me 598 - lecture 1 - overview of materials characterization...

7/23/2019 Me 598 - Lecture 1 - Overview of Materials Characterization Techniques.20110215.4d5ad7e0f3d0e6.28002081

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Lecture 1:

Overview of materials characterization:the need for complementary techniques

Ivan Petrov

[email protected]

1January 18, 2011


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Nanotechnology/Nanoscience

Nanotechnology is the study of manipulating matter on an atomic

and molecular scale.

Nanostructures - sizes 1 to 100 nanometer in at least one dimension.

Nanoscience the knowledge base of nanotechnology:understanding, measuring, predicting, designing properties of

.

1 nm equals ~ 5 atomic diameters.

1 nm3 contains ~ 125 atoms. 98 are surface

atoms and 27 are in the bulk.

Surfaces and uantum effect determine new

properties.

DNA double-helix diameter ~ 2 nm

2

Nano- Biotechnology converge

M.F. Crommie, C.P. Lutz, D.M. Eigler, E.J. Heller.Waves on a metal surface and quantum corrals.

Surface Review and Letters 2 (1), 127-137 (1995).


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Nanotechnology

Two major approaches:

Bottom-up" approach: synthesis of molecules and structureswith controlled shape and functionality that self-assemble

Top-down" approach: nano-objects are constructed using

tools for exam le litho ra h or scannin robe microsco

3


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This course

, van e rov arac er za on ec n ques, nc u ng e ec ron

microscopy, scanning probe microscopy (specifically AFM), spectroscopy,FIB, X-ray diffraction. Fundamentals of thin film growth.

MNMS cleanroom, Bruce Flachsbart : This section will concentrate on

other aspects of processes, emerging process and recipe development, , .

MNTL, Rashid Bashir and colleagues: The concentration here will be on

cr stal rowth, ALD, e-beam litho ra h , im rint litho ra h , and bioMEMS

processing and technology.

4


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Week 1Tuesday January 18th 12:30 to 1:50pm, Ivan Petrov Overview Nanocharacterization

Thursday, January 20th 9 to 11:50am Ivan Petrov MRL tour

Thursday, January 20th 12:30 to 1:50pm Scott MacLaren, Scanning probes

Week 2

Tuesday January 25th 12:30 to 1:50pm Jim Mabon, Scanning Electron Miccroscopy/Focused

Ion BeamThursday, January 27th 9 to 11:50am MacLaren AFM, Mabon SEM

Thursday, January 27th 12:30 to 1:50pm Rick Haasch X-ray photoelectron and Auger electron

spectroscopy

Week 3

Tuesday, February 1

st

12:30 to 1:50pm, Tim Spila, Secondary ion mass spectrometry andRutherford backscattering spectroscopy

Thursday, February 3rd 9 to 11:50am Haasch and Spila XPS SIMS

Thursday, February 3rd 12:30 to 1:50pm Julio Soares Optical spectroscopies

Week 4

Tuesday, February 8th 12:30 to 1:50pm Mauro Sardela X-ray diffraction

Thursday, February 10th 9 to 11:50am Soares, Sardela Thursday, February 10th 12:30 to 1:50pm Ivan Petrov Thin Film Growth

Week 5

Tuesday, February 15th 12:30 to 1:50pm Ivan Petrov Thin Film Growth

5

Thursday, February 17th 9 to 11:50am Bharat, Tao evaporation, sputtering

Thursday, February 17th 12:30 to 1:50pm Jianguo Wen Transmission electron microscopy


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Why materials analysis?

needed: In order to understand/control the s nthesis rocesses

In order to understand why materials, micro-, and

nanosystems and devices work or fail

Understand

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Main questions to answer

1. What are the building blocks elemental and

2. What is the arrangement of the building blocks

3. What is the electronic structure

4. What are the surface mor holo and bulk

nanostructure imaging from micron to sub-

nanometer scale

7


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Wide variety of methods for materials analysis

Ions Ions

Primary beam

(source, gun)Secondary beam

(spectrometers, detectors)

ElectronsPhotons

ElectronsPhotons

* with ions and electrons: the sample is in vacuum

** exception: scanning probe microscopy


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9

http://www.eaglabs.com/


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FSMRL Center for Microanalysis of Materials

ompre ens ve se o ec n ques rom rou ne o mos a vance

24 h access to qualified users

Staff 14 scientists and engineers for > 40 major instruments

. ur ace na ys s

Cameca IMS 5f SIMSPHI 660 AugerPHI 5400 XPSSmall-spot imaging XPSPHI TOF-SIMS 2003

. ransm ss on ec ron croscopy

Philips CM12JEOL 2010 F STEM/TEMJEOL 2011 TEMIBM Low-Energy Electron MicroscopyJEOL 2100 Cryo (2006)

Van de Graaff for ion beam analysis

6. Laser and Optical SpectroscopiesRaman spectroscopy/

PhotoluminescenceS ectro hotometr /FTIR

JEOL 2200FSTEM/STEM (2008)

2. Scanning Electron MicroscopySEM/Focused ion-beam microscopy

Hitachi S-4700, SEM S-4800 (2008)JEOL 6060 low-vacuum SEM(2004)Pump/probe spectroscopySum frequency generationEllipsometryNear-Field Scanning Optical MicroscopySolar cell efficiency (2010)Solar spectrum simulator (2010)

ana yt ca

3. Scanning Probe MicroscopyDigital Instruments AFM

Advanced Asylum Research AFM (2) (2005)Asylum Research Cypher (2010)

a vern nstruments etas zerContact Angle Goniometers (2010)Ultrafast Confocal microscope (2011)MicroRaman (2011)

7. Property Measurement

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4. X-ray ScatteringPhilips X'pert: high-resolution, reciprocal mapsPhilips X'pert: powder, pole figuresRigaku D-Max: powder

10

erent a scan. ca or metry ermogr. ana ys sHysitron TI 950 Triboindenter (2010)Hysitron Picoindenter (2010)

Quantum Design MPMS (2011)Quantum Design PPMS (2011)

-Anton Paar DHS900 hot stage (2010)Energy Dispersive X-Ray Fluorescence


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A comprehensive characterization approach

interaction with ANL:

High-power lithium-ion battery failure mechanisms

6000

7000

8000

graphite

-(CF2-CH2)n--(CF2-CH2)n-

-(CH2)n-

-C-O-

-OCO2-

XPS, C1s spectrumPositive electrode

50C, 60% SOC, 16 wk test

-C=O

Imaging Spectroscopy (XPS) Elemental analysisFresh

0.5 m

Aged

3000

4000

5000

6000

7000

8000 LiF

-(CF2-CH2)n-

XPS, F1s spectrum50C, 60% SOC, 16 wk test

0

1000

2000

3000

4000

5000

2 82 2 83 2 84 2 85 2 86 2 87 2 88 2 89 2 90 2 91 2 92 2 93 2 94

Binding Energy, eV

-O-C=O

C Li

0.5 m 01000

2000

682 683 684 685 686 687 688 689 690 691 692

Binding energy, eV

0.00

0.01

0.02

Bulk O K-edge

HRTEM, Crystallography, and EELS(003)

-structure

refinement

Ni All

530 535 540 545 550 555 560 565 570 575 580 585 590eV

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

m

0.00

0.02

Bulk

Ni L-edge

Particle Surface

(006)(113)

(110)

(018)

(107)(015)

(012)

(101)

C(002)

Intensity(a.u.)

11

20 nm

850 860 870 880 890 900 910eV

0.04

0.06

0.08

0.10

m

2-theta (o)


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8 monolayers AuPd


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40 monolayers AuPd


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8 monolayers AuPd


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40 monolayers AuPd


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8 ML 40 ML

2 nm


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Ions Ions

Primary beam

(source, gun)Secondary beam

(spectrometers, detectors)

ElectronsPhotons ElectronsPhotons

* with ions and electrons: the sample is in vacuum

** exception: scanning probe microscopy


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Scattering cross section one target atom

nbeam[beam particles cm-3]

Beam Flux: Jbeam= nbeamv[beam particles cm-2s-1]

vbeam particle velocity

vt= r2

Nevents= nbeamV = nbeamvt = Jbeamt

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= Nevents_per-seccond/Jbeam


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Scattering cross section many target atoms

Nevents-per-second= JbeamNtarget

=Nevents-per-second

JbeamNtar et

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Scattering cross section binary target

Detector

Igreen = Tinstr*Nevents-per-second= JbeamT

instrgrNgrgr gr

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Iorange = Tns r*Nevents-per-second= Jbeam T

ns rorNoror or


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Mean free path

= r2

vt V = vt

= n V = n t

Traveled distance vt

= Number of events = ntargetvt

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= 1/ ntarget (cm/events)


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Scattering cross-section -

probability that a scattering process occurs

beam target v

N number of events of certain type per sec (elastic, inner shell ionization, etc)

beam

ntarget target atom density (atoms/cm3)

mean free path

= 1/ ntar et (cm/events)

If several different scattering processes can occur (i)

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total i


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X-ray scattering

X-ray/Matter InteractionsCoherent

scatteringh0

h0

Fluorescence

Incoherent

scatteringIncident x-ray photons XRD

XRF

1h2 Photoelectron

Auger electrone-

e- XPS

Coherent scattering (Thompson scattering / diffraction):

50 m 5 cm

m

Sample

volumeh: photone-: electron

incident photon ho interacts with e- with no energy loss and no phase change

Incoherent scattering (Compton scattering): (a) e- absorbes incident energy ho (excited photoelectron);(b) part of the energy is emitted at different energy h1 and different phase.

- - - o cascade down filling the holes causing secondary photons emission (h2).

Photoelectron emission:

h0 energy is used to eject electron e- with kinetic energy = ho B.E.(binding energy).

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Auger electron emission:

(a) incident h0 used to eject e- from atom; (b) 2nd e- falls to lower levels to fill the holeand a photon isemitted; (c) the emitted photon is absorbed by valance e-, which ionizes and leaves the atom.


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Electron-Beam/Matter Interactions

Incident

BeamUV/Visible/IR

LightEDS/WDSEDS/WDS

CLCLBackscattered

electrons (BSE)

SecondaryCharacteristicX-rays Augerelectrons ImagingImaging

X-rays

Elastic Scattering

Heat

Inelastic Scattering

Micron-size Interaction Volume

Specimen CurrentImagingImaging

Is c

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Is c Ib Ib Ib Ib 1


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Ion-Beam/Matter Interactions

Inelastic Effects

Ion beam with an energy

Ei+

IElastic EffectsSIMS

depth profile

UV/visible photonsSputtered Particles

T0, T*, Tn T+, I+

T-, I-

(+)(-) Ions(AES,XPS)

X-rays

Secondary

ElectronsReflected Particles, I0

,I

*

RBS,ERD

Implanted Particles Target

25Figure after G.M. McCracken, Rep. Prog Phys. 28, 241 (1975).


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Beam particles properties

0.0122

26


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. at are t e u ng oc s e ementa an c em caanalysis

crystallographic analysis3. What is the electronic structure

4. What are the surface morphology and bulk nanostructure

imaging from micron to sub-nanometer scale

using

elastic (coherent) electron and x-ray scatteringdiffraction analysis (reciprocal space mapping)

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Coherent diffraction by a crystal

plane normal1 1

Plane wave(x-ray or electron)

2 2

i Kd

= oe2x/

B

dKi

K= oe x

b definition wave vector K = 1/

C

n sinragg s aw:,

scattering vector: |K|/2 = |Kd| sin

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|K|= 2sin/ = 1/d


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Fundaments of diffractionReal space Reciprocal spaceF

d

1/d

origin

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Fundaments of diffractionReal space Reciprocal spaceF

origin

30


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Real and reciprocal space

001 zone axis 011 zone axis 111 zone axis

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TEM


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Real and reciprocal space in TEMTEM

Sam le

Incident Electrons

< 500 nm

Objective Lens

d

Back Focal Plane

First Image Plane

Reciprocal space image

Real space imageBraggs Law2 d sin = n|K|= 2sin/= 1/d

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JG WEN


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. a are e u ng oc s e emen a anchemical analysis

.

crystallographic analysis3. What is the electronic structure


imaging from micron to sub-nanometer scale

using

inelastic electron and x-ray scattering

(ionization and relaxation processes)

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Inelastic scattering of x-rays and electrons

Ionization XPS and EELS

Relaxation Auger electron spectroscopy and characteristic x-rays (EDS, WDS, XRF)

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Elemental analysis by inelastic processes

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photoelectrons characteristic x-rays Auger electrons

40

50 3s3p3d4s4p

30

A

to

m

ic

N

u

m

b

er

2s

2p

10

20

1s

0

0 200 400 600 800 1000 1200 1400

Binding Energy (eV)

35


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Ionization

BE = h (known) KE(measured) BE = Eo(measured) Eloss(measured)

o oe ec ron pec roscopy Electron Energy-Loss Spectroscopy

Eincident X-ray = h Eincident electron = EoSpectrometer, KE

Conduction BandConduction Band

Fermi

Conduction BandConduction Band

Valence Band

eve

2pBE

Valence Band

2pBE

2s

1s

2s

36Spectrometer, Eo, Eloss


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Elemental Shifts:An Example

Metal and N Auger Lines

N1s

Sc2p

Sc2s

rs - ow rans on e a r es: c , , , an r

ScN

its) Ti2p

Ti2s

Sc3p

Sc3s

TiN

(

arb.u

N1s

V2p

V2s

Ti3s

Ti3p

VN

Count

Cr2pV3s

p

CrN

s

Cr3s

r p

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Binding energy (eV)

Surface Science Spectra, 7, 167-280, 2000.


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Relaxation

Incident particle Ejected Electron Emitted Auger Electron

Emitted X-ray Photonionization

Conduction BandConduction BandFermi

Conduction Band

ree ec ron eve

Valence Band

Level

Valence Band

2s

2, 3

L1

1s K

KLL Auger electron

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Auger - 2,3 - 2,3

EX-ray = E(K) E(L2,3)

STEM


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Elemental analysis by electron microscopy

1O primary e-beam

0.5-30 keV

Scanning electron microscopy (SEM)primary e-beam

100-300 keV

cann n ransm ss onelectron microscopy (STEM)

backscatteredelectrons

characteristic &

Bremsstrahlun

secondary

electrons 1 keV, the cascade is linear, i.e. approximated by a series of binary collisions

41P.Sigmund, Sputtering by ion bombardment: theoretical concepts, in Sputtering by particle bombardment I, edited by R. Behrish, Springer-Verlag, 1981

.


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Ion impact collision cascade

Energy increasing (dependent on Mi/Mt)

Threshold regime Linear cascade Spike regimerecoils sputtered, but

no (limited) cascadesa series of binary collisions high density of recoils

recoiled target atoms in turn collide with atom at rest generating a collision cascade. The initial ion energy and momentum are distributed to among the target recoil atoms.

When Ei > 1 keV, the cascade is linear, i.e. approximated by a series of binary collisions


.


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Ion stopping cross section

( )( )) (en S EdE

N N SS E Edx

0

'

( ')

EdE

RangeNS E

Sn

(E) - nuclear stopping; target atoms set in motion

Se(E) - electronic stopping; electrons set in motion

E/d

x)

Se(E)

spercml

og(d

Sn(E)

1-2 keV

energy

los

1-2 MeV(log E)




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. at are t e u ng oc s e ementa an c em caanalysis

.

3. What is the arrangement of the building blocks crystallographic analysis

4. What are the surface morphology and bulk

nanostructure imaging from micron to sub-nanometer

usingScanning probe microscopy

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Scanning electron microscopy

At i f i


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Atomic force microscopy

Split photodetector

Reflect laser off cantilever in split photodetector

Magnifies small displacements both vertical and twisting

45

V.L. Mironov, Fundamental of scanning probe microscopy, (Russian Academy of Sciences, Nizhny Novgorod, 2004) http://www.ntmdt.ru

f h l l d


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AFM: Surface morphology evolution during Ge MBE

46

Quantitative information of height allows histograms of slopes


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Imaging with secondary electrons

Reveals surface morphology with exceptional depth of focus

47


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Imaging spheresAFM SEM

48



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1. What are the building blocks elemental and chemical

2. What is the electronic structure3. What is the arrangement of the building blocks

crystallographic analysis


-

with sub-nanometer resolution

Transmission electron microscopy

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Analytical (Scanning ) Transmission Electron Microscopy (S)TEM


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Analytical (Scanning ) Transmission Electron Microscopy (S)TEM

primary e-beam

100-300 keV

Coherent

Scattering

(i.e. Interference)characteristic &

Bremsstrahlun

Incoherent

x-rays

Probe sizeScattering

i.e. Rutherford

0.18 nm

Thickness


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p p 2 ( )

[110] XTEM & [001] plan[110] XTEM & [001] plan--view TEMview TEM

HighHigh--resolution [110] XTEMresolution [110] XTEM

c

d glue

ZZ--contrast HRcontrast HR--STEM & EELSSTEM & EELS

b a

CoSi2

Si

rb.units)

rb.units)

5 nm

d

O K-edge

Intensit

y

(

Intensit

y

(

ab Co L -edge

2

Co L -edge3

Energy loss (eV)Energy loss (eV)

Lim, Greene, Petrov, JAP, 100, 013510, (2006)

Materials characterization: the need for complementary techniques


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Materials characterization: the need for complementary techniques

T ical se uence to stud a set of sam les:

1/ non-destructive analysis with no sample preparation to map out phasecomposition (XRD), surface morphology (AFM, SEM), elemental

composition (RBS, EDS)

2/ measure physical properties - electrical, mechanical, optical etc.

3/ analysis selected samples by surface analysis (e.g. AES, XPS) depthprofiling, cross-sectional SEM

4/ Select key samples for plan-view and cross-section TEM to understand

critical behavior physical properties

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Manipulating [AlN] in Hf1 xAlxN using Ei


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p g [ ] 1-x x g i

Ei = 80eV

Ei = 60eV

Ei = 50eV

Ei

= 40eV

Ei = 30eV

Ei = 20eV

Ei = 10eV

Brandon Howe

Manipulating [AlN] in Hf1-xAlxN using Ei


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p g [ ] 1-x x g i

002 022

002 022

020

Z-contrast

Brandon Howe

Hf0 70Al0 30N/HfN Superlattices by Ei modulation


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Hf0.70Al0.30N/HfN Superlattices by Ei modulation

002 022 = 3.4 nm

= 3.4 nm

50nm Hf0.7Al0.3N buffer layer (Ei=10eV)ayers; sec i= e , sec i= e

= 3.4 nm

Brandon Howe

Hf0 70Al0 30N/HfN Superlattices by Ei modulation


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Hf0.70Al0.30N/HfN Superlattices by Ei modulation

= 1 nm

= 3 nm

= 2 nm

= 4 nm

= 6 nm

= nm

Hysitron TI 950 Triboindenter

[0 0 2] map

Brandon Howe

FSMRL Center for Microanalysis of Materials


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y

ompre ens ve se o ec n ques rom rou ne o mos a vance24 h access to qualified users

Staff 14 scientists and engineers for > 40 major instruments

. ur ace na ys sCameca IMS 5f SIMS

PHI 660 AugerPHI 5400 XPSSmall-spot imaging XPSPHI TOF-SIMS 2003

. ransm ss on ec ron croscopyPhilips CM12

JEOL 2010 F STEM/TEMJEOL 2011 TEMIBM Low-Energy Electron MicroscopyJEOL 2100 Cryo (2006)

Van de Graaff for ion beam analysis

6. Laser and Optical SpectroscopiesRaman spectroscopy/Photoluminescence

S ectro hotometr /FTIR

JEOL 2200FSTEM/STEM (2008)

2. Scanning Electron MicroscopySEM/Focused ion-beam microscopyHitachi S-4700, SEM S-4800 (2008)

JEOL 6060 low-vacuum SEM(2004)Pump/probe spectroscopySum frequency generationEllipsometryNear-Field Scanning Optical MicroscopySolar cell efficiency (2010)Solar spectrum simulator (2010)

ana yt ca

3. Scanning Probe MicroscopyDigital Instruments AFM

Advanced Asylum Research AFM (2) (2005)Asylum Research Cypher (2010)

a vern nstruments etas zer

Contact Angle Goniometers (2010)Ultrafast Confocal microscope (2011)MicroRaman (2011)

7. Property Measurement

m cron -

4. X-ray ScatteringPhilips X'pert: high-resolution, reciprocal mapsPhilips X'pert: powder, pole figuresRigaku D-Max: powder

57

erent a scan. ca or metry ermogr. ana ys sHysitron TI 950 Triboindenter (2010)Hysitron Picoindenter (2010)Quantum Design MPMS (2011)

Quantum Design PPMS (2011)

-Anton Paar DHS900 hot stage (2010)Energy Dispersive X-Ray Fluorescence

me 598 - lecture 1 - overview of materials characterization...

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