vickerman - surface analysis the principal techniques

8/9/2019 Vickerman - Surface Analysis the Principal Techniques

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S urface A n alys is

The Pr incipal

Techniques

2nd Edition

Editors

JOHNC.VICKERMAN

Man chester Interdisciplinary

Biocentre

niv rsityof

Manchester

UK

IA N S . GILMORE

National PhysicalLaboratory

Teddington UK

W I L Y

A John Wiley and Sons, Ltd., Pu blication


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Contents

List of Contribu tors xv

Preface xvi i

1 Intro d uction 1

John

C

Vickerman

1.1

1.2

1.3

1.4

1.5

1.6

How do we Define the Surface?

How Many Atoms in a Surface?

Information Required

Surface Sensitivity

Radiation Effects - Surface Damage

Com plexity of the Data

2 Auger E lectron Spectro sco py

Hans

2.1

2.2

2.3

;

JorgMathieu

Introduction

Principle of the Aug er Process

2.2.1 Kinetic Energies of Auger Peaks

2.2.2 Ionization Cross-Section ;

2.2.3 Comparison of Auger and Photon Emission

2.2.4 Electron Backscattering

2.2.5 Escape Depth

2.2.6 Chemical Shifts

Instrumentation

2.3.1 Electron Sources

2.3.2 Spectrometers

2.3.3 Modes of Acquisition

2.3.4 Detection Limits

2.3.5 Instrument Calibration

1

2

3

5

7

8

9

9

10

11

15

16

17

18

19

21

22

24

24

29

30


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V I ONTENTS

2.4 Quantitative Analysis 31

2.5 Depth Profile Analysis 33

2.5.1 Thin Film Calibration Standard 34

2.5.2 Depth Resolution 36

2.5.3 Sputter Rates 37

2.5.4 Preferential Sputtering 40

2.5.5 X-Correction 41

2.5.6 Chemical Shifts in AES Profiles 42

2.6 Summary 43

References 44

Problems 45

Electron Spectroscopy

for

Chemical nalysis

7

BuddyD .Rattiera nd David

G

Castner

3.1 Overview 47

3.1.1 The Basic ESCA Experiment 48

3.1.2 A History of the Photoelectric Effect and ESCA 48

3.1.3 Information Provided by ESCA 49

3.2 X-ray Interaction with Matter, the Photoelectron Effect

and Photoemission from Solids 50

3.3 Binding Energy and the Chemical Shift 52

3.3.1 Koopmans' Theorem 53

3.3.2 Initial State Effects 53

3.3.3 Final State Effects 57

3.3.4 Binding Energy Referencing 58

3.3.5 Charge Compensation in Insulators 60

3.3.6 Peak Widths 61

3.3.7 Peak Fitting 62

3.4 Inelastic Mean Free Path and Sampling Depth 63

3.5 Quantification 67

3.5.1 Quantification Methods 68

3.5.2 Quantification Standards 70

3.5.3 Quantification Example 71

3.6 Spectral Features 73

3.7 Instrumentation 80

3.7.1 Vacuum Systems for ESCA Experiments 80

3.7.2 X-ray Sources 82


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CONTENTS

3.8

3.9

3.10

3.11

3.12

-- ' 3.13

3.14

3.7.3 Analyzers

3.7.4 Data Systems

3.7.5 Accessories

Spectral Q uality

Depth Profiling

X-Y M apping and Imaging

Chemical Derivatization

Valence Band

Perspectives

Conclusions

Acknowledgements

References

Problems

4 Mo lecular Surface M ass Spectr o metr y by SIMS

JohnC

4.1

4.2

4.3

4.4

>

4.5

4.6

Z. Vickerman

Introduction

Basic Concepts

4.2.1 The Basic Equation

4.2.2 Sputtering

4.2.3 Ionization

4.2.4 The Static Limit and Depth Profiling

4.2.5 Surface Charging

Experimental R equirements

4.3.1 Primary Beam

4.3.2 Mass Analysers

Secondary Ion Formation

4.4.1 Introduction

4.4.2 Models of Sputtering

4.4.3 Ionization

4.4.4 Influence of the Matrix Effect in Organic

Materials A nalysis

M odes of A nalysis

4.5.1 Spectral Analysis

4.5.2 SIMSImaging or Scanning SIMS

4.5.3 Depth Profiling and 3D Imaging

Ionization of the Sputtered Neutrals

VII

84

86

88

88

89

94

96

96

99

100

101

101

109

113

113

116

116

116

121

123

124

125

125

131

140

140

143

149

151

155

155

166

173

183


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VIM

4.7

4.6.1

4.6.2

CONTENTS

Photon Induced Post-Ionization

Photon Post-Ionization and SIMS

Ambient Methods of Desorption Mass Spectrometry

References

Problems

5 Dynamic SIMS

David

McPhail

and Mark Dowsett

5:1

5.2

5.3

5.4

5.5

-

' Fundamentals and Attributes

5.1.1

5.1.2

5.1.3

5.1.4

5.1.5

Areas

5.2.1

5.2.2

5.2.3

5.2.4

Introduction

Variations on a Theme

The Interaction of the Primary Beam

with the Sample

Depth Profiling

Complimentary Techniques and D ata

Comparison

and Methods of Application

Dopant and Impurity Profiling

Profiling High Concentration Species

Use ofSIMSin Near Surface Regions

Applications of

SIMS

Depth Profiling

in M aterials Science

Quantification of Data

5.3.1

5.3.2

5.3.3

5.3.4

Novel

5.4.1

5.4.2

5.4.3

Quantification of Depth Profiles

Fabrication of S tandards

Depth Measurement and Calibration of the

Depth Scale

Sources of Error in Depth Profiles

Approaches

Bevelling and Imaging or Line Scanning

Reverse-Side Depth Profiling

Two-Dimensional Analysis

Instrumentation

5.5.1

5.5.2

5.5.3

5.5.4

Overview

Secondary Ion Optics

Dual Beam M ethods and ToF

Gating

184

190

194

199

203

2 0 7

207

207

211

214

217

224

226

226

227

230

233

233

233

239

241

242

246

246

250

251

252

252

253

254

254


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CONTENTS IX

5.6

Conclusions

References

Problems

6 Low E nergy Ion Scatt er ing and Rutherford Backscatt ering

Edmund

Taglauer

6.1

6.2

6.3

6.4

Introduction

Physical Basis

6.2.1 The Scattering Process

6.2.2 Collision Kinem atics

6.2.3 Interaction Potentials and Cross-sections

6.2.4 Shadow Cone

6.2.5 Computer Simulation

Rutherford Backscattering

6.3.1 Energy Loss

6.3.2 Apparatus

6.3.3 Beam Effects

6.3.4 Quantitative Layer Analysis

6.3.5 Structure Analysis

6.3.6 Medium-Energy Ion Scattering (MEIS)

6.3.7 The Value of RBS and Com parison to Related

Techniques

Low-Energy Ion Scattering

6.4.1 Neutralization

6.4.2 Apparatus

6.4.3 Surface Com position Analysis

6.4.4 Structure Analysis

6.4.5 Conclusions

Acknowledgement

References

Problems

Key Facts

256

257

267

269

269

271

271

272

275

278

281

284

284

287

289

290

293

297

298

300

300

303

307

316

323

324

324

330

330

7 Vib rationa l Spectroscopy from Surfaces

MartynE.Pemble and Peter Gardner

7.1 Intro duction 333

7.2 Infrared Spectroscopy from Surfaces 334


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CONTENTS

7.2.1 Tran sm ission IR Spec troscopy

335

7.2.2 Pho toacou stic Spectrosc opy

340

7.2.3 Reflectance M eth od s

342

7.3 Elec tron En erg y Loss Sp ectro sco py (EELS) 361

7.3.1 Inelastic

or

'Imp act ' Scattering

362

7.3.2 Elasticor 'Dipole' Scattering 365

7.3.3 Th e EELS (HREELS) Ex pe rim en t 367

7.4 TheG r o u p T h e o r yofSurface V ibrat ions 368

7*.4.1

General Approach

368

7.4.2 G rou p Theory AnalysisofEthyne Ad sorbedat a

Flat, Featureless Surface

369

7.4.3 G rou p Theo ry AnalysisofEthyne A dsorbedat a

(100) Surface

of an

FCC Metal

373

7.4.4 The Expected Formof the RAIRSand Dipolar

EELS (HREELS) Sp ectra 374

7.5 Laser Ra m an Spec troscopy from Surfaces 375

7.5.1 TheoryofRa ma n Scattering 376

7.5.2 The Stu dyofCollective Surface Vib rations

(Phonons) using Raman Spectroscopy 377

7.5.3 Ra m an Spectrosc opy from M etal Surfaces 379

7.5.4 Sp atial Re solu tion

in

Surface Ra m an

Spectroscopy 380

7.5.5 Fou rier Transfo rm Surface Ra m an Tec hniq ues 380

7.6 Inelast ic N eu tro n Scat ter ing (INS) 381

7.6.1 IntroductiontoIN S 381

7.6.2 The INS Sp ectru m

382

7.6.3 INS Spe ctraofHydrodesesulfurizat ion Catalysts 382

7 7

Sum-Frequency Generation Methods 383

References 386

Problems 389

8 Su r face S tructure Determinat ion

by

In te r fe r e n c e T e c h n iq u e s

39

hristopher

A . Lucas

8.1 Int roduct ion

391

8.1.1 Basic Th eo ryofD iffraction - Three Dimensions 392

8.1.2 ExtensiontoSurfaces- Two Dimensions 398

8.2 Elec tron Diffraction Te ch niq ue s 402

8.2.1 Ge nera l Intro du ction 402


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CONTENTS XI

8.2.2 Lo w En erg y Electro n Diffraction 403

8.2.3 Reflection H ig h En erg y Elec tron Diffraction

(RHEED) 418

8.3 X-ray Tec hn ique s 424

8.3.1 Ge nera l Intro du ction 424

8.3.2 X-ray A ds orp tion Spec troscopy 427

8.3.3 Surface X-ray Diffraction (SXRD) 447

8.3.4 X-ray Sta nd ing W ave s (XSWs) 456

-... -

8.4 Ph oto ele ctro n Diffraction 464

8.4.1 Intro du ctio n 464

8.4.2 Theo retical Co nsid eratio ns 465

8.4.3 Ex perim ental Details 469

8.4.4 Ap plicatio ns of XPD an d Ph D 470

References 474

9 Scanning Probe Microscopy 479

Graham

J Leggett

9.1 Intr od uc t ion 479

9.2 Scann ing Tun nel l ing M icroscopy 480

9.2.1 Basic Prin cip les of the STM 481

9.2.2 Instrum entatio n and Basic Op eration Param eters 487

9.2.3 Atom ic Reso lution an d Spectrosco py: Surface

Crystal an d Electronic Struc ture 489

9.3 Ato m ic Force M icrosco py 511

9.3.1 Basic Prin ciple s of the AFM 511

9.3.2 Ch em ical Force M icroscopy 524

9.3.3 Friction Force M icros cop y 526

9.3.4 Biological A pp lica tion s of the AFM 532

9.4 Sca nnin g Ne ar-Field Op tical M icrosco py 537

9.4.1 Op tical Fibre Ne ar-Field M icroscopy 537

9.4.2 Ap ertu reless SNO M 541

9.5 O ther Scanning Probe M icroscopy Techn iques 542

9.6 L i thog raphy Us ing P robe Mic roscopy M ethod s 544

9.6.1 STM Lith og rap hy 544

9.6.2 AFM Lith og rap hy 545

9.6.3 Nea r-Field Ph oto litho gra ph y 549

9.6.4 The 'M illipe de ' 550


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XII CONTENTS

9.7 Co nclusio ns 551

References 552

Problems 559

10 T h e A p p l ic a t io n of Mu l t iv a r i a t e D a ta A n a l y s i s T e c h n i q u e s in

S u r fa c e A n a l y s i s 5 63

Joanna

L.S.

Lee and

Ian S. Gilmore

10.1 Int ro duc t ion 563

10.2 Basic C on ce pt s 565

10.2.1 M atrix an d Vector R epr ese nta tion of Data 565

10.2.2 Dim ens iona lity an d Ra nk 567

10.2.3 Relation to M ultiv aria te An alysis 568

10.2.4 Ch oosing the A pp rop riate M ultivariate M ethod 568

10.3 Facto r A na lys is for Iden tification 569

10.3.1 Term inolo gy 570

10.3.2 M athe m atical Ba ckg roun d 570

10.3.3 Principal C om po ne nt An alysis 571

10.3.4 M ultiva riate C ur ve Re solu tion 579

10.3.5 An alysis of M ultiv ariate Im age s 582

10.4 Re gress ion M eth od s for Qu antif icat ion 591

10.4.1 Term inolog y 591

10.4.2 M athe m atical Ba ckg roun d 592

10.4.3 Principal C om po ne nt Regression 594

10.4.4 Partial Least Sq uare s Reg ression 595

10.4.5 Calibration, Validation an d Pred iction 596

10.4.6 Exam ple - Co rrelating ToF -SIM S Spectra w ith

Polym er W ettability Using PLS 598

10.5 M et h o d s for Classification 600

10.5.1 D iscrim inan t Fu nction An alysis 601

10.5.2 H ierarc hal Clu ster An alysis 602

10.5.3 Artificial N eu ra l N etw or ks 603

10.6 Su m m ary an d Co nclusion 606

A c know l e dge me n t s 608

References 608

Problems 611


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CONTENTS XIII

Ap pen dix 1 VacuumTec hn ology forAp p l ied Sur face Sc ience

6 3

Rod W ilson

Al.l Introduction: Gases and Vapours 613

A1.2 The Pressure Regions of Vacuum Technology and

their Characteristics 619

A1.3 Production of a Vacuum 622

Al.3.1 Types of Pump 622

Al.3.2 Evacuation of a Chamber 634

* - ' Al.3.3 Choice of Pumping System 635

Al.3.4 Determination of the Size of Backing Pumps 636

Al.3.5 Flanges and their Seals 636

A1.4 Measurement of Low Pressures 637

Al.4.1 Gauges for Direct Pressure Measurement 638

Al.4.2 Gauges Using Indirect Means of Pressure

Measurement 640

Al.4.3 Partial Pressure Measuring Instruments 644

Acknowledgement 647

References 647

A p p e n d i x

2

Un i ts Fundame nta l Ph ys ica l Constants

and

Conversions 649

A2.1 Base Units of the SI 649

A2.2 Fundamental Physical Constants 650

A2.3 Other Units and Conversions to SI 651

References 652

Index 653

vickerman - surface analysis the principal techniques

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