THIN FILM

PHENOMENA
KASTURI L. CHOPRA
Staff Scientist, Ledgemont L a b o r a t o r y ,
Kennecott Copper Corporation
Lexington, Massachusetts

Adjunct Professor o f Mechanical Engineering

N o r t h e a s t e r n University
Boston, Massachusetts

McGRAW-HILL BOOK COMPANY New York St. Louis

San Francisco London Sydney Toronto Mexico Panama
 CONTENTS

Preface vii

1 INTRODUCTION 1

П THIN FILM DEPOSITION TECHNOLOGY 10

1. Introduction 10
2. Thermal Evaporation 11
2.1 General Considerations 11
2.2 Evaporation Methods 14
Resistive Heating; Flash Evaporation; Arc Evaporation; Ex-
ploding-wire Technique; Laser Evaporation; RF Heating;
Electron-bombardment Heating
3. Cathodic Sputtering 23
3.1 Sputtering Process 23
3.2 Glow-discharge Sputtering 29
Pressure; Deposit Distribution; Current and Voltage Depend­
ence; Cathode; Contamination Problem; Deposition Control
3.3 Sputtering Variants 34
xi
XÜ Contents

3.4 Low-pressure Sputtering 36

Magnetic Field; Assisted (Triode) Sputtering; RF Sputtering;
Ion-beam Sputtering
3.5 Reactive Sputtering 41
3.6 Sputtering of Multicomponent Materials 42
4. Chemical Methods 43
4.1 Introduction 43
4.2 Electrodeposition 44
Electrolytic Deposition; Electroless Deposition; Anodic Oxi-
dation
4.3 Chemical Vapor Deposition (CVD) 46
Pyrolysis (Thermal Decomposition); Hydrogen Reduction;
Halide Disproportionation; Transfer Reactions; Polymeri-
zation
4.4 Miscellaneous Methods 51
5. Vacuum-deposition Apparatus . 55
5.1 Vacuum Systems 55
5.2 Substrate-deposition Technology 61
Substrate Materials; Substrate Cleaning; Uniform and Non-
uniform Deposits; Masks and Connections; Multiple-film
Deposition
6. Conclusions 67
7. Appendix 69
References 76

III THICKNESS MEASUREMENT AND ANALYTICAL TECHNIQUES . . . 83

1. Thickness Measurement 83
1.1 Electrical Methods 84
Film Resistance; Capacitance Monitors; Ionization
Monitors
1.2 Microbalance Monitors 90
Microbalances; Quartz-crystal Monitor
1.3 Mechanical Method (Stylus) 96
1.4 Radiation-absorption and Radiation-emission Methods . . 97
1.5 Optical-interference Methods 99
Photometric Method; Spectrophotometry Method; Inter-
ference Fringes; X-ray Interference Fringes
1.6 Summary of Methods 105
2. Analytical Techniques 108
2.1 Chemical Analysis. 108
2.2 Structural Analysis 110
2.3 Surface Structure 110
Optical Methods; Low-energy Electron Diffraction (LEED);
Auger-electron Spectroscopy; Field-emission, Field-ion, and
 Contents xiii

Sputter-ion Microscopy; Reflection Electron Diffrac-

tion; Replica Electron Microscopy
2.4 Volume Structure 121
X-ray Diffraction; X-ray Microscopy (Topographic Methods);
Transmission Electron-diffraction and Electron-microscope
Methods
3. Conclusions 129
References 130

IV NUCLEATION, GROWTH, AND STRUCTURE OF FILMS 137

1. Nucleation 137
1.1 Condensation Process 138
1.2 Langmuir-Frenkel Theory of Condensation 140
1.3 Theories of Nucleation 142
Capillarity Theory; Statistical or Atomistic Theory; Miscel-
laneous Models; Further Deductions of the Nucleation
Theories
1.4 Experimental Results 149
Sticking Coefficient; Observations on Nucleation; Condensa-
tion Centers; Condensate Temperature
2. Growth Processes 163
2.1 General Description 163
2.2 Liquid-like Coalescence 166
Experimental Observations; Coalescence Model
2.3 Influence of Deposition Parameters 171
General Aspects; Kinetic-energy Effect; Oblique Deposition;
Electrostatic Effects
3. Some Aspects of the Physical Structure of Films 182
Crystallite Size; Surface Roughness; Density of Thin Films
4. Crystaflographic Structure of Films 189
4.1 Lattice Constant of Thin Films 191
Size Effect; Surface Pseudomorphism
4.2 Disordered and Amorphous Structures 195
Impurity Stabilization; Vapor Quenching (VQ): Codeposit
Quenching
4.3 Abnormal Metastable Crystalline Structures 199
Amorphous-Crystalline Transformation; Codeposit
Quenching of Metastable Alloys; Deposition-parameter-
controlled and Nucleated Metastable Structures; Pseu-
domorphs and Superstructures; Conclusions; Meta-
stabilization Mechanisms
4.4 Two-dimensional Superstructures 214
4.5 Fiber Texture (Oriented Overgrowth) 220
4.6 Alloy Superlattices 223
xiv Contents

5. Epitaxial-growth Phenomenon 224

5.1 Influence of Substrate and Deposition Conditions . . . . 225
Substrate; Substrate Temperature; Deposition Rate; Con-
tamination; Film Thickness; Electrostatic Effects; Depo-
sition Methods; Summary
5.2 Theories of Epitaxy 238
Royer Hypothesis; van der Merwe Theory; Brück-Engel
Theory; Nucleation Theories; Summary
6. Structural Defects in Thin Films 244
7. Concluding Remarks 252
References 254

V MECHANICAL EFFECTS IN THIN FILMS 266

1. Introduction 266
2. Internal Stresses 267
2.1 Experimental Techniques 267
Bending-plate or-beam Methods; X-ray and Electron-
diffraction Methods; Other Techniques
2.2 Experimental Results 271
Thermal Stress; Intrinsic Stress; Substrate Temperature
Dependence; Thickness Dependence; Deposition Rate
and Angle-of-incidence Dependence; Annealing Effects;
Anisotropic Stresses; Stresses in Chemically Prepared
Films
2.3 Origin of Intrinsic Stress 287
Thermal Effect; Volume Changes; Surface Layer; Surface
Tension; Electrostatic Effects; Lattice-misfit Accommo-
dation Model; Structural-defect Hypothesis; Crystallite-
boundary Mismatch Model; Anisotropic Growth
3. Mechanical Properties 295
3.1 Experimental Techniques 296
High-speed Rotor; Bulge Test; Tensile Test; Electron-
microscope Devices; Direct Measurement of Strain
3.2 Experimental Results 298
Stress-Strain Curves; Tensile Strength; Microhardness
3.3 Origin of the Tensile-strength Effects 306
Structural-defect Hypothesis; Surface Effects; Volume
Effects; Phenomenological Approach
3.4 Films vs. Whiskers 310
3.5 Stress Relief 311
4. Adhesion of Films 313
4.1 Measurement of Adhesion 314
4.2 Experimental Results 316
4.3 Origin of Adhesion 321
 Contents XV

5. Concluding Remarks 322

References 323

VI ELECTRON-TRANSPORT PHENOMENA IN METAL FILMS 328

1. Introduction 328
2. Electrical Conduction in Discontinuous Films 329
2.1 Conduction Mechanisms 329
Thermionic (Schottky) Emission; Quantum-mechanical
Tunneling; Activated Tunneling; Tunneling between
Allowed States; Tunneling via Substrate and Traps
2.2 Experimental Results 335
2.3 Temperature Coefficient of Resistivity (TCR) 340
2.4 Network (Porous) Films 342
2.5 Elastoresistance 344
3. Electrical Conduction in Continuous Films 344
3.1 Theories of Size Effect 345
3.2 Experimental Results 355
Thickness Dependence; Low-temperature Results; Size-effect
Anisotropy; Magnetic Boundary Scattering; Superimposed
Films
3.3 Temperature Coefficient of Resistivity (TCR) 365
Theory; Experimental Results
3.4 Specular Scattering 368
3.5 Field Effect 375
3.6 Influence of Absorption and Adsorption on Con-
ductivity 378
3.7 Conductivity Changes Due to Annealing 381
3.8 High-resistivity Films 387
4. Galvanomagnetic Size Effects in Thin Films 390
4.1 Introduction 390
4.2 Longitudinal Magnetoresistance 392
4.3 Transverse Magnetoresistance (Field Perpendicular to the
Film Surface-Hl) 396
4.4 Transverse Magnetoresistance (Field Parallel to the Film
Surface-H||) 398
4.5 Hall Effect in Thin Films 401
4.6 The Anomalous Skin Effect 405
4.7 Eddy-current Size Effects 409
5. Transport of Hot Electrons 411
6. Thermal Transport 417
6.1 Thermal Conductivity 417
6.2 Thermoelectric Power 419
6.3 Heat Transport across Film - Insulator Interface 423
Contents

7. Concluding Remarks 425

References 425

TRANSPORT PHENOMENA IN SEMICONDUCTING FILMS 434

1. Introduction 434
2. Theoretical Considerations 435
Mobility; Galvanomagnetic Surface Effects; Anisotropy Effects;
Quantum Size Effects
3. Experimental Results 440
3.1 Size Effects 440
3.2 Transport Properties of Thick Films 444
4. Photoconduction in Semiconductor Films 452
4.1 Activation Process 452
4.2 Photoconductivity Mechanisms 454
4.3 High-voltage Photovoltaic Effect 455
5. Field Effect - Thin-film Transistor (TFT) 456
6. Concluding Remarks 459
References 460

TRANSPORT PHENOMENA IN INSULATOR FILMS 465

1. Introduction 465
2. Dielectric Properties 466
2.1 Thin Films 466
2.2 Thick Films 470
2.3 Dielectric Losses 471
3. Piezoelectric Films 477
4. Electrical Conduction in Insulator Films 479
4.1 Conduction Mechanisms 479
4.2 Thermionic (Schottky) Emission 481
4.3 Quantum-mechanical Tunneling 483
Theories; Image-force Correction; Temperature-field (TF)
Emission; Temperature Dependence; Experimental Re-
sults; Conclusions
4.4 Bulk-limited Conduction 499
Space-charge-limited Current (SCLC) Flow; Trap and Im-
purity Effects
4.5 Voltage-controlled Negative Resistance (VCNR) . . . . 503
4.6 Current-controlled Negative Resistance (CCNR) 506
4.7 Tunnel Emission (Hot-electron Transport) 508
4.8 Tunnel Spectroscopy 514
5. Photoeffects in Tunnel Structures 516
5.1 Electroluminescence 516
 Contents xvii

5.2 Photoconduction and Photoemission 518

6. Concluding Remarks 522
References 522

IX SUPERCONDUCTIVITY IN THIN FILMS 529

1. Introduction 529
2. Basic Concepts 530
3. Transition Temperature of Thin-film Superconductors . . . . 535
3.1 Introduction 535
3.2 Thickness Dependence 537
3.3 Superconductivity-enhancement Phenomenon 539
3.4 Mechanisms of Enhanced Superconductivity 544
3.5 Influence of Stress 547
3.6 Influence of Impurities- 548
3.7 Electrostatic-charge (Field) Effect 549
3.8 Proximity Effects in Superimposed Films 550
4. Critical Magnetic Field 555
4.1 Type I Films 556
4.2 Type II Films 560
4.3 Mean-free-path Dependence of Я р 562
4.4 Transverse Critical Field 563
5. Critical Current 566
6. Propagation of Normal and Superconducting Phases . . . . 572
7. Superconductive Tunneling 573
7.1 Experimental Results 576
General; Tunneling in Superimposed Films; Gapless
Superconductivity
7.2 Supercurrent (Josephson) Tunneling 582
8. Infrared Transmission through Thin Films 586
9. Superconductive Thin-film Devices 588
9.1 Cryotrons 588
Wirewound Cryotron; Crossed-film Cryotron (CFC); The
Shielded CFC; In-line Cryotron; Multicrossover Cryotron
(MCC); Ferromagnetic Cryotron Configuration
9.2 Computer Memory Devices 593
Crowe Cell; Persistor, Persistatron, and Continuous-film
Memory (CFM)
9.3 Superconducting Magnets 595
9.4 Low-frequency Devices 596
9.5 Bolometers — Radiation Detectors 598
9.6 Tunnel Devices 598
10. Concluding Remarks 599
References 600
XVÜi Contents

X FERROMAGNETISM IN FILMS (by M. H.Cohen) 608

1. Introduction 608
2. Magnetization vs. Thickness 610
3. Stoner-Wohlfarth Model (A First Approximation) 614
4. Magnetic Anisotropy 619
4.1 Shape Anisotropy 619
4.2 Magnetocrystalline Anisotropy 620
4.3 Strain-Magnetostriction Anisotropy 621
4.4 M-induced Uniaxial Anisotropy 622
4.5 Oblique-incidence Uniaxial Anisotropy 629
4.6 Unidirectional Anisotropy 633
4.7 Perpendicular Anisotropy 633
5. Magnetization Ripple 635
5.1 Anisotropy-dispersion Model 638
5.2 Micromagnetic Model 639
Hoffmann's Theory; Harte's Theory
6. Quasi-static Manifestations of Ripple 649
6.1 Rotational Hysteresis 649
6.2 HA Domain Splitting (HA Fallback) 652
6.3 Initial Susceptibility 654
6.4 Effects of High KD/KU 658
7. Domain Walls 659
7.1 Structure of Walls 659
Bloch Walls; Ne'el Walls; Crosstie Walls; Other Wall Cal-
culations; Experimental Results
7.2 Wall Motion 666
Domain Nucleation and Growth; Coercive Force;
Wall Velocity; Magnetic Viscosity; Creep; Wall
Streaming
8. Resonance 677
8.1 Ferromagnetic Resonance 677
8.2 Spin-wave Resonance 681
8.3 Energy-loss Mechanisms 685
9. Switching 685
9.1 Coherent Rotation Theory 685
9.2 Experimental Results 687
9.3 Interpretation 691
10. Complex Magnetization Configurations 692
10.1 M Normal to Film Plane 693
MnBi Films (К]_ < 0); Stripe Domains (Ki > 0)
10.2 Multilayer Films 696
Interaction Mechanisms; Domain Wall Interactions
10.3 Cylindrical Films 698
 Contents XIX

11. Measurement Techniques 699

11.1 Microscopic Observations 699
Bitter Technique; Kerr and Faraday Magneto-optical
Effects; Lorentz Electron Microscopy
11.2 Macroscopic Measurements 702
Mechanical Detection (Torque Magnetometer); Flux-
pickup Detection; Magneto-optic Detection; Magneto-
resistive or Hall-effect Detection; Ripple-independent
H„ Determinations
12. Applications 706
12.1 Flat-film Memory 707
12.2 Cylindrical-film Memory 709
12.3 Future Developments 710
References 710

XI OPTICAL PROPERTIES OF THIN FILMS 721

1. Introduction 721
2. Thin Film Optics 722
2.1 Reflection and Transmission at an Interface 723
2.2 Reflection and Transmission by a Single Film . . . . 724
2.3 Anisotropic and Inhomogeneous Films 728
2.4 Multilayer Films 728
2.5 Optical Absorption 729
3. Optical Constants of Thin Films 732
3.1 Experimental Methods 732
Reflection Methods; Reflectance and Transmittance
Methods; Interferometric Methods; Spectrophoto-
metric Methods; Critical-angle Method; Polarimetrie
Methods (Ellipsometry); Summary
3.2 Results on Optical Constants 741
General Remarks; Metal Films; Abnormal Absorp-
tion Phenomenon; Maxwell-Garnett Theory of
Abnormal Absorption; Dielectric and Semicon-
ducting Films
3.3 Size Effects in Optical Properties 757
Semiconductor and Dielectric Films; Metal Films
4. Thin Film Absorption and Photoemission Phenomena . . . . 761
4.1 Infrared Absorption 761
Optical Modes; Surface Modes
4.2 Magneto-optical Absorption 763
4.3 Plasma-resonance Absorption 764
4.4 Ultraviolet Absorption 767
4.5 Photoemission from Metal Films 767
XX Contents

5. Multilayer Optical Systems 769

5.1 Antireflection Coatings 770
Inhomogeneous Films; Homogeneous Single Films; Multi-
layer Films; Infrared Antireflection Coatings
5.2 Reflection Coatings 777
Metal Mirrors; All-dielectric System
5.3 Interference Filters 781
Reflection Filters; Transmission Interference Filters;
Frustrated Total-re flection Filter
5.4 Absorptance and Thermal Emittance of Coatings . . . 785
5.5 Thin-film Polarizers 786
6. Concluding Remarks 786
References 787

Author Index 795

Subject Index 827