison with the example spectra in Reference 50 shows this to be -Fe2 O3 (maghemite). In this case we can use the areas of the two components to calculate the Fe2+ /Fe3+ ratio and the Fe3 O4 /Fe2 O3 ratio. Taking y as the the proportion of Fe2 O3 to the whole (between 0, pure Fe3 O4 , and 1, pure Fe2 O3 ) y= N2 N1 + N2 (8.1)
where N1 is the number of Fe atoms in the Fe3 O4 compound and N2 is the number of Fe atoms in the Fe2 O3 compound. The ratio of the areas of the two components, R, can be used to calculate y from the following relation:50 1 + 0.94 5y 3 R= 0.94(2 2y)
(8.2)
where the factor of 0.94 arises from the Fe ions on the B sites having a slightly
This is not 1:2 as the recoil-free fraction of the B sites is a factor of 0.94 smaller than that of the A site.51
CHAPTER 8. MAGNETIC IRON OXIDES A-site QS Field Area IS (mm/s) (kG) % (mm/s) 0.02 494.2 60 +0.72 0.02 489.7 46 +0.66 0.01 489.0 50 +0.65 0.02 491.3 66 +0.64 0.02 492.7 63 +0.67
110 B-site QS Field Area (mm/s) (kG) % +0.02 459.4 40 +0.02 457.5 54 0.01 456.6 50 +0.01 454.1 34 +0.01 456.6 37
Sample L1 L2 C1 C2 C3
IS (mm/s) +0.35 +0.28 +0.29 +0.31 +0.30
Table 8.1: Final room temperature t parameters for all toner powder samples.
smaller recoil-free fraction.51 Once y is obtained the ratio of Fe2+ /Fe3+ is given by: F e2+ 1y = (8.3) 3+ Fe 2 + 0.67y Laporte supplied ve samples for study: two of their own (L1 and L2) and three competiting brands (C1, C2 and C3). No information was given concerning the composition of any of the samples. The room temperature Mssbauer spectra obtained from these samples are shown in Figure 8.1 and o the tting parameters in Table 8.1. Using Equations 8.2 and 8.3 the ratio of Fe2+ to Fe3+ can be calculated. These values are shown in Table 8.2. Rearranging Equation 8.1 to obtain the ratio of atoms, N1 :N2 , gives the relation N1 1y = N2 y (8.4)
the results of which are also shown in Table 8.2. The molecular ratio of Fe3 O4 to -Fe2 O3 can be obtained by multiplying the N1 :N2 ratio by a factor of 0.67, to take account of the fact that a molecule of -Fe2 O3 contains 2 Fe atoms while a molecule of Fe3 O4 contains 3. The ratio of magnetite to maghemite was thus calculated to an accuracy between 1% and 17% from these results, where higher concentrations of magnetite have a larger error. Mssbauer spectra were recorded from the same samples at 77 K. These o spectra are shown in Figure 8.2. At 77 K the samples are below the Verwey transition temperature, Tv , of 119 K. The single B site component has now become two separate components for 2+ and 3+ ions. The hyperne elds for Fe3+ A sites and Fe3+ B sites in magnetite and the Fe3+ A and B sites all lie close to each other, mean-
CHAPTER 8. MAGNETIC IRON OXIDES Sample L1 L2 C1 C2 C3 Fe3 O4 R 1.56 .05 0.84 .05 1.01 .05 1.92 .05 1.71 .05 0.53 y 0.43 .01 0.18 .03 0.26 .02 0.50 .01 0.46 .01 0 Fe2+ :Fe3+ 0.25 .01 0.39 .03 0.34 .01 0.21 .01 0.23 .01 0.50 N1 :N2 1.33 .03 4.56 .75 2.85 .20 1.00 .02 1.17 .02 NA
111
Table 8.2: Calculated Fe2+ :Fe3+ and N1 :N2 ratios for the room temperature spectra.
ing they overlap in the spectrum. This, combined with the broad linewidth of the Fe2+ B site makes these data much less reliable for accurate assessment of area ratios than the room temperature spectra. Thus the nal results were based on the room temperature ts only.
8.3
Single Crystal Fe3O4 Thin Films
In collaboration with F. Schedin, P. Morrel and G. Thornton of the Department of Chemistry in the University of Manchester, we have investigated the growth of [111] oriented magnetite thin lms using Mssbauer spectroscopy. o
8.3.1
Introduction
In recent years, high values of magnetoresistance (MR) have been obtained in ferromagnetic tunnel junctions and spin valve structures involving exchangebiasing antiferromagnetic metal oxide layers.52 In particular magnetite has been suggested as a promising material for magnetoresistive sensors because of its signicant spin polarisation at the Fermi level at room temperature. Magnetites half-metallic nature could, in principle, lead to MR tending towards innity.53 Fe2 O3 , Fe3 O4 and FeO share a common oxygen close packed plane leading to good epitaxial growth of one phase upon another along the [111] direction.54 Fe3 O4 (111) has been shown to have a sizeable magnetoresistance ( 7%) at room temperature whilst [100] orientated layers show none at this temperature.55 The study thus focusses on [111] oriented oxide layers as base layers for further epitaxial growth (eg -Fe2 O3 ). The Fe stacking sequence of Fe3 O4 in the (111) direction is comprised of alternating antiferromagnetically coupled octahedrally and tetrahedrally
CHAPTER 8. MAGNETIC IRON OXIDES Sample Fe3 O4 /Pt IS (mm/s) 0.24 0.65 0.35 0.32 0.66 0.45 0.33 QS (mm/s) 0.06 +0.00 +0.00 +0.00 +0.04 0.08 +0.89 Field Area (kG) (%) 479.8 28 450.6 62 0 10 490.2 21 451.2 79 (Fig. 8.4) 80 0 20
112
Fe3 O4 /Al2 O3 A Fe3 O4 /Al2 O3 B
Table 8.3: Best t parameters for magnetite thin lm samples. The magnetic hyperne eld for the Fe3 O4 /Al2 O3 B sample is a distribution, shown in Figure 8.4(b).
coordinated sites. Hence each layer along the (111) direction has a well dened magnetisation direction in the plane of the sample. Heteroepitaxial Fe3 O4 (111) thin lms were grown on two subtrates, Pt(111) and Al2 O3 (0001). Two dierent processes were used for deposition on Al2 O3 : A) standard sputtering source and B) using an oxygen plasma source. The oxygen plasma source gives higher quality epitaxial lms on alumina substrates.56 The three samples produced are named Fe3 O4 /Pt, Fe3 O4 /Al2 O3 A and Fe3 O4 /Al2 O3 B for samples grown on Pt(111), Al2 O3 (0001) with the oxygen plasma source and Al2 O3 (0001) with a normal source, respectively. The sample Fe3 O4 /Pt was grown, using iron enriched with the 57 Fe isotope, to a thickness of 54 . Samples Fe3 O4 /Al2 O3 A and Fe3 O4 /Al2 O3 B A were grown each with non-enriched iron to a nominal thickness of 100 . A CEMS was used to determine the magnetic hyperne interactions, moment orientation, and the growth quality of the lm.
8.3.2
Results
The CEMS t results are shown in Table 8.3 and the spectra are shown in Figures 8.3 and 8.4. The spectrum for Fe3 O4 /Pt shows good crystalline growth of magnetite. The spectrum can be tted well with three components: two magnetic sextets and one non-magnetic singlet. The two sextets show an exact match with the bulk hyperne parameters for Fe3 O4 A and B sites.57, 58 The non-magnetic singlet, with an isomer shift of 0.35 mm/s, matches exactly that for iron in a platinum matrix.7 Thus we conclude that this com-
113
ponent is obtained from iron diused into the platinum substrate. The ratio of A sites to B sites for this spectrum is 0.45:1 which is slightly less than that of bulk samples where this ratio is 0.53:1. In this system there are a limited number of layers. With A and B layers stacking one on the other it is possible that there is an uneven number of A sites, giving a smaller fraction of A sites than in an innite lattice. If B sites were formed on the upper and lower extent of the thin lm this would give a ratio of A:B of 0.45:1 for a 54 lm assuming the bulk lattice constant of 8.39 .59 A A The spectrum for the Fe3 O4 /Al2 O3 A sample also shows good crystalline growth. This spectrum requires only two components to give a good t: two magnetic sextets. The hyperne parameters for the two sextet components again are consistent with those for bulk samples. The statistics of the Fe3 O4 /Al2 O3 A spectrum are too poor to give accurate information about the relative intensity of the A and B sites: the A site linewidth needs to be xed to give a sensible result. The spectrum for the Fe3 O4 /Al2 O3 B sample is shown in Figure 8.4(a). This has been tted with two components: a distribution of magnetic sextets and a doublet. The population of hyperne elds in the distribution is shown in Figure 8.4(b). The distribution has an average isomer shift of 0.45 mm/s. This is inbetween the values for A and B site isomer shifts in magnetite and is due to the single distribution component combining both the A and B site components as would be expected in a spectrum from a more crystalline sample. The distribution population reaches a peak and then ends at 470 kG, consistent with an iron oxide, most probably magnetite as evidenced by the isomer shift value. The hyperne eld depends sensitively upon the local environment of the Mssbauer atom. A distribution of hyperne elds indicates a distribution o of inequivalent iron sites. The distribution shows that the most likely environment is that of normal, crystalline magnetite. There is also, however, a substantial area of iron at a reduced hyperne eld, showing a reduced number of magnetic neighbours or an increased spacing between them. The majority of the reduced hyperne eld component occurs between 280 kG and 380 kG. A small peak at 330 kG may indicate the presence of some metallic bcc iron. Both eects point to substantial defects in the thin lm and that the normal sputtering source is not capable of producing lms on Al2 O3 substrates of the quality necessary for MR applications. The doublet has an isomer of shift of 0.33 mm/s, indicative of an Fe3+ charge state. A possible cause is a small amount of iron pentrating into the substrate and substituting for aluminium in the Al2 O3 compound. At low concentrations in the Al2 O3 substrate the Fe3+ ions would not be mag-
114
netically ordered and at room temperature the spin-lattice relaxation times would be much shorter than the Mssbauer sensing time (see Section 2.4) o resulting in a doublet component.
115
0 2 4 6 0 5 10
L1
300 K
L2
Percent Absorption
0 2 4 6 0 1 2 3 4 0 2
C1
C2
C3
15 10 5 0 5 Velocity (mm/s)
10
15
20
Figure 8.1: Room temperature Mssbauer spectra for all toner samples. o
116
0 5
L1
77 K
0 5 10
L2
Percent Absorption
0 5
C1
0 2 4 0 1 2 3 10
C2
C3
5 0 5 Velocity (mm/s)
10
Figure 8.2: 77K Mssbauer spectra for all toner samples. o
117
Figure 8.3: Fe3 O4 thin lms on (a) platinum and (b) sapphire substrates. Sample (b) was grown using an oxygen plasma source.
118
Figure 8.4: Fe3 O4 thin lm on a sapphire substrate, grown with a standard sputtering source. (a) shows the tted spectrum and (b) shows the hyperne eld distribution.
Chapter 9 Concluding Remarks

Winding breeze, through paths will Airs contain from course and journey, Which stir the secret, resting still, Picked anew by restless air to carry, As eck, a ight in feather til... We have investigated some of the mechanisms working in nanoscale systems, particularly multilayers. The eects of strain and layer thicknesses have been observed in a number of multilayer and thin lm samples. The composition and growth quality of thin lm structures has been investigated. The room temperature CEMS results for all of the REFe2 Laves Phase samples show a low symmetry magnetic easy axis as expected from earlier studies on similar systems. The analysis of dipolar and contact hyperne elds showed the magnetic easy axis to be close to the [ 241] and [ 351] directions. Mssbauer spectroscopy on these samples appears to lack the reso olution necessary to determine the easy axis with great accuracy using this method. Persistent problems in determining angular data from these spectra have been the overlap of the components and the multidomain nature of the untrained samples. The analysis of the hyperne eld contributions is sensitive to small dierences in hyperne eld and quadrupole splitting, dierences which are smeared by the close proximity of the four components. There is ample room in the spectra for reducing the velocity range of the attenuator and thus increasing the energy resolution of the spectra. A eld trained sample, where one of the equivalent easy axis directions is preferentially populated, would allow the use of peak intensities to be used for angular information as well as peak positions. The spin moments in all REFe2 Laves Phase samples have been seen to lie out of plane in all samples by approximately 22 , indicating a signicant 119
CHAPTER 9. CONCLUDING REMARKS
120
magneto-elastic anisotropy. The use of 2.5 kOe in plane applied eld measurements indicated a much larger magnitude of magnetocrystalline anisotropy in the DyFe2 system than in the YFe2 system as expected from the large single ion anisotropy of the dysprosium moments. In the DyFe2 /YFe2 multilayer samples the anisotropy is seen to be dominated by the dysprosium single-ion anisotropy. The DyFe2 (50 )/YFe2 (50 ) A A sample shows average hyperne elds consistent with the DyFe2 and YFe2 thin lm results, whilst samples with thinner layers show an enhanced hyperne eld of up to 17%. The current data do not provide any information on the basis of this eect. Although the calibration of these spectra has been checked, sequential runs of at least some of these samples would validate the ndings of the data. More samples with thinner layers still, if possible, would investigate further this eect. The DyFe2 /Dy multilayers have shown identical zero eld properties to the DyFe2 thin lm system down to a DyFe2 thickness of 50 . Although the A results are rather uninteresting they do provide complementary information for the multilayers of two magnetic layers, helping to isolate the sources of structural eects in other samples. In all samples studied under applied eld the hyperne elds were reduced. This is expected in YFe2 where only the iron atoms possess a moment. It would be expected in all other systems containing dysprosium for the hyperne elds to increase. Sample alignment with respect to applied elds is very important in systems with signicant magnetic anisotropy and this alignment is not known and cannot be easily measured. In any future work care must be taken to record the positioning of the samples within equipment where possible. Preliminary SQUID magnetometry data were taken from these samples but the rather large YFe2 seed layer producing exchange springs and diculties in sample alignment to the applied eld precluded any further magnetometry work. Other groups have countered these problems by using samples with only a thin Fe seed layer to remove the unwanted exchange springs and Vector VSM equipment to allow precise angular positioning of the samples. Any further samples studied should therefore follow the same example, allowing magnetometry data to be taken to complement the Mssbauer data. o SQUID magnetometry results from the Ce/Fe multilayers show that most of the samples exhibit antiferromagnetic coupling, with a TN ranging between 125 K and 190 K, dependent upon both cerium and iron layer thicknesses. The poor signal to noise ratio of much of the data has made some of the interpretation dicult and prevented denite conclusions to be drawn on behaviour trends with layer thickness. A lack of sample area measurements has also prevented a full comparison of some of the data recorded. Retaking
CHAPTER 9. CONCLUDING REMARKS
121
some of the data with known sample sizes would enhance the analysis greatly. The exchange coupling constant, J(z), has been calculated for the antiferromagnetically coupled samples and shows an oscillatory z dependence. The number of data points does not allow a real comparison with theoretical predictions for exchange coupling across nonmagnetic layers, although the data so far suggest an RKKY-like z dependence. CEMS results from the U/Fe multilayers shows that each iron layer is composed of BCC iron, a poorly-crystalline iron layer with a reduced hyperne eld of up to 3% and a doublet from a paramagnetic UFe2 layer. The hyperne parameters for the paramagnetic doublet match best UFe2 but other intermetallics cannot be totally discounted. Low temperature work below TC = 167 K for UFe2 on these samples would help corroborate this nding. The relative thicknesses of the constituent layers within the U/Fe iron layer scale nonlinearly with the thickness of the deposited iron layer below 60 . Above this thickness the disordered iron and UFe2 layers reach maxiA mum thicknesses of 20 and 18 respectively. Where the uranium layer has A A poor crystalline growth this is propagated into the iron layer and increases these thicknesses. This sets a layer thickness limit on the growth of good uranium layers of 22 . A Room temperature Mssbauer spectroscopy results from a selection of o printer toner powders were used to produce the ratio of magnetite to maghemite in the powders. CEMS results on magnetite thin lms showed good crystal growth on a Pt(111) substrate, with some iron forming a non-magnetic layer diused in the platinum. The amount of iron in such sites may have been exaggerated by the substrate preparation history. Magnetite deposited on Al2 O3 (0001) substrates showed good crystal growth when using an oxygen plasma source. The statistics on the spectrum obtained from this sample are very poor, preventing any quantitative analysis of site occupancy. A longer run on this sample would be benecial, particularly as this sample is the most favourable type for technological applications. A sample produced from a normal sputtering source showed a distribution of hyperne elds and a paramagnetic contribution from iron substituting for aluminium in the substrate. This shows the benets of the oxygen plasma source for producing quality thin lms on the Al2 O3 substrate.
Appendix A Publications
Magnetic Anisotropy in Multilayers. M F Thomas, J Bland, G S Case, J A Hutchings and O Nikolov, Hyperne Interactions, 126:37786 (2000) O-Center Sn Atoms in PbSnTeSe Studied by the Mssbauer Eect. o J Bland, M F Thomas and T M Tkachenka, Hyperne Interactions, 131:6165 (2000) Temperature Dependent Mssbauer Study at Sn Sites in Some IV-VI o Semiconductors Containing O-Center Atoms. J Bland, M F Thomas and T M Tkachenka, Physica Status Solidi, 221:61724 (2000) Tin Germanate Glasses. D Holland, M E Smith, I J F Poplett, J A Johnson, M F Thomas and J Bland, Journal of Non-Crystalline Solids, 293-295:175181 (2001) Mssbauer eect study of o-centre atoms in IV-VI semiconductors. o J Bland, M F Thomas, V A Virchenko, V S Kuzmin and T M Tkachenko, Semiconductors, 35:1520 (2001) Redox processes in Sb-containing mixed oxides used in oxidation catalysis. I. Tin dioxide assisted antimony oxidation in solid state. M Calderaru, M F Thomas, J Bland and D Spranceana, Applied Catalysis A: General., 209:38390 (2001) Mssbauer study of the superspin glass transition in nanogranular Al49 Fe30 Cu21 . o J A de Toro, M A lopez de la Torre, J M Riveiro, J Bland, J P Go and M F Thomas, Physical Review B, 64:2244216 (2001)
122
APPENDIX A. PUBLICATIONS
123
Magnetic anisotropy studies in Ce/Fe and U/Fe multilayers M F Thomas, G S Case, J Bland, C A Lucas, A Herring, W G Stirling, P Boni, S Tixier, R C C Ward, M R Wells and S Langridge, Physica Status Solidi, 189:53743 (2002) A Mssbauer study of DyFe2 , YFe2 and HoFe2 thin lms and multilayo ers. J Bland, M F Thomas, M R Wells and R C C Ward, Physica Status Solidi, 189:91921 (2002) Magnetic nano granularity and spin glass behaviour in mechanically alloyed Fe35 Al50 B15 . J A de Toro, M A Lolez de la Torre, J M Riveiro, J Bland, J P Go and M F Thomas, Accepted for publication in Journal of Applied Physics Studies of Rare-Earth/Iron and Actinide/Iron multilayers. M F Thomas, G S Case, J Bland, A Herring, W G Stirling, S Tixier, P Boni, R C C Ward, M R Wells and S Langridge, Accepted for publication in Hyperne Interactions Cation Coordination in Oxychloride Glasses. J A Johnson, D Holland, J Bland, C E Johnson and M F Thomas, Submitted to Journal of Non-Crystalline Solids
Bibliography
[1] U. Gradmann. Handbook of Magnetic Materials, volume 7. [2] J.A.C. Bland and B. Heinrich, editors. Ultrathin Magnetic Structures, volume 1&2. Springer, Berlin. [3] G.S. Case. Mssbauer Spectroscopic and Structural Studies of Magnetic o Multilayers. PhD thesis, Oliver Lodge Laboratory, University of Liverpool, 2000. [4] R.L. Mssbauer. Z. Physik, 151:124, 1958. o [5] N.N. Greenwood and T.C. Gibb. Mssbauer Spectroscopy. Chapman o and Hall Ltd, London, 1971. [6] H.H. Wickman and I.J. Gruverman. Mssbauer Eect Methodology. o Plenum Press, New York, 1966. [7] J.G. Stevens and V.E. Stevens, editors. Mssbauer Eect Data Index. o IFI/Plenum, New York, 1975. [8] B.D. Cullity. Introduction to Magnetic Materials. Addison-Wesley, Massachusetts, 1972. [9] G. Bertotti. Hysteresis in Magnetism. Academic Press, San Diego, 1998. [10] S. Chikazumi and S.H. Charap. Physics of Magnetism. Krieger Publishing Company, Malabar, Florida, 1978. [11] J. Clarke. Scientic American, 271 #2:46, 1994. [12] A.C. Rose-Innes and E.H. Rhoderick. Introduction to Superconductivity, Second Edition. Pergamon Press, Oxford, 1978. [13] N.W. Ashcroft and N.D. Mermin. Solid State Physics. Holt Saunders, Japan, 1981. 124
BIBLIOGRAPHY [14] B.D. Josephson. Phys. Lett., 1:251, 1962. [15] O. Nikolov. Private Communication.
125
[16] J.G. Stevens, V.E. Stevens, and W.L. Gettys. Mssbauer Eect Refero ence and Data Journal, 3:99, 1980. [17] Quantum Design. MPMS XL Options Manual, 1999. [18] H.J.G Draaisma et al. J. Magn. Magn. Mat., 66:351, 1987. [19] L. Nel. J. Physique Radium, 15:225, 1954. e [20] M.T. Johnson et al. Rep. Prog. Phys., 59:1409, 1997. [21] K. Xia, W. Zhang, M. Lu, and H. Zhai. Phys. Rev. B, 55:125615, 1997. [22] M.A. Ruderman and C. Kittel. Phys. Rev., 96:99102, 1954. [23] A.J. Freeman. Magnetic Properties of Rare Earth Metals. [24] K.H.J Buschow. Rep. Prog. Phys., 40:11791256, 1977. [25] J.H Wernick and S Geller. Trans. Am. Inst. Min. Metall. Petrol. Engrs, 218:8668, 1960. [26] R.L. Cohen. Phys. Rev., 134:A948, 1964. [27] G.J. Bowden, D.ST.P. Bunbury, A.P. Guimar`es, and R.E. Snyder. J. a Phys. C, 1:137687, 1968. [28] E. Burzo. Solid State Communications, 14:129598, 1974. [29] V. Oderno, C. Dufour, K. Dumesnil, Ph. Bauer, Ph. Mangin, and G. Marchal. Phys. Rev. B, 54:3758, 1996. [30] A. Mougin, C. Doufour, K. Dumesnil, and Ph. Mangin. Phys. Rev. B, 52:951731, 2000. [31] G.J. Bowden et al. Physica B, 86-88:179, 1977. [32] G.J. Bowden. J. Phys. F: Metal Phys., 3:22062217, 1973. [33] G.J. Bowden, J.M.L. Beaujour, S. Gordeev, P.A.J. de Groot, B.D. Rainford, and M. Sawicki. J. Phys.: Condes. Matt., 12:933546, 2000.
BIBLIOGRAPHY
126
[34] E.E. Fullerton, J.S. Jiang, and S.D. Bader. J. Magn. Magn. Mater., 200:392, 1999. [35] J.M.D. Coey and R. Skomski. Phys. Scr., 49:315, 1993. [36] S.N. Gordeev, J.-M.L. Beaujour, G.J. Bowden, B.D. Rainford, P.A.J. de Groot, R.C.C. Ward, M.R. Wells, and A.G.M Jansen. Phys. Rev. Lett., 87:18680814, 2001. [37] A. Mohamed. M.Phys. Project. Oliver Lodge Laboratory, University of Liverpool, 2002. [38] M. Arend. Phys. Rev. B, 57:217487, 1998. [39] W. Felsch, M. Arend, M. Finazzi, O. Schutti, M. Mnzenberg, A.-M. u Dias, F. Baudlet, Ch. Giorgetti, E. Dartyge, P. Schaaf, J.-P. Kappler, and G. Krill. Phys. Rev. B, 57:217487, 1998. [40] J. Barnas and Y. Brugnesaed. Phys. Rev. B, 53:5449, 1996. [41] S.S.P. Parkin. Phys. Rev. Lett., 67:3598601, 1991. [42] M. van Schilfgaarde and W.A. Harrison. Phys. Rev. Lett., 71:38703, 1993. [43] P. Bruno and C. Chappert. Phys. Rev. Lett., 67:16025, 1991. [44] A.J. Freeman and G.H. Lander, editors. Handbook on the Physics and Chemistry of the Actinides, volume 1. North Holland, Amsterdam. [45] S. Blow. J. Phys. C, 3:83544, 1970. [46] S. Tsutsui, M. Nakada, Y. Kobayashi, S. Nasu, Y. Haga, and Y. Onuki. Hyperne Interactions, 133:1721, 2001. [47] D.Mannix. X-ray and neutron scattering studies of f-electron multilayers and single crystals. PhD thesis, Oliver Lodge Laboratory, University of Liverpool, 1998. [48] R.E. Vandenberghe and E de Grave. Mssbauer Spectroscopy Applied to o Inorganic Chemistry, 3:59182, 1989. [49] R.S. Hargrove and W. Kndig. Solid State Communications, 8:3038, u 1970.
[50] G.N. da Costa, E. de Grave, P.M.A de Bakker, and R.E. Vandenberghe. Clays and Clay Minerals, 43 #6:65668, 1995. [51] G.A. Sawatzky, F. Van der Woude, and A.H. Morrish. Phys. Rev., 183:3836, 1969. [52] C.H. Shang, G.P. Berera, and J.S. Moodera. Appl. Phys. Lett., 72:605, 1998. [53] A.M. Bratkovsky. Appl. Phys. Lett., 72:2334, 1998. [54] N.G. Condon, F.M. Leibsle, T. Parker, A.R. Lennie, D.J. Vaughan, and G. Thornton. Phys. Rev. B, 55:15885, 1997. [55] S.B. Ogale, K. Ghosh, R.P. Sharma, R.L. Greene, R. Ramesh, and T. Venkatesan. Phys. Rev. B, 57:7823, 1998. [56] Gota et al. Proceedings of the 2nd International Workshop on Oxide Surfaces, 2001. [57] E. de Grave, R.M. Persoons, R.E. Vandenberghe, and P.M.A de Bakker. Phys. Rev. B, 47:5881, 1993. [58] L. Hggstrm, H. Annersten, T. Ericsson, R Wppling, W. Karner, and a o a S. Bjarman. Hyperne Interactions, 5:20114, 1978. [59] R.W.G. Wycko. Crystal Structure, volume 3. John Wiley and Sons, New York.
127
I do not know what I may appear to the world; but to myself I seem to have been only like a boy, playing on the sea-shore, and diverting myself, in now and then nding a smoother pebble, or a prettier shell than ordinary, whilst the great ocean of truth lay all undiscovered before me. Sir Isaac Newton
128

A Mossbauer Spectroscopy and Magnetometry Study of Magnetic Multilayers and Oxides - John Bland

Enviado por

Dados do documento

Descrição original:

Título original

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

A Mossbauer Spectroscopy and Magnetometry Study of Magnetic Multilayers and Oxides - John Bland

Enviado por

Direitos autorais:

Formatos disponíveis

A Mssbauer Spectroscopy and Magnetometry o Study of Magnetic Multilayers and Oxides

John Bland, M.Phys. (Hons)

3.3 3.4 3.5

4.2 4.3 4.4

6.1 6.2 6.3 6.4 6.5 6.6

8.2 8.3 8.4

3.1 6.1 6.2

8.1 8.2 8.3

Chapter 2 Mssbauer Spectroscopy o

The Mssbauer Eect o

CHAPTER 2. MOSSBAUER SPECTROSCOPY

Figure 2.1: Recoil in a free nucleus during gamma ray emission.

CHAPTER 2. MOSSBAUER SPECTROSCOPY

CHAPTER 2. MOSSBAUER SPECTROSCOPY

CHAPTER 2. MOSSBAUER SPECTROSCOPY

CHAPTER 2. MOSSBAUER SPECTROSCOPY

CHAPTER 2. MOSSBAUER SPECTROSCOPY

Electric Quadrupole Splitting

Magnetic Hyperne Splitting

CHAPTER 2. MOSSBAUER SPECTROSCOPY

CHAPTER 2. MOSSBAUER SPECTROSCOPY

CHAPTER 2. MOSSBAUER SPECTROSCOPY

Combined Magnetic and Quadrupole Interactions

CHAPTER 2. MOSSBAUER SPECTROSCOPY

Spectrum Line Intensities

Clebsch-Gordan coecient C 2 (J) = I1 J m1 m|I2 m2

CHAPTER 2. MOSSBAUER SPECTROSCOPY

CHAPTER 2. MOSSBAUER SPECTROSCOPY

Conversion Electron Mssbauer Spectroo scopy

CEMS Decay Scheme

CHAPTER 2. MOSSBAUER SPECTROSCOPY

Figure 2.7: Decay scheme of

Fe following excitation of the 14.41 keV state.

CHAPTER 2. MOSSBAUER SPECTROSCOPY

This is often shortened to simply Magnetisation.

and and and and and

negative positive positive positive positive

Diamagnetism and Paramagnetism

Figure 3.4: The process of magnetisation in a demagnetised ferromagnet.

where is a specic temperature for a particular substance (equal to 0 for

J(J + 1)N g 2 m2 3k(T )

Figure 3.9: Superconductor enclosing a non-superconducting region.

Superconducting Quantum Interference Device (SQUID)

Figure 3.10: Superconducting quantum interference device (SQUID) as a simple magnetometer.

circulating current, i , can be obtained |i | = ic sin a 0 (3.30)

Figure 3.11: Critical measuring current, Ic , as a function of applied magnetic eld.

current, Ic from Equation 3.34 as Ic = 2ic cos a 0 (3.35)

Chapter 4 Experimental Techniques

CHAPTER 4. EXPERIMENTAL TECHNIQUES

Basic Mssbauer Spectrometer o

CHAPTER 4. EXPERIMENTAL TECHNIQUES

Figure 4.2: Mssbauer spectrometer schematic. o

CHAPTER 4. EXPERIMENTAL TECHNIQUES moves relative to the absorber and detector.

CHAPTER 4. EXPERIMENTAL TECHNIQUES

Figure 4.3: CEMS detector used at Liverpool University.

CHAPTER 4. EXPERIMENTAL TECHNIQUES

CHAPTER 4. EXPERIMENTAL TECHNIQUES

CHAPTER 4. EXPERIMENTAL TECHNIQUES

CHAPTER 4. EXPERIMENTAL TECHNIQUES

Chapter 5 Magnetic Interactions

CHAPTER 5. MAGNETIC INTERACTIONS

Interface and Volume Anisotropy