Scanning Electron

Microscopy and
X-Ray Microanalysis
THIRD EDITION
Joseph

l.

Goldstein

Massachusetts
Massachusetts

Charles E. Lyman

University of

Lehigh University

Amherst,

Bethlehem, Pennsylvania

Dale E.

Newbury

National Institute of Standards

and

kchnology

Eric Lifshin
State University at Albany
Albany, New York

Gaithersburg, Maryland

Patrick

Linda Sawyer

Echlin

Cambridge Analytical Microscopy

Cambridge, England

David c.

loy

University of Tbnnessee
Knoxville, Tbnnessee

,cona LLC

Ltd.

Summit, New Jersey

!i"if!"i."?;Jjj!ff'
Albuquerque, New Mexico

Kluwer Academic / Plenum Publishers

New York Boston, Dordrecht, London, Moscow

Contents
1. Introduction

l.l.
1.2.
1.3.
1.4.

ImagingCapabilities

StructureAnalysis
ElementalAnalysts
Summary and Outline of This Book
Appendix A. Overview of Scanning Electron Microscopy
Appendix B. Overview of Electron Probe X-Ray Microanalysis

2. The SEM and lts Modes of Operation

2.2.

l0
17
18

t9
20

References

2.1.

2
10

How the SEM Works

2.1.1. Functions of the SEM Subsystems
2.1 .1.1. Electron Gun and Lenses Produce a Small
Electron Beam
2.1.1.2. Deflection System Controls Magnification
2.1.1.3. Electron Detector Collects the Signal
2.1.1.4. Camera or Computer Records the Image .
2.1.1.5. Operator Controls
2.1.2. SEM Imaging Modes
2.1.2.1. Resolution Mode
2.1.2.2. High-Current Mode
2.1.2.3. Depth-of-Focus Mode
2.1.2.4. Low-Voltage Mode
2.1.3. Why Learn about Electron Optics?
Electron Guns
2.2.1. Tungsten Hairpin Electron Guns .
2.2.1.1. Filament

2.2.1.2.
2.2.1.3.
2.2.1.4.
2.2.1.5.

Grid Cap
Anode
Emission Current and Beam Current
Operator Control of the Electron Gun

2t
2t
2t
22

))

24
25
25
25

27
27
28

"29
29
29
30
30
31
31

32
32

vil

2.2.2.

vtrr
CONTENTS

2.2.3.

2.3.

2.2.4.

2.2.2.2.
2.2.2.3.
2.2.2.4.
2.2.2.5.

2.3.3.
2.3.4.
2.3.5.

Lifetime

34

Source Size, Energy Spread Beam Stability

Improved Electron Gun Characteristics
Lanthanum Hexaboride (LaB6) Electron Guns

2.2.3.1. Introduction
2.2.3.2. Operation of the LaB6 Source

4l

42
42
42
44
44

2.3.2.2. Obiective Lenses

2.3.2.3. Real and Virtual Objective Apertures
Operator Control of SEM Lenses

2.3.3.1. Effect of Aperture Size

2.3.3.2. Effect of Working Distance
2.3.3.3. Effect of Condenser Lens Strength

45
45

46
47
48
48
49

Gaussian Probe Diameter

LensAberrations

Spherical Aberration
Aperture Diffraction
Chromatic Aberration
Astigmatism
Aberrations in the Objective Lens
Electron Probe Diameter versus Electron Probe Current
2.4.1. Calculation of d.;n and imax

Minimum Probe Size

Minimum Probe Size at l0-30 kV
Maximum Probe Current at l0-30

kV

50
51
53

54

54
54
54
.

Low-Voltage Operation
2.4.1..5. Graphical Summary
Performance in the SEM Modes
2.4.2.1. Resolution Mode
2.4.2.2. High-Current Mode
2.4.2.3. Depth-of-Focus Mode
2.4.2.4. Low-Voltage SEM
2.4.2.5. Environmental Barriers to High-Resolution
Imaging

55
55
56

56
56
58
59
59
59

60

References

3. Electron Beam-Specimen lnteractions

The Story So Far

34
35
35
36

)t

2.3.5.1.
2.3.5.2.
2.3.5.3.
2.3.5.4.
2.3.5.5.

2.4.2.

34

40
40
40

Lenses in SEMs
2.3.2.1. Condenser Lenses

2.4.1.1.
2.4.1.2.
2.4.1.3.
2.4.1.4.

3.1.
3.2.
3.3.

33
JJ
JJ

Brightness

Field Emission Electron Guns

Electron Lenses
2.3.1. Making the Beam Smaller
2.3.1.1. Electron Focusing
2.3.1.2. Demagnification of the Beam

2.3.2.

2.4.

Electron Gun Characteristics

2.2.2.1. Electron Emission Current

The Beam Enters the Specimen

The Interaction Volume
3.3. I .
Visualizing the Interaction Volume
3.3.2. Simulating the Interaction Volume

6l
6l
6t
65
65
67

-l

- -J

--1

lnfluence of Beam and Specimen Parameters on

the Interaction Volume
3.3.3.1. Influence of Beam Energy on the
Interaction Volume
3.3.3.2. Influence of Atomic Number on the
Interaction Volume
3.3.3.3. Influence of Specimen Surface Tilt on the

Interaction Volume
Electron Range: A Simple Measure of the
Interaction Volume
3.3.4.1. Introduction
3.3.4.2. The Electron Range at Low Beam Energy
Imaging Signals from the Interaction Volume

3.3.4.

3.4.

3.4.1.

3.4.2.

Backscattered Electrons

3.4.1.1.
3.4.1.2.
3.4.1.3.
3.4.1.4.
3.4.1.5.
3.4.1.6.
3.4.1.7.

Beam Energy Dependence of BSE

Tilt Dependence of BSE
Angular Distribution of BSE
Energy Distribution of BSE
Lateral Spatial Distribution of BSE

3.4.2.1.
3.4.2.2.
3.4.2.3.
3.4.2.4.
3.4.2.5.
3.4.2.6.
3.4.2.7.
3.4.2.8.

Definition and Origin of SE

SE Yield with Primary Beam Energy
SE Energy Distribution
Range and Escape Depth of SE
Relative Contributions of SE1 and SEz .
Specimen Composition Dependence of SE
Specimen Tilt Dependence of SE
Angular Distribution of SE .

Atomic Number Dependence of BSE

Sampling Depth of BSE

SecondaryElectrons

References

4.2.

and lnterpretation

Scanning Action
Image Construction

72
72

l3
75
75
75
77

79
80
82
84
86
88
88
89

9t
91

93
95
96
97

99

(Mapping)

4.2.2.1. Line Scans

4.2.2.2. Image (Area) Scanning
4.2.2.3. Digital Imaging: Collection and Display

4.2.7.1. Projection Distortion: Gnomonic Projection

.2.

Projection Distortion: Image Foreshortening

4.2.7.3. Scan Distortion: Pathological Defects
4.2.7

4.2.7.4. Moir6 Effects

Detectors

4.3.1.

7l

99

4.2.3. Magnification
4.2.4. Picture Element (Pixel) Size
4.2.5. Low-Magaification Operation
4.2.6. Depth of Field (Focus)
4.2.7. ImageDistortion

4.3.

69

99

The Story So Far

The Basic SEM Imaging Process

4.2.1.
4.2.2.

CONTENTS
68

97

4. lmage Formation

4.1.

ix
68

Introduction

101

103
103

104
107
108

l0
l4
t4
18
18

t9
23
25
125
125

4.3.2.

Electron Detectors
4.3.2.1. Everhart-Thornley Detector
4.3.2.2. "Through-the-Lens" (TTL) Detector

t27

4.3.2.3. Dedicated Backscattered Electron Detectors

133

The Roles of the Specimen and Detector ia Contrast Formation

4.4.1. Contrast
4.4.2. Compositional (Atomic Number) Contrast

139

CO:NTENTS

4.4.

128

t32

Introduction
4.4.2.2. Compositional Contrast with Backscattered
4.4.2.1

Topographic Contrast
4.4.3.1. Origins of Topographic Contrast
4.4.3.2. Topographic Contrast with the Everhart-

Thornley Detector

4.5.
4.6.

5.3.
5.4.
5.5.
5.6.

151

Other Detectors
Image Quality
Image Processing for the Display of Contrast Information
4.6.1. The Signal Chain
4.6.2. The Visibility Problem
4.6.3. Analog and Digital Image Processing
4.6.4. Basic Digital Image Processing
4.6.4.1. Digital Image Enhancement
4.6.4.2. Digital Image Measurements

158
173

High-Resolution Imaging
5.1.1. The Resolution Problem
5.1.2. Achieving High Resolution at High Beam Energy
5.1.3. High-Resolution Imaging at Low Voltage
STEM-in-SEM: High Resolution for the Special Case
of Thin Specimens
Surface Imaging at Low Voltage
Making Dimensional Measurements in the SEM .
Recovering the Third Dimension: Stereomicroscopy
5.5.1. Qualitative Stereo Imaging and Presentation
5.5.2. Quantitative Stereo Microscopy
Variable-Pressure and Environmental SEM
5.6.1. Currentlnstruments
5.6.2. Gas in the Specimen Chamber
5.6.2.1. Units of Gas Pressure

5.6.3. Electron Interactions with Gases

5.6.4. The Effect of the Gas on Charging
5.6.5. Imaging in the ESEM and the VPSEM
5.6.6. X-Ray Microanalysis in the Presence of a Gas
Special Contrast Mechanisms
5 .7 .1. Electric Fields
5.7.2. Magnetic Fields

178
178
180

r82
184
187

192
192
195

5.6.2.2. The Vacuum System

5.1

r46
147

5. SpecialTopics in Scanning Electron Microscopy

5.2.

r45

4.4.3.3. LightOptical Analogy

4.4.3.4. Interpreting Topographic Contrast with

References

5.1.

t4l

141
141

E.lectrons

4.4.3.

139

195
195
197

201
203
207
209

2t2
2t2
217
220
221

222
222
222
225
231
236
241
242
243
245

5.8.

.2.1.
.2.2.

Type I Magnetic Contrast

'lype 2 Magnetic Contrast
5.7 .3 .
Crystallographic Contrast
ElectronBackscatterPatterns
5.8.1. Origin of EBSD Patterns
5.8.2. Hardware for EBSD
5.8.3. Resolution of EBSD
5.8.3.1. Lateral Spatial Resolution
5.8.3.2. Depth Resolution
Applications
5.8.4.
5.8.4.1. Orientation Mapping
5.8.4.2. Phase Identification
5.7

5 .7

24s
247
247

2s6
260
262
264
264
266
267
261
267
269

References

6. Generation of X-Rays in the SEM Specimen

6.1.
6.2.

6.3.

6.4.
6.5.

Continuum X-Ray Production (Bremsstrahlung)

Characteristic X-RayProduction

6.2.1. Origin
6.2.2. FluorescenceYield
6.2.3. Electron Shells
6.2.4. Energy-Level Diagram
6.2.5. Electron Transitions
6.2.6. Critical Ionization Energy
6.2.7. Moseley's Law
6.2.8. Families of Characteristic Lines
6.2.9. Natural Width of Characteristic X-Ray Lines
6.2.10.
6.2.11.
6.2.12.
6.2.13.
6.2.14.

Weights of Lines
Cross Section for Inner Shell Ionization

X-Ray Production in Thin Foils

X-Ray Production in Thick Targets
X-Ray Peak-to-Background Ratio
Depth of X-Ray Production (X-Ray Range)
6.3 .1 .
Anderson-Hasler X-Ray Range
6.3.2. X-Ray Spatial Resolution
6.3.3. Sampling Volume and Specimen Homogeneity
6.3.4. Depth Distribution of X-Ray Production, Q@z)
X-Ray Absorption
6.4.1. Mass Absorption Coefficient for an Element
6.4.2. Effect of Absorption Edge on Spectrum
6.4.3. Absorption Coefficient forMixed-ElementAbsorbers
X-RayFluorescence

6.5.1. Characteristic Fluorescence

6.5.2. ContinuumFluorescence
6.5.3. Range of Fluorescence Radiation

References

7. X-Ray Spectral Measurement:

7.1.
7.2.

271
271

274
214
275

276
277
211
2',78

279
279

28r
282
283

284
284
285

286
286
286
288
288
289
290

29t
291
292
293

294
295

29s

EDS and WDS

Introduction
Energy-Dispersive X-Ray Spectrometer
7 .2.1. Operating Principles

297
297
297
297

x,
CONTENTS

xii

7.2.2.
7.2.3.
1.2.4.

The Detection Process

Charge-to-Voltage Conversion .
Pulse-Shapin g Linear Amplifi er and Pileup

7.2.5.
7.2.6.
7.2.7.

The Computer X-Ray Analyzer

Digital Pulse Processing
Spectral Modification Resulting from the Detection

CONTENTS

Rejection Circuitry

Process

7.2.7.1.
7.2.7.2.
7

.2.7

.3.

Peak Broadening
Peak Distortion
Silicon X-Ray Escape Peaks

7.2.7.4. Absorption Edges

7.2.8.
1.2.9.

.5.

Silicon Internal Fluorescence Peak

Artifacts from the Detector Environment
Summary of EDS Operation and Artifacts
7

.2.7

Wavelength-Dispersive Spectrometer

. Introduction
7.3.2. BasicDescription' . : . . . . . :
7.3.3. Diffraction Conditions
7 .3.4. Diffracting Crystals
7.3.5. The X-Ray Proportional Counter
7 .3 .6. Detector Electronics
7

7.4.

7.5.

Comparison ofWavelength-Dispersive Spectrometers with

Conventional Energy-Dispersive Spectrometers
7.4.1. Geometric Collection Effrciency

7.4.2. QuantumEfficiency
7.4.3. Resolution
7.4.4. Spectral Acceptance Range
7.4.5. Maximum Count Rate
7.4.6. Minimum Probe Size
7.4.7. Speed of Analysis
7.4.8. SpectralArtifacts

l.

311

312
312
316
317
318

320
321
322

324
325

327
330
333
340

340

34t
342

344
344
344
346
346

EmergingDetectorTechnologies

341

7.5.1. X-RayMicrocalorimetery
7.5.2. Silicon Drift Detectors
7 .5.3 .
Parallel Optic Diffraction-Based

347

8. Oualitative
8.2.

303
308

323
323

.3.1

Spectrometers

349
350
353

References

8.

301

302

X-Ray Analysis

Introduction
EDS Qualitative Analysrs
8.2.1. X-Ray Peaks
8.2.2. Guidelines for EDS Qualitative Analysis
8.2.2.1. General Guidelines for EDS Qualitative
Analysis
8.2.2.2. Specific Guidelines for EDS Qualitative
Analysis
8.2.3. Examples of Manual EDS Qualitative Analysis
8.2.4. Pathological Overlaps in EDS Qualitative
Analysis

35s
355

3s7
3s7
366
368

369
372
374

10.7

.3.2. Overvoltage Effects

sl5

"Low-Voltage" versus "Conventional" Microanalysis

518
518

10.7.4.
10.8. Low-Voltage Microanalysis
1

0. 8.

512
514

10.1.3.3. Absorption Effects

Light Element Quantification

10.8.2. X-Ray Production

Range

10.8.2.1. Contribution of the Beam Size to the X-Ray

Analytical Resolution
10.8.2.2. A Consequence of the X-Ray Range under
Low-Voltage Conditions
10.8.3. X-Ray Spectrometry in Low-Voltage Microanalysis
10.8.3. 1 . The Oxygen and Carbon Problem
10.8.3.2. Quantitative X-Ray Microanalysis at Low

519
520
523

525
526

s28

Voltage

10.9. Report of Analysis

531

References

535

11. Specimen Preparation of Hard Materials: Metals,

Ceramics, Rocks, Minerals, Microelectronic and
Packaged Devices, Particles, and Fibers

11.1. Metals
11.1.1.
11.1.2.

Specimen Preparation for Surface Topography

Specimen Preparation for Microstructural and

Microchemical Analysis
11.1.2.1. Initial Sample Selection and Specimen
Preparation

11.2.

Steps

11.1.2.2. Final Polishing Steps

11.1.2.3. Preparation for Microanalysis
Ceramics and Geological Samples

537
537
537
538
538

539
540
541

11.2.1. Initial Specimen Preparation: Topography and

Microstructure

s42

11.2.2. Mounting and Polishing for Microstructural and

Microchemical Analysis
Final Specimen Preparation for Microstructural and
Microchemical Analysis
Microelectronics and Packages
11.2.3

1.3.

I I .3. I . Initial Specimen Preparation

11.3.2. Polishing
I 1.3.3. Final Preparation

11.4. Imaging of Semiconductors

I 1.4.1. Voltage Contrast
11.4.2. Charge Collection

I1.5.
1

1.6.

Preparation for Electron Diffraction in the SEM

I 1.5.1. Channeling Patterns and Channeling Contrast
11.5.2. Electron Backscatter Diffraction
Special Techniques
I 1.6.1. Plasma Cleaning
11.6.2. Focused-Ion-Beam Sample Preparation for SEM
11.6.2.1. Application of FIB for Semiconductors

542
542
543
543

544
545
545
s46
546
547
547
547
551
551
553

554

11.6.2.2. Applications of FIB in Materials

Science

555

xv
CONTENTS

xvi

11.7

Particles and Fibers

11 .7

.1.

CONTENTS
l.'7.2.
1.7.3.
t.7 .4.
| .7 .5.

557
559

Supports
Substrates
Supports
Techniques
Filters

Particle Substrates and

1 1.7.1.1. Bulk Particle
11.1.1.2. Thin Particle
Particle Mounting
Particles Collected on
Particles in a Solid Matnx
Transfer of Individual Particles

559
560
560

562
563
563
564

References

12. Specimen Preparation of Polymer Materials

r2.1.
12.2.

12.3.

565

Inffoduction
Microscopy of Polymers
12.2.1. Radiation Effects
12.2.2. Imaging Compromises
12.2.3. Metal Coating Polymers for Imaging
12.2.4. X-Ray Microanalysis of Polymers
Specimen Preparation Methods for Polymers
12.3.1. Simple Preparation Methods
12.3.2. Polishing of Polymers
12.3.3. Microtomy of Polymers
12.3.4. Fracture of Polymer Materials
12.3.5. Staining of Polymers
123.5.1. Osmium Tetroxide and Ruthenium

565
565

566
567
567
570
570
571
571

572
573
576

Tetroxide

578
578

Acid

578
579
s80
580
580

12.3.5.2. Ebonite
12.3.5.3. Chlorosulfonic Acid and Phosphotungstic

12.3.6. Etching of Polymers

12.3

.1

Replication of Polymers

12.3.8. Rapid Cooling and Drying Methods for Polymers

12.3.8.1. Simple Cooling Methods
12.3.8.2. Freeze-Drying
12.3.8.3. Critical-Point Drying
12.4. Choosing Specimen Preparation Methods

12.4.1.
12.4.2.
12.4.3.
12.4.4.

12.5.
12.6.

13.

581
581
581

Fibers

582

Films and Membranes

Engineering Resins and Plastics
Emulsions and Adhesives
Problem-Solving Protocol
Image Interpretation and Artifacts

582
583
581

References

588
589
590

Ambient-Temperature Specimen Preparation

of Biological Material

591

13.1. Introduction
13.2. Preparative p.ocedures rotin" s*"*iuiSEM of Single
Cells, Biological Particles, and Fibers
13.2.1. Particulate, Cellular, and Fibrous Organic Material
13.2.2. Dry Organic Particles and Fibers

59t

592
592
593

13.2.2.1. Organic Particles and Fibers on a Filter

13.2.2.2. Organic Particles and Fibers Entrained

within a Filter

594

xvt,

594

CONTENTS

13.2.2.3. Organic Particulate Matter Suspended in a

Liquid

13.3.

594

13.2.2.4. Manipulating Individual Organic Particles

Preparative Procedures for the Structural Observation of
Large Soft Biological Specimens

13.3.1. Introduction
13.3.2. Sample Handling before Fixation
13.3-3. Fixation
13.3.4. Microwave Fixation
13.3.5. Conductive Infiltration
13.3.6. Dehydration
13.3.1. Embedding
13.3.8. Exposing the Internal Contents of Bulk Specimens
13.3.8. 1. Mechanical Dissection

13.3.8.2. High-Energy-Beam Surface Erosion

3.3.8.3. Chemical Dissection

13.3.8.4. Surface Replicas and Corrosion Casts
13.3.9. Specimen Supports and Methods of Sample
Attachment
13.3.10. Artifacts
Preparative Procedures for the in Situ Chemical Analysis
of Biological Specimens in the SEM
13.4.1. Introduction
13.4.2. Preparative Procedures for Elemental Analysis Using
X-Ray Microanalysis
13.4.2.1. The Nature and Extent of the Problem
13.4.2.2. Types of Sample That May be Analyzed
13.4.2.3. The General Strategy for Sample

13.4.3.

Preparation
13.4.2.4. Criteria for Judging Satisfactory Sample
Preparation
13.4.2.5. Fixation and Stabilization
13 .4.2.6. Precipitation Techniques
13.4.2.1 . Procedures for Sample Dehydration,
Embedding, and Staining
13.4.2.8. Specimen Supports
Preparative Procedures for Localizing

Molecules Using Histochemistry

13.4.3.1. Staining and Histochemical Methods
13.4.3.2. Atomic Number Contrast with
Backscattered

Electrons

13.4.4. Preparative Procedures for Localizing Macromolecues

Usinglmmunocytochemistry. .

l3.4.4.l.Introduction

13.4.4.2. The Antibody-Antigen Reaction

13.4.4.3. General Features of Specimen Preparation
for Immunocytochemistry
13.4.4.4. Imaging Procedures in the SEM
References

596
596
596
596
591
591
597

602
602
602

13.4.

595

602
603

604
605
607

607
607
608
608

609
609
610
610
611
611
611

612
612
613
614
614
614

6ts
616
618

15.5.

Sputter Coating
15.5.1. Plasma Magnetron Sputter Coating
15.5.2. Ion Beam and Penning Sputtering
15.6. High-Resolution Coating Methods
15.7. Coating for Analytical Studies
15.8. Coating Procedures for Samples Maintained
at Low Temperatures
15.9. Coating Thickness
15.10. Damage and Artifacts on Coated Samples
15.11. Summary of Coating Guidelines
References

661
662

664
667
669
669
670
672
673
673

675

Enhancements GD

xix
CONTENTS