DIFFUSION

PHENOMENA
IN THIN FILMS AND
MICROELECTRONIC
MATERIALS
Edited by

Devendra Gupta and Paul S. Ho

IBM Thomas J. Watson Research Center
Yorktown Heights, New York

np

NOYES PUBLICATIONS
Park Ridge, New Jersey, U.S.A.

Contents

1. SOME FORMAL ASPECTS OF DIFFUSION: BULK SOLIDS

AND THIN FILMS
Devendra Gupta
Introduction
Mathematical Basis of Diffusion
Single Crystals
Fick's First Law
Fick's Second Law
Instantaneous Source Geometry
Thick Layer Geometry
Infinite Couple with Surface Composition Constant
Boltzmann-Matano Analysis
Structurally Inhomogeneous Samples
Experimental Techniques
Microsectioning Diffusion Measurements
Surface Accumulation Techniques
Thermodynamical Considerations
Driving Force F on Individual Atoms Is Zero
Pressure and Mass Dependence of Diffusion
Pressure Dependence
Mass Dependence
Driving Force F on Individual Atoms Is Finite-Linear Chemical
Diffusion Regime
Non Linear Chemical Diffusion Regime
Structure of Grain Boundaries, Mobile Defects and Diffusion
Hierarchy
Grain Boundary Structure and State of Mobile Defects
Mechanism of Grain Boundary Diffusion
Anisotropy and Orientation of Grain-Boundary Diffusion
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Contents
Diffusion Data in Grain Boundaries and Thin Films:
Diffusion Hierarchy
Relationship Among GB Diffusion, Lattice Diffusion and GB
Energy
Influence of Solute Segregation on GB Self-Diffusion and Its
Relationship with GB Energy, Solute Segregation and GB
Diffusion
Thermal Behavior of KSDJ,
Composition Dependence of K8l)\y
Estimating Grain Boundary Segregation Parameters from
Diffusion Measurements
Variable Effects of Solutes on GB Diffusion
Concluding Remarks
References

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2. ANELASTIC RELAXATION AND DIFFUSION IN THIN-LAYER

MATERIALS
73
Brian S. Berry
Introduction
73
Anelastic Relaxation Behavior
74
Quasi-Static Response Functions
75
Dynamic Anelastic Behavior: The Internal Friction Peak
79
Anelastic Behavior with Multiple or Distributed Relaxation
Times
83
Thermally-Activated Relaxation Behavior
84
Experimental Methods
88
Vibrating-Reed Apparatus
89
The Mandrel Method for Quasi-Static Measurements
94
Accommodation Stress and the Bending Bilayer
97
Interstitial Solute Diffusion in BCC Metals
99
The Snoek Relaxation
100
Experimental Results
104
Hydrogen Diffusion in Metallic Glasses
Ill
The Hydrogen Reorientation Relaxation
112
The Gorsky Relaxation. .
117
Other Thermally-Activated Processes in Metallic Glasses
121
Grain-Boundary Diffusion in Pure and Alloyed Aluminum Films . . 123
Point-Defect Relaxations in Ion-Implanted Silicon
128
Structural Relaxation in Silicon Monoxide
133
Concluding Remarks
136
Appendix: Frequencies and Internal Friction of a Multilayered
Reed
137
References
141
3. DIFFUSION IN ARTIFICIALLY MODULATED FILMS
A. Lindsay Greer
Introduction
Theory

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Contents
Interdiffusion in a Steep Concentration Gradient
Gradient Energy Effects
Strain Effects
Non-Linear Diffusion Effects
Measurement Techniques
Relationship to Other Diffusion Measurements
Stability of Modulated Structures
Experimental Results on Crystalline Metals
Early Work
Gold-Silver
Copper-Palladium
Gold-Nickel
Copper-Gold
Copper-Nickel
Silver-Palladium
Ternary Systems
Experimental Results on Amorphous Metals
Introduction to Amorphous Metals
Interdiffusion Measurements
Discussion
Experimental Results on Semiconductors
GaAs-AlAs
GaSb-InSb
Amorphous Si-Ge
Discussion
Conclusions
References
4. DIFFUSION AND GROWTH IN OXIDE FILMS
Alan Atkinson
Introduction
Experimental Techniques
Secondary Ion Mass Spectroscopy (SIMS) Sectioning
Nuclear Reaction Depth Profiling
Sputter-Sectioning of Radioactive Tracers
Chemical Dissolution
Gaseous Exchange
Diffusion in Growing Oxide Films
Lattice Diffusion in Oxides
Point Defects in Oxides
Self-Diffusion
Cation Self-Diffusion
Oxygen Ion Self-Diffusion
Diffusion in Doped Oxides
Heterovalent Doping
Homoyalent Doping
Solute Diffusion
Tracer Solute Diffusion

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Contents
Dilute Limit
Non-Dilute
Amorphous Oxides
Theoretical Estimates of Diffusion Parameters
Short-Circuit Diffusion
Dislocation Diffusion
Grain Boundary Diffusion
Surface Diffusion
Theoretical Studies of Dislocations, Grain Boundaries and
Surfaces
Dislocations
Grain Boundaries
Oxide Film Growth by Thermal Oxidation
Theory of Oxide Film Growth
Thick Films
Thin Films
Defects Injected at the Metal/Oxide Interface
Defects Injected at the Oxide/Gas Interface
Oxide Films Growing by Outward Cation Transport
Growth of CoO
Growth of NiO
Growth of Other Oxides by Cation Transport
Oxide Films Growing by Inward Oxygen Transport
Growth of Highly Protective Films
Oxidation of Alloys
Protection by Incorporated Coatings
Concluding Remarks
References

5. DIFFUSION-INDUCED GRAIN BOUNDARY MIGRATION IN

THIN FILMS
Carol A. Handwerker
Introduction
Morphology and Kinetics of DIGM, DIR, and Liquid Film
Migration
Systems Exhibiting DIGM and DIR
Grain Morphology of DIGM
Crystallographic Orientation of Alloyed Regions
Surface Relief
Kinetics of Migration
Compositions of Alloyed Regions
Nucleation of New GrainsDiffusion-Induced
Recrystallization
Liquid Film Migration
Driving Force for Grain Boundary/Interface Motion
Distinctions Between Free Energy Changes and Driving
Forces
Diffusional Transport in Polycrystals with Migrating Grain
Boundaries

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Contents

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Driving Force for DIGM, DIR, and LFM

274
Effect of Coherency Strain on Interface Migration
276
Model for Coherency Strain Energy
277
Migration of Liquid Films
279
Migration Regimes for Liquid Films
282
Stress Relaxation Mechanisms
283
Migration Velocities and Morphology of the Migrating
Interface
284
Controlled Variation of Strain
285
Tests of the Coherency Strain Theory for liquid Film
Migration
286
Migration Velocities
287
Controlled Variation of Strain
288
Morphology of Migrating Interfaces
288
Other Driving Forces for Boundary Migration
289
liquid Film Migration in Ceramics
290
Effect of Diffusion-Induced Strain on Grain Boundary
Migration
291
Distinctions Between Grain Boundaries and liquid Films
291
Qualitative Test of the Coherency Strain Theory for DIGM. . . . 292
Critical Values of Dg/V
295
Features of Grain Boundaries Required to Quantitatively
Model DIGM
297
Unequal Grain Boundary Diffusivities
297
Unequal Lattice Diffusivities of the Solute and Solvent
Species
298
Grain Boundaries as Sources/Sinks for Vacancies
299
Geometrical Constraints
300
Grain Boundary Structure Effects in DIGM
301
Relative Rates of Grain Boundary and Lattice Diffusion. . . . 301
Stress Relief Mechanisms
302
Other Driving Forces
303
Mechanism Maps for DIGM and DIR
303
Special Considerations for Thin Films
312
References
314
6. EFFECTS OF AMBIENTS ON THIN FILM INTERACTIONS
Chin-An Chang
Introduction
Observed Ambient Effects
Enhanced Interactions
Reduced Interactions
Mechanisms for the Ambient Effects
Sinking Effect Model
Surface Energy Model
Interface Oxide Model
Surface Potential Model
Observation of Other Ambient Effects from the Surface
Potential Model

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xiv

Contents
Reduced Interaction in Au Systems by CO
330
Reduced Interactions in Pt Systems by Oxygen
332
Reduced Interactions by Oxygen for the Ni and Cu Systems . . . 333
Competing Ambient Effects
335
Diffusion Through a Less-Electronegative Metal Layer
340
Ambient Effects on Competing Interactions and on
Preferential Reactions
344
Oxidation Effects of the Outdiffused Species
346
Effect of Oxygen on the Suicide Formation
34 7
Applications and Future Studies.
354
Summary
365
References
366

7. ELECTROMIGRATION IN METALLIC THIN FILMS

Thomas Kwok and Paul S. Ho
Introduction
Electromigration in Bulk Metals
Phenomenological Description
Theory of Electromigration
Techniques of Measurement
Electromigration in Substitutional Systems
Electromigration in Metallic Thin Films
Nature of Electromigration in Metallic Thin Films
Damage Formation and Kinetics
Structural and Thermal Effects
Lifetime Measurement
Methods to Improve Electromigration Resistance
Electromigration in Fine Lines
Scaling Trends
Process and Material Related Aspects
Effect of Microstructure
Effect of Metal Line Geometry
Linelength Dependence
Linewidth Dependence
Effect of Film Thickness
Pulsed Current Powering Characteristics
Electromigration in Multilevel Interconnection
Electromigration at Contacts
Current Crowding and Local Heating in Studs and Vias
Summary
References
8. DIFFUSION BARRIERS IN SEMICONDUCTOR CONTACT
METALLIZATION
Hannu P. Kattelus and Marc A. Nicolet
Introduction
General Considerations.
Functions of a Diffusion Barrier

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Contents
Electrical Requirements in Contacts
Summary
Importance of the Choice of the Material and of the
Deposition Process
Basic Considerations
Single Crystalline Versus Non-Single Crystalline Films
Summary
Polycrystalline Films Consisting of One Single Layer
Elemental Metallic Films
Effect of ImpuritiesStuffed Barrier
Compound FilmInert Barrier
From Elemental to Compound Films
Single Phase Compounds
Multiphase Compounds
Summary
Amorphous Films Consisting of One Single Layer
General Observations
Examples of Amorphous Diffusion Barriers
Summary
Multilayer Configurations
Sacrificial Barrier
Contacting Layers
Tandem Barriers
Summary
References
9. THERMAL STABILITY OF Pb-ALLOY JOSEPHSON JUNCTIONS.
Masanori Murakami
Introduction
Thermal Strain of Films on Rigid Substrates
Thermal Stability Below Room Temperature
Pb Thin Films
Strain Behavior
Microstructure Changes After Repeated Thermal Cycling
Reduction of Strain Relaxation
Pb-In-Au Base Electrode Material
Strain Behavior
Microstructure Change After Repeated Thermal Cycling.
Correlation Between Device Reliability and Microstructure Change
Pb-Bi Counterelectrode Material
Strain Behavior
Microstructure Change After Repeated Thermal Cycling.
Correlation Between Device Reliability and Microstructure Changes
Thermal Stability Above Room Temperature
Strain Behavior
Primary Strain Relaxation Process

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Contents
Secondary Relaxation Process
Hillock Formation of Pb-In-Au Base Electrode
Mechanism
Reduction of Hillock Formation
Summary
References

10. DIFFUSION AND ELECTROMIGRATION OF IMPURITIES IN

LEAD SOLDERS
Chao-Kun and Hillard B. Huntington
Introduction
Fast Diffusers in Pure Lead
Diffusion
Electromigration
Dilute Impurities in Lead-Tin Solders
Impurities Subjected to Trapping by the Added Tin
Diffusion
Electromigration
An Impurity Not Subject to TrappingSilver
Diffusion
Electromigration
Experiments With 1000 ppm Nickel
Diffusion
Electromigration
Dilute Impurities in Lead-Indium Solders
Diffusion in Lead-Indium Alloys
Electromigration
Conclusion
References
INDEX

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