Microscopy: From Optical To TEM: Goran Dražić

1st BioTiNet Workshop: Advanced Methods for Materials Characterization 23-27 October 2011, Ljubljana-Slovenia, Hotel Slon
Microscopy: from optical to TEM

Goran Drai
Dept. Nanostructured Materials Joef Stefan Institute, Ljubljana, Slovenia
in collaboration with: Prof. Spomenka Kobe, Dr. Kristina Zuzek, Dr. Saa Novak, Ms. Tea Topliek, Prof. Marija Kosec, Prof. Boris Orel, Dr. Sreko kapin, Dr. Stanko Hocevar, Dr. Ursa Opara Krasovec, Dr. Adrian Silva (P), Dr. Botjan Janar, Dr. Zorica Cernjak Orel, Mr. Marko Bitenc, Dr. Kostas Cefalas (GR), Dr. Maja Buljan (CRO) and Ms. Medeja Gec (sample preparation)
Goran Drai AEM February 5, 2005 Chateau dOex, CH
Workshop on AEM of PZT based materials Goran Drai structural characterisation
universes
introduction strategy of microstructural investigation resolution & limits history, instrumentation, basic principles sample preparation imaging different types of contrast -> atomic resolution chemistry EDXS (quantitative, corrections) chemical homogeneity, nano precipitates, clusters
outline
structure electron diffraction (SAED, CBED, simulations) micro -> nano -> amorphous
conclusions
methods
Bulk composition (chemical & phase): classical (wet) chemical analysis ICP - inductively coupled plasma emission spectros. AA - atomic absorption XRD - X-ray diffraction EXAFS - extended X-ray analysis fine structure Neutron diffraction XRF - X-ray fluorescence NAA - Neutron activation analysis IR - infrared spectroscopy Raman spectroscopy Moessbauer spectroscopy Microscopic imaging: OM - optical microscopy SEM - scanning electron microscopy TEM - transmission electron microscopy STEM - scanning transmission electron microscopy SAM - Scanning acoustic microscopy MRI - magnetic resonance imaging XM - X-ray microscopy Electron microanalysis: EDXS - energy-dispersive X-ray spectroscopy WDS - wavelength dispersive spectroscopy EELS - electron energy-loss spectroscopy Surface methods (imaging/microanalysis): STM - scanning tunnelling microscopy AFM - atomic force microscopy XPS, ESCA - X-ray photoelectron spectroscopy AES - Auger electron spectroscopy SIMS - secondary ion mass spectroscopy UPS - ultraviolet photoelectron spectroscopy Applicable to all types of microscopy: Quantitative image analysis (Stereology) 3D imaging (tomography)
strategy of microstructural investigation

optical: CaTiO3-NdAlO3 SEM: thin PZT/LSCO/Pt/Si film
CTEM: Ni-Cr sandwich structure
HAADF low angle GB in NdFeB-Ga
analytical microscopy
techniques - methods
AEM
dedicated analytical electron microscope CTEM (conventional TEM) ED (various techniques of electron diffraction) HRTEM (high-resolution TEM) EDXS (X-ray energy dispersive spectroscopy) EELS (electron energy-loss spectroscopy) STEM (scanning transmission electron micr.) HAADF (high-angle annular dark-field detector)
Jeol 2010 F FEG TEM / STEM
electron beam/specimen interaction

light
electron microscopes
SEM
FEG-SEM
FEG-Auger
SEM/EDXS/WDS
CTEM/EDXS
FEG-TEM/EDXS/EELS
Goran Drai AEM
Workshop on structural characterisation
Resolution
Goran Drai AEM Polecer 2003 Bled, Slovenia
Workshop on structural characterisation Goran Drazi - Exploring the world of microstructure
optical microscopy
resolution limit (Abbe)
history the resolution By mid-19th century, became evident that theoretical limits of light were reached. Above magnification of 1500, resolution is lost. Image was larger, but blurred (empty magnification). In 1870, Ernst Abbe derived mathematical expression for resolution of microscope: Resolution is limited to approx. 1/2 the wavelength of illuminating source.
Blue light has a wavelength of 0.47 um Resolution max - 0.2 um (200 nm) Cannot go beyond this even with better optics.
Ernst Abbe 1840 - 1905
Solution? Use illumination of shorter wavelength
Goran Drai AEM
STED Stimulated Emission Depletion Microscopy

Stefan Hell (1994, 1999)
physical limit of the resolution
electromagnetic spectrum
Resolution
Blue light has a wavelength of 0.47 um Resolution max - 0.2 um (200 nm) Cannot go beyond this even with better optics. Solution? Use illumination of shorter wavelength
what about electrons?

(1897, J. J. Thompson)
electrons
dual nature of electrons
Louis de Broglie 1923
h = Planck's constant m = mass of an electron (9.11 X 10-28 gram ) v = velocity of the electron
electrons
wavelength of electrons
= h/[2moeV(1+eV/2moc2)]1/2
Modern TEM: Wavelength of a 200kV beam: ~3pm (0.003nm) Image resolution: ~ 1.2 Typical scattering angles: 10-3 rad
Berlin 1932
history of TEM
Ernst Ruska & Max Knoll 1932
Knoll and Ruska 1986 Nobel Prize winners
chasing resolution
1960s high voltage TEM
With a field emission source one can achieve resolutions that are in the range of 0.5
A million volt (MeV) TEM must maintain an accelerating voltage that is stable to within 0.5 volts.
resolution & penetration
extremely high voltage TEM
100 keV
200 keV
1 MeV
Hitachi 3 MeV is the most powerful TEM ever made
TEM
lens aberrations
Cc
Cs
Cs & condenser correctors
aberration free T E M
resolution ...... < ...... 1
~ 0,45
TEM
image / diffraction
TEM
image / diffraction
projection
electron microscopies
3D >>>>>> 2D
SEM surface (section)

BaTiO3 grains (polished & fractured surface)
200 nm
TEM 2D projection
dislocations in steel
OM - SEM - TEM
calcite rhombohedra
CaCO3 - calcite (R-3cH)
optical microscopy
2 m
scanning electron microsocpy
transmission electron microsocpy
Kobe, S., Drai, G., Cefalas, A., Sarantopoulou, E., Straiar, J. "Nucleation And Crystallization Of CaCO3 In Applied Magnetic Fields". Cryst. Eng.,Vol. 5, Str. 243-253, 2002
cubic CeO2 nanocrystals
3D >>>>>> 2D
cubic CeO2 nanocrystals
3D >>>>>> 2D
TEM Sample preparation
thinning
t 150 nm
TEM sample preparation
thinned TEM sample
grindign, dimpling and ion milling
sample in sample holder
TEM sample preparation powders

small particles: direct transfer to holy carbon Cu grid ultrasonic dispersion of suspension on Cu/C membrane filtration and subsequent dissolution of the filter
powders
100 nm
large particles: phenyl formaldehyde resin

CeO2 MnO2 TiO2 particles (holes in Cu/C grid)
La2RuO5 particles embedded in resin
Mn-Zn ferit
La2RuO5
TEM sample preparation bulk

ceramics: mechanical grinding, polishing, dimpling ion erosion tripod polishing FIB metals: mechanical grinding and polishing, electrolytic polishing (ion erosion) organic materials: freeze drying, embedding microtomy
grain boundaries in Si3N4
ceramics, metals, glasses
FE domains in PZT
dislocations in steel
nanocrystals in glasses
TEM image contrasts
amplitude contrast
Mass -Thickness Contrast

High-Z (i.e., high-mass) regions of a specimen scatter more electrons than low-Z regions of the same thickness. for imaging non-crystalline materials such as glass, amorphous secondary phase, tissues and polymers. Tthicker regions will scatter more electrons than thinner regions of the same average Z, all other factors being constant. In a BF image, thicker and/or higher-mass areas will appear darker than thinner and/or lower-mass areas. For DF image the contrast is reversed
bright field / dark field

BF - bright-field imaging
TEM Diffraction Contrast
CuO CeO2
CDF (central) dark-field imaging
BF
CDF
TEM
basic experiments
BF / DF
amorphous - nanocrystalline
BF ZnO nano powder
DF
KAPIN, Sreo D., DRAI, Goran, CRNJAK OREL, Zorica. Microstructure of nanoscale zinc oxide crystallites. Mater. Lett, 2007
phase contrast
coherent ilumination: plane waves with
Phase-Contrast Images
specimen introduces small, locally varying phase shift lens aberrations cause additional phase shifts
examples of HRTEM
comparison of experimental and simulated HRTEM images for new compound La2RuO3
1nm thick amorphous secondary phase between two Si3N4 grains
HRTEM
20 25
nanoclusters in CaF2 monocrystal

30 35 defocus (nm)
CaF2 in [110]
0 5 10 15 Calculated HRTEM images for ideal CaF2 structure for various defocus values at foil thickness of 10 nm 20 25 30 35 defocus (nm)
5 10 15 Calculated HRTEM images for a model structure
Examples for in-situ stages:
In situ heating experiments

Coarsening and facetting of Au nanoparticles during heating
50 nm
50 nm
50 nm
50 nm
50 nm
50 nm
50 nm
50 nm
50 nm
50 nm
50 nm
50 nm
TEM images of an Au nanoparticle on a Ce-Ti-O support with a Ce/Ti ratio of 1:1 at: (a) - room temperature, (b) - after heating at 200C, (c) - 300C, (d) - 400C, (e) - 500C, (f) - 600C, (g) - 700C, (h) - 800C, (i) - 900C, (j) - 990C after 5 min, (k) - 30 min and (l) - 60 min.
Carabineiro SAC, Silva AMT, Drai G, Figueiredo JL. In situ observation upon heating of Au nanoparticles on a Ce-Ti-O support, Catal. Today, 2011
Chemical composition
electron-specimen interaction
XEDS analysis
ionization of atoms
light
Electron trajectories:
Characteristic X-ray emission
Auger electron emission

R. Castaing, Thesis, University of Paris, ONREA Publ. #55, 1951
Quantitative XEDS
->average number of ionizations per electron
->number (intensity) of X-rays per electron Monte Carlo simulations ->thin foil: R = 1, QA f(E), el. path = t ->rearrangement
->ratio of two elements

N Avogadro number CA mass fraction (wt.%) AA atomic weight density E0 working energy Ec critical energy t - thickness QA ionization cross-section 1-R back-scattered coefficient A - fluorescent yield
Cliff - Lorimer
February 5, 2005
Goran Drai AEM
Chateau dOex, CH
Goran Drai AEM of PZT based materials
XEDS
3-grain junction (secondary phase)
geometry of analysed phases
1nm amorphous phase at sI3n4 grain boundary
normal grain
fibers, needles
c
Py phase in amorphous matrix grain boundary 2D defects isolated particle nano particles in matrix material
examples of possible geometry
XEDS
Electron beam induced damage
ZnO needle-like crystals
large fluctuations in composition
BITENC, Marko, DRAI, Goran, CRNJAK OREL, Zorica. Characterization of crystalline zinc oxide in the form of hexagonal bipods. Cryst. growth des., 2009,
Goran Drai AEM
TiO2 (rutile) coating with Al-Si-O-(OH) phase
TiO2 pigments: to improve properties: coating with different species
TEM (DF) TiO2 particles coated with an amorphous secondary phase

Center of Excellence: Nanoscience and Nanotechnology
Cinkarna Celje

spatial resolution - FEG
TiO2 (rutile) coating with Al-Si-O-(OH) phase
Al-O is preferentially bound to the TiO2 surface
HRTEM of the TiO2 / Al-Si-O inferface
Goran Drai AEM
surface of the particles
oxygen containing surface layer

surface of SiC particles is partly oxidized
EDXS spectra
HRTEM of SiC powder particle surface
DRAI, Goran, NOVAK, Saa, DANEU, Nina, MEJAK, Katja. Preparation and analytical electron microscopy of SiC continuous fiber ceramic composite. J. mater. eng. perform., 2005, vol. 14, p. 424-429
Fusion related materials
Goran Drai AEM
XEDS
chemical homogeneity
EDXS analysis
using electron beam with variuous diameters (d) 1. homogeneous composition spread of results is independent of d 2. compositional fluctuations spread of results is a function of d large d: spread in smaller small d: spread is larger
small fluctuations in composition
large fluctuations in composition
TEM - XEDS
standard deviation of measurements
counting statistics:
Tm doped CaF2
chemical homogeneity
1 +/- 0.1 wt.% 50 nm beam diameter

(nominal concentration: 1 wt. %)
for 95% accuracy at least 4x104 counts should be acquired for 2% error limit
a. b.
1 +/- 0.5 wt.% 2 nm beam diameter

(nominal concentration: 1 wt. %)
Calculated (a.) and experimental (b.) standard deviation of measurements of Tm concentration
presence of nanoclusters ?
DRAI, Goran, KOBE, Spomenka, CEFALAS, Alciviadis-Constantinos, SARANTOPOULOU, Evangelia, KOLLIA, Zoe. Observation of nanostructured cluster formation of Tm ions in CaF2 crystals. Mater. sci. eng., B, Solid-state mater. adv. technol., 2008
Diffraction
Goran Drai AEM

February 5, 2005
Chateau dOex, CH
tilting sample holder
electron diffraction
monocrystalline diffraction
The transmitted electrons will be brought to convergence in the back focal plane of the objective lens (Y). Likewise the diffracted electrons will also be brought to convergence in the back focal plane of the lens but at a different spot (X).
Crystal structure
Crystal structure
Opal photonic (colloid) crystals
Goran Drai AEM

February 5, 2005
Chateau dOex, CH
Quantum dots Ion implantation Ge / SiO2

- magnetron sputtering (SiO2/Ge // SiO2) - ion implantation (oxygen) - annealing (800 C)
Si Ge + Si < Si >
Goran Drai AEM

February 5, 2005
Chateau dOex, CH
Self assembly of quantum dots

unit cell of ordered structure
examples of (delicious) ordering
QualRef -JCrystalSoft
# h1 h2 h3 h4 h5 h6 Theta d qe qi x y z
1 1 1 2 1 1 3 1 1 4 1 1 5 1 1 ..
1 1 1 1 1
1 1 1 1 0
1 1 1 0 1 -1 0 1 0 1
16.09324 14.52949 14.62061 14.52949 3.63887
2.78115 3.07296 3.05422 3.07296 3.26944
0.35956 0.32542 0.32742 0.32542 0.30586
0.61803 0.59630 0.91059 0.59630 0.32492
0.00000 -0.03071 -0.06142 -0.09938 -0.13009
0.00000 -0.09452 -0.18903 0.00000 -0.09452
0.35956 0.30987 0.26018 0.30987 0.26018
No translational symetry. (patterns with 5, 8,10, 12 fold symetry)
Ti40Ni20Zr40
melt - spining
TEM micrographs (bright an dark field) and SAED pattern (inset) of the sample prepared with meltspinning, right - HRTEM image of the quasi-crystal grain. Inset is FFT processed central part of the image
SAED selected area ED Poblem 1.

Index SAED pattern and find crystallographic relations between <Si> and grains in textured PZT thin film.
single crystal diffraction pattern
CBED Convergent-beam Electron Diffraction
I.
II.
experimental I.
experimental II.
simulated
BITENC, Marko, DRAI, Goran, CRNJAK OREL, Zorica. Characterization of crystalline zinc oxide in the form of hexagonal bipods. Cryst. growth design, online 2009
February 5, 2005
Goran Drai AEM
Chateau dOex, CH
February 5, 2005
Goran Drai AEM
Chateau dOex, CH
50 nm
Pt large
Pt small
February 5, 2005
Goran Drai AEM
Chateau dOex, CH
From results those crystallographic relations could be concluded:
(-11-1)Au // (0001)ZnO
Beside that also close (within few degres) relations are with: (1-1-1)Au // (01-1-1)ZnO (001)Au // (0-11-1)ZnO and zone axis: [110]Au // [-2110]ZnO
February 5, 2005
Goran Drai AEM
Chateau dOex, CH
2,0 A 2,0 A (200)Au (200)Au
5,2 A 5,2 A (0001)ZnO (0001)ZnO 2,8 A 2,8 A ((--1100)ZnO 1100)ZnO
(200)Au // (-1100)ZnO ZnO is very close to one low-zone axis [-1010]

Au ZnO
February 5, 2005
Goran Drai AEM
Chateau dOex, CH
- Zn
-O
- Au
(atomic/ionic radii: Zn2+ = 0,6A, O2- = 1.4A, Au = 1,4)
February 5, 2005
Goran Drai AEM
Chateau dOex, CH

Microscopy: From Optical To TEM: Goran Dražić

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1st BioTiNet Workshop: Advanced Methods for Materials Characterization 23-27 October 2011, Ljubljana-Slovenia, Hotel Slon

Microscopy: from optical to TEM

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

strategy of microstructural investigation

CTEM: Ni-Cr sandwich structure

HAADF low angle GB in NdFeB-Ga

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

electron beam/specimen interaction

Goran Drai AEM

Workshop on structural characterisation

Goran Drai AEM Polecer 2003 Bled, Slovenia

Workshop on structural characterisation Goran Drazi - Exploring the world of microstructure

Ernst Abbe 1840 - 1905

Solution? Use illumination of shorter wavelength

Goran Drai AEM

Workshop on structural characterisation

STED Stimulated Emission Depletion Microscopy

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

physical limit of the resolution

what about electrons?

Goran Drai AEM Polecer 2003 Bled, Slovenia

Workshop on structural characterisation Goran Drazi - Exploring the world of microstructure

dual nature of electrons

Louis de Broglie 1923

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

Goran Drai AEM Polecer 2003 Bled, Slovenia

Workshop on structural characterisation Goran Drazi - Exploring the world of microstructure

Ernst Ruska & Max Knoll 1932

Knoll and Ruska 1986 Nobel Prize winners

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

1960s high voltage TEM

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

resolution & penetration

extremely high voltage TEM

Hitachi 3 MeV is the most powerful TEM ever made

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

Cs & condenser correctors

resolution ...... < ...... 1

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

SEM surface (section)

Goran Drai AEM February 5, 2005 Chateau dOex, CH

Workshop on AEM of PZT based materials Goran Drai structural characterisation

CaCO3 - calcite (R-3cH)

scanning electron microsocpy