9th MMM-Intermag,

Jan 5-9, 2004. Anaheim, California

Improved Synthesis of FePt (CoPt) Nanoparticles

Min Chen, Hao Zeng, Shouheng Sun
IBM T. J. Watson Research Center, Yorktown Heights, New York 10598, USA

In collaboration with
C. Murray, H. Hamann, G. Held (IBM Watson)
S. Raoux, M. Toney, J. Baglin, T. Thomson, B. Terris (IBM Almaden)
J. Li, Z. L. Wang (Georgia Institute of Technology)
J. P. Liu (Univ. of Texas, Arlington)
S. Wang, R. White (Stanford Univ.)
Support in part by DARPA/ARO 19-03-1-0038 and DARPA/ONR N00014-01-1-0885

¾Motivation
¾Current synthesis.
¾Improved synthesis.
¾Application potential.
FePt: Interesting bi-component materials
FePt structure is composition dependent,
Fe3Pt(fcc) FePt (fct) FePt3(fcc).

Face centered tetragonal (fct)

structure, also called L10
structure

Fct structured FePt has large anisotropy

constant, K, and is magnetically hard,
meaning smaller FePt particles can still
be ferromagnetic with large coercivity.

∆E ~KV/kT
 2 
  kB T  tP f O   3 
H C = H O ⋅ 1 −  ⋅ ln   
  U K V  ln 2  
 
- Sharrock
 FePt: High anisotropy constant

CoSm
100 FePt
CoCr15Pt12.
CoPt
CoCrxPt12
anisotropy (106erg/cc)

CoCr15Ptx
CoCr20Pt10B6
CoCrxTa4
FePt
10
CoPt
FePd
∆E ~KV/kT
Co5Sm
Co3Pt Relaxation time
Charap
τ = τ0eKV/2kT
1

0 2 4 6 8 10 12 14
2 5
MS (10 erg/cc)

D. Weller, A. Moser, IEEE Trans. Mag. 2000, 35, 4423. Ku V >> kT KuV < kT
 FePt: Interesting chemistry

The binding of Fe with Pt makes

Fe much more stable against deep
oxidation. FePt is chemically more
stable than other well-known hard
Fe Pt magnetic materials, e.g. Sm-Co &
Nd-Fe-B.
Pt Fe
Fe Pt
Surface Pt can bind to S
Pt Fe strongly to form Pt-S
bond, facilitating site
Pt Fe specific bonding of the
particles to biomolecules
for highly sensitive bio-
separation and detection.

Gu et al, Chem. Commun. 2003, 1966.

 Potential applications (3 examples)

¾Data storage media

(large Hc > 3000 Oe)

¾Permanent magnet
(Large Hc + high moment)

H H ¾Bio-separation &
N detection.

H H Mr Ms

Hc

S
H H
FePt synthesis via decomposition/reduction
CO
CO
OC Fe [Fe]
CO
CO CO
[Fe-Pt]
CH3 CH3
O O reduction
2+ [Pt]
Pt
O O
CH3 CH3 acac

Fe(CO)5 Pt(acac)2
R-NH2
R-COOH
Reduction
Fe

R-NH2 Pt

FePt

Sun et al, Science 2000, 287, 1889.

 FePt composition control
Fe
Pt
80
Fe Pt Fe

Fe Pt 70
Pt

x in FexPt(100-x)
Fe Pt Fe 60

Fe
Pt 50

40

30

0.5 1.0 1.5 2.0 2.5 3.0

mmoles of Fe(CO)5

Fe(CO)5+ Pt(acac)2 + Oleic acid + Oleylamine

? mmol 0.5 mmol 0.5 mmol 0.5 mmol

Oleic acid: CH3(CH2)7CH=CH(CH2)7-COOH

Oleyl amine: CH3(CH2)7CH=CH(CH2)7-CH2-NH2

Sun et al, IEEE Trans. Magn., 37, 1239 (2001).

Surfactant bonding to FePt surface –FTIR studies
N. Shukla, et al, J. Magn. Magn. Mater. 2003, 266, 178

O
Monodendate form
O
Fe
H2N
Pt NH2 bonds to Pt via electron donation
O
Fe C H
H
Bidendate form
O Pt N
Pt H2N R
Fe
 FePt Nanoparticle Structure

As-syn particle thin film

Fe/Pt

Annealing
Disordered FCC structure

C C CC C C C CC C C C C C Fe
CC C C C CC
CCC C C C C C C C C CC C C C C C
C
CC C C CC CC CC
CCC CCC CCC C
CC CC C CC C CC
CC C C C C C CC
C C C C C C C CC C C C CC CC C
C C C C
C CCC C C C C C C C C Pt
C
N2, 580C, 30 min
Fe70Pt30

Intensity (normalized)
Nanocrystalline thin film
Fe56Pt44
Ordered FCT intermetallic structure

Formation of fct structure depends Fe48Pt42

on annealing conditions and Fe/Pt

composition. Fe38Pt62

Sun et al, Science 2000, 287, 1889; IEEE Trans. Magn. 2001, 37, 1239. 20 30 40 50 60 70 80 90
Klemmer et al, Appl. Phys. Lett. 2002, 81, 2220. 2θ
 10000
Hc of FePt Nanoparticles Annealed FePt
N2, 580C 30 min
8000
5000 300 K Hc
4500 As-syn FePt 6000
5 K Hc

Hc (Oe)
4000
4000
3500

3000 2000
Hc (Oe)

2500

2000
0

1500 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75
1000
X in FexPt(1-x)
500
IEEE Trans. Magn., 37, 1239 (2001).
0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75

X in Fe x Pt(1-x)

500C annealed

550C annealed

Gong, et al, JAP, 84, 4403 (1998).

Weller, et al, IEEE Trans. Magn., 36, 10 (2000).
580C annealed

‰ Coercivity of FePt NPs depends on Fe/Pt composition and annealing conditions.

‰ Fe-rich Fe55Pt45 films show the largest HC in evaporated, sputtered and chemically
synthesized films.
 Current concerns
‰ It is difficult to make FePt nanoparticles larger than 4 nm, preventing
one from studying size-dependent structure transformation (from fcc to
fct) and magnetic properties. Seed-mediated growth can be used to
make bigger particles (up to 10 nm), but FePt compositions from one
size range to another varies, making direct comparison of size-
dependent properties impossible.
A: Fe, Pt order
‰ To make fully ordered fct FePt needs parameter
high temperature annealing, but this high B: (111) coherence
temperature annealing also results in length
particle sintering. He, 725C
J. Phys. Chem. B
2003, 107, 5419
===========================================================
Alternative efforts in making isolated ferromagnetic FePt particle arrays:
1) Making MFePt with M = Cu, Ag, Au to lower L10 phase formation temperature. e.g. Kang et al,
Nano Lett. 2002, 2, 1033; JAP 2003, 93, 7178. Sun et al, JAP 2003, 93, 7337.
2) By doping more organic surfactant, the array can stand up to 800C, Momose et al, Jpn. J. Appl.
Phys. 2003, 42, L1252.
===========================================================
‰ There is no known method to align magnetic easy axis of the particles
in an array.
 Size/Temperature effect on Hc – Sharrock’s law
 2  For a magnetically isolated and
  kB T  tP f O   3 
H C = H O ⋅ 1 −     random oriented particle system
⋅ ln
  KU V  ln 2   
 

¾ A larger particle is thermally

more stable than the smaller one
(KuV ~ kT).
¾ For the same value of Hc at
room temperature, larger particle
can have smaller Ku.
¾ Smaller Ku means lower
annealing temperature, thus less
aggregation problems.
 Improved synthesis

‰ Co-reduction of metal salts

= FeCl2 + Pt(acac)2 + LiBEt3H Composition control
Sun et al, J. Phys. Chem. B 2003, 107, 5419. (~4 nm FePt) LiBEt3H
FeCl2 + Pt(acac)2 FexPt(1-x)
= Fe(acac)3 + Pt(acac)2 + 1,2-C16H32(OH)2
0.5mmol 0.5mmol Fe50Pt50
Elkins et al, Nano Lett. 2003, 3, 1647. (~2 nm FePt)
0.6mmol 0.4mmol Fe60Pt40
= Fe(acac)3 + Pt(acac)2 + ethylene glycol Sun et al, J. Phys. Chem. B 2003, 107, 5419.
Jeyadevan et al, J. Appl. Phys. 2003, 93, 7547.
Direct synthesis of partially ordered fct-FePt, but needs
improvements in dispersion stability.

‰ From core/shell Pt/Fe2O3 to FePt

Coating with Fe2O3 Reductive annealing
Pt(acac)2 Pt Pt FePt

Teng et al, J. Am. Chem. Soc. 2003, 125, 14559.

Potentially a good method to prepare large FePt nanoparticles, but it needs to solve the sintering problem
under high temp (>550C) reductive annealing condition.
 Improved synthesis
- One step synthesis of larger FePt nanoparticles
CO
CO
OC Fe
CO
CO RCOO H/R-NH 2

CH 3 CH 3
O O
2+
Pt
O O
CH 3 CH 3

• No polyol reduction (to slow down FePt nuclei formation rate).

• Size control
– By adjusting concentration of oleic acid and Pt(acac)2.
– By adjusting the reaction time at 140oC.
• Shape control
– Cubic FePt nanoparticles were obtained by adding oleic acid at room temperature and
adding oleylamine immediately before the increase of temperature from 140 to 220 oC
• Composition control
– Molar ratio of Fe(CO)5/Pt(acac)2
– Molar ratio of oleic acid/oleylamine (or acidity of the solution).
 Spherical FePt nanoparticles

6 nm spherical nanoparticles 8 nm spherical nanoparticles

Cubic-like 7 nm FePt nanoparticles
 Discreet fct ordered
8 nm FePt nanoparticles

8 nm FePt, 560C 30 min, N2

 Thermally annealed 8 nm FePt assemblies
4500

4000 (111) 4000

(111)
N2, 600C 1h d ~ 8.5 nm
Lorentz fit to get β 3500

3000
3000 Almost no sintering
Scherrer’s equation

Intensity
Intensity

2500
2000 Lhkl = Kλ/βcosθ
to get (111) coherence
2000

1000
length. 1500

1000

500
0
30 40 50 60
44 46 48 50 52
2θ
2θ

16000
14000
(111)
12000 N2, 700C 1h 12000 (111)
d ~ 32 nm
to get β
Lorentz fit10000 sintering
Intensity

8000
8000
Intensity

Scherrer’s equation
Lhkl = Kλ/βcos θ
6000
4000
to get (111) coherence
4000

length. 2000
0

0
30 40 50 60

2θ 46 47 48 49 50

2θ
 Improved synthesis
- Core/shell nanoparticles
Fe(CO)5, air
Pt(acac)2 + Fe(CO)5 ------ FePt ------------- FePt/Fe2O3

6 nm FePt core 7 nm FePt core

with 1.2 nm Fe2O3 shell with 1.2 nm Fe2O3 shell
 Anti-sintering effect of the Fe2O3 shell
FePt/Fe2O3 (7nm/1.2nm) FePt (7nm)

w1/2 peak: 1.01883 10000

2000
Size: 10 nm w1/2 peak: 0.77231 48.1
8000
Intensity

Size: 13.0 nm

Intensity
1000 6000

4000
55.4
0 2000 27.9 38.3
57.7
25 30 35 40 45 50 55 60
Co Kα 2 θ (°) 0
25 30 35 40 45 50 55 60
2000 10000
original 48
Lorentz fit 8000 Original
Lorentz fit

Intensity
Intensity

6000
1000
4000

2000

0 0
45 46 47 48 49 50 51 46 47 48 kα 2θ (°) 49
Co 50
Co Kα 2 θ (°) X Axis Title

Annealing under N2 at 650 oC for 1 hour. Annealing under N2 at 600 oC for 1 hour.
Fct FePt grain size is about 10 nm, no Fct FePt grain size is increased to ~13 nm.
obvious sintering.
 Hc of annealed FePt/Fe2O3 nanoparticles
(Moment is not normalized)

0.040

Annealed under forming

Magnetic Moment (emu) 0.020 gas at 650C for 1h, Hc
~11 kOe.

0.000

Annealed under N2 at
650C for 1h, Hc ~16
-0.020 kOe.

-0.040
-40000 -20000 0 20000 40000
Magnetic Field (Oe)

Important conclusion: Nanoparticles annealed under N2 show less

degree of aggregation and large coercivity. They can be used to study
single particle magnetism.
 CoPt nanoparticles
Co(acac)3 + Pt(acac)2 + Polyol/Hydrazine

4 nm CoPt nanoparticles 5 nm CoPt nanoparticles

 Effect of composition and annealing
temperature on coercivity

Hc (at 675 oC)

Hc (Fe at.%=45.7)

20000 20000

15000 15000
Coercivity (Oe)

Coercivity (Oe)
10000 10000

5000 5000

0 0
20 30 40 50 60 70 580 600 620 640 660 680 700 720
Fe at. % in FePt Annealing Tem perature (o)

Optimum composition is Co:Pt=1:1 Optimum annealing temperature

(under N2 gas) is 675 oC
Hysteresis loop of CoPt nanoparticles

0.05

0.03
Magnetic Moment (emu)

0.00

-0.03

-0.05
-60000 -30000 0 30000 60000
Magnetic Field (Oe)

CoPt (Co:Pt=49.7%:50.3%) nanoparticle assembly

annealed under N2 at 675 oC for 1 hr.
Hc=16950 Oe
 Next step: Control magnetic easy axis direction

One method:
‰ Directly synthesizing fct-FePt
nanoparticle dispersion
‰ Assembling these particles under a
magnetic field.
Add H field
H-Loop of Co Particle Assembly at 300K Solvent evaporation
The particles were deposited on SiO2/Si under in-plane field of 0.5T

-5
8.0x10
-5
1.5x10

in-plane loop out-of-plane loop

-5
6.0x10

-5
1.0x10
M (emu)

-5
M (emu)

4.0x10

-6
5.0x10
-5
2.0x10

0.0 0.0

-150 -100 -50 0 50 100 150 -150 -100 -50 0 50 100 150
H-Field (Oe) H-Field (Oe)
Next step: Control magnetic easy axis direction

Alternative methods:
1) Magnetic annealing.
2) Shape controlled
assembly

Cobalt nanoparticles

annealing
under H (??)

BaCrO4 nanorods
Kim et al, J. Am. Chem. Soc. 2001, 123, 4360.

Shape induced alignment seems to be more promising.

 FePt NP array for ultra-high density data storage

SA film, ~ 120 nm thick

4 500 fc/mm
2
0 Key challenges:
-2
-4 ¾To have an exchange-decoupled
MR signal [mV]

-6 array.
-8
-10
¾To have a uniform 2D assembly.
-12
-14
¾To control magnetic easy axis
-16
-18 direction.
5000 fc/mm
-20
0 5 10 15 20 25
x [µm] Weller & Moser, IEEE Trans. Magn. 2000, 35, 4423.
Sun et al, Science 2000, 287, 1989.
 Exchange-spring nanocomposites
for high density magnetic energy storage

Soft Hard Soft ¾An exchange-spring composite contains

H
Illustration of a modulated hard-
soft exchange-coupled system
two modulated phases that are in intimate
contact with one being magnetically hard
and another magnetically soft.
¾The system can store high density
magnetic energy because it has both large
coercivity and high magnetic moment.
¾The key for high performance composites:
The size of the soft phase is at ~<10nm;
Magnetic easy axis is aligned.

H H Phys. Rev. B, 48, 15812 (1993).
Magnetic hysteresis loops for a non-
exchange coupled system (top) and
an exchange-coupled system
(bottom).
H H
N ‰Kneller, E. F., Hawig, R. IEEE
Trans. Magn., 27, 3588 (1991).
‰ Skomski, R., Coey, J. M. D.
‰ Schrefl, T., Kronmüller, H.,
Fidler, J. J. Magn. Mag. Mater.,
S 127, L273 (1993).
H H
 Isotropic nanocomposites
10
(A) Fe58Pt42
8 (B) FePt:Fe3Pt

6 (BH)max ~
20.1 MGOe

B (kG)
0.4 4 nm:4 nm
4
(160 kJ/m3)
0.2 (BH)max~
m (arb. unit)

2
0.0 14.7 MGOe
0 (117 kJ/m3)
-0.2
-0.4 -2
A
-8 -6 -4 -2 0
-60 -40 -20 0 20 40 60 H (kOe)
H (kOe) 12
0.2 Ms = 1050 emu/cc
4 nm:8 nm 10
0.1 Hc = 2.4 T
m (arb.unit)

8 (BH)max ~24 MGOe

0.0 (191 kJ/m3)

B (kG)
6
-0.1
4

-0.2 B
2
-60 -40 -20 0 20 40 60
H (kOe) 0

H-loops for the FePt-Fe3Pt composites -10 -8 -6 -4 -2 0

made from self assembly and reductive
annealing of 4nm-4nm and 4nm-8nm
FePt-Fe3O4 binary nanoparticles.
Zeng et al, Nature 2002, 420, 395.
H (kOe)
(BH)max, energy product, reflects the ability
for a composite to store magnetic energy, the
larger the better.
Conclusion remarks
1) There are a lot rooms for improvements in FePt (CoPt)
synthesis.
2) Large FePt (CoPt) nanoparticles can be made by one-step
chemical synthesis.
3) Core/shell structure with hard inorganic shell may be
necessary for anti-sintering during high temperature
annealing (an alternative anti-sintering route is via doping
more organic surfactant into the assembly), and rod-
shaped particles may induce much needed magnetic easy
axis alignment.
4) The particle assemblies with controlled interparticle
interactions and magnetic easy axis direction should have
great potential for future ultra-high density information
storage applications. (For bio-magnetic applications, see
FB-03 & FB-07.)
 60 ⋅ k B ⋅ T 3
Minimal Stable Grain Diameter DP =
K
alloy material K: Ms: Hk: Dp:
system anisotropy saturation anisotropy minimal
in 1e7 magnetizati field in stable
erg/cc on in kOe diameter
emu/cc in nm

CoCrPtX 0.20 200-300 15-20 8-10

Co-alloys Co 0.45 1400 6.4 8
hex Co3Pt 2.0 1100 36 4.8

FePd 1.8 1100 33 5.0

L10 FePt 6.6-10 1140 116 2.8-3.3
phases
CoPt 4.9 800 123 3.6
MnAl 1.7 560 69 5.1

RE-TM Nd2Fe14B 4.6 1270 73 3.7

Co5Sm 11-20 910 240-400 2.2-2.7

See e.g. D. Weller and A. Moser, IEEE Trans. Magn.35, 4423(1999)

 Nanocomposite High Ku Materials

SmCo//Cr Lambeth (1991);Liu et al.(1995)

PrCo//Cr Malhotra et al.(1996)
am. CoSm Kubota, Marinero, Toney (1999)

FePt:ZrOx Coffey et al. (1995)

CoPt:SiO2 Ichihara et al. (1998)
FePt:B Li, Lairson, Kwon (1999)
CoPt:M (Ag, C) Stavroyiannis et al.(1998)
CoPt:C Yu, Liu, Sellmyer (1999)
Fe/Pt/Al2O3 Bian, Laughlin... (1999)

FePt:C Sun, Murray, Weller, Moser, Folks (2000)

 Formation of ordered L1o-FePt phase
HRTEM image of Fourier transform of
an individual the corresponding
Fe52Pt48 HRTEM image
nanocrystal after
annealing at 530
°C for 1 hour Simulated electron
diffraction pattern

Enlarged HRTEM Corresponding

image of the simulated HRTEM
chemically image
ordered L1o-FePt
structure

Dai, Sun, Wang,

NanoLett., 1, 443 (2001).
 1.0
650 C 5 min N2 Remanence curves of
700 C 60 min FG
self-assembled Fe58Pt42
0.5
nanoparticles annealed
at different conditions.
m (a.u.)

0.0

-0.5 1.0

700 C 60 min FG
-1.0 600 C 60 min FG
550 C 60 min FG
-70 -60 -50 -40 -30 -20 -10 0

H (kOe) 0.5

δM
δM plots for self-assembled
Fe58Pt42 nanoparticles
annealed at different 0.0
conditions
0 5 10 15 20 25 30 35 40 45 50

H (kOe)
H. Zeng et al, APL, 80, 2583(2002)
 Hc=4.6 kOe

0.05
0.04 Thin film magnetics
Polar Kerr angle (deg)

0.03
0.02
0.01
0
-20 -10 -0.01 0 10 20
-0.02 300 K
-0.03 10 K
-0.04
-0.05
H (kOe)

Kerr, 3 layers, 4nm particles

580C, 30min, N2
Hc=2.4 kOe

0.02
0.015
Polar Kerr angle (deg)

0.01
0.005
0
-20 -10 -40 -30 -20 -10 0
-0.005 0 10 20

-0.01 H (KOe)
-0.015
-0.02
Remanence Curves
H (kOe)
2 layers, 4 nm Fe58Pt42 particles
Kerr, 2 layers, 4nm particles 650C, 5 min, N2.
580C 30 min, N2
 Magnetic recording on
3 Layer 4nm FePt Nanoparticles

Computer V I First static read/write test

on 3 layer thick sample
(low density of 650 fc/mm)

Servo
Electronics
Slider
>

Sample

> X-Y Piezo Scanning Stage

to piezos

Static read/write tester by A. Moser S. Anders

 Polymer Assisted Layer-by-Layer Assembly
- Assembly Thickness Control

Sun, et al, J. Am. Chem. Soc., 124, 2884 (2002)

Mass density of a 3-layer FePt

assembly from X-ray reflectivity.

Mike Toney, IBM Almaden

 Nanoparticle Media Perspective
Lubricant
Carbon
Co-alloy
CrV
NiAl

glass substrate

35 Gbit/in2 Media >100 Gbit/in2 Terabit/in2 Regime

Grains: ~ 9 nm Co-M Grains: ~4 nm FePt Grains: < 5 nm FePt
Hc 3000-5000 Oe Each dot as a bit
Thickness < 10 nm ……
……