Crystal Growth - 2nd Edition - ISBN: 9780080250434, 9781483161464

Crystal Growth

2nd Edition

International Series on the Science of the Solid State

Editors: Brian R. Pamplin
eBook ISBN: 9781483161464
Imprint: Pergamon
Published Date: 1st January 1980
Page Count: 628
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Crystal Growth, Second Edition deals with crystal growth methods and the relationships between them. The chemical physics of crystal growth is discussed, along with solid growth techniques such as annealing, sintering, and hot pressing; melt growth techniques such as normal freezing, cooled seed method, crystal pulling, and zone melting; solution growth methods; and vapor phase growth. This book is comprised of 15 chapters and opens with a bibliography of books and source material, highlighted by a classification of crystal growth techniques. The following chapters focus on the molecular state of a crystal when in equilibrium with respect to growth or dissolution; the fundamentals of classical and modern hydrodynamics as applied to crystal growth processes; creation, control, and measurement of the environment in which a crystal with desired properties can grow; and growth processes where transport occurs through the vapor phase. The reader is also introduced to crystal growth with molecular beam epitaxy; crystal pulling as a crystal growth method; and zone refining and its applications. This monograph will be of interest to physicists and crystallographers.

Table of Contents

1. Introduction to Crystal Growth Methods

1.1. Main Categories of Crystal Growth Methods

1.2. The Chemical Physics of Crystal Growth

1.3. Solid Growth Techniques

1.3.1. Introduction

1.3.2. Annealing Techniques

1.3.3. Sintering and Hot Pressing

1.4. Melt Growth Techniques

1.4.1. Introduction

1.4.2. Normal Freezing, Directional Freezing, or Bridgman-Stockbarger Method

1.4.3. Cooled Seed Method

1.4.4. Crystal Pulling

1.4.5. Zone Melting

1.4.6. Flame Fusion Techniques

1.4.7. Arc Fusion Techniques

1.5. Solution Growth Methods

1.6. Vapor Phase Growth

1.7. Choosing a Crystal Growth Method

1.8. The Literature of Crystal Growth

2. Nucleation and Growth Theory

2.1. Introduction

2.2. Crystal Models

2.2.1. Atomic Bonding

2.2.2. Formation Energy of Clusters on a Crystal Plane

2.2.3. Surface Diffusion

2.3. Supersaturation, Supercooling, and Volume Energy

2.3.1. Growth from the Vapor

2.3.2. Growth from the Melt

2.3.3. Growth from Solution

2.4. Basic Nucleation Theory

2.5. Three-dimensional Nucleation

2.5.1. Nucleus Formation Energy

2.5.2. The Formation Energy of Liquid Nuclei

2.5.3. The Formation Energy of Crystalline Nuclei

2.5.4. Nucleation Rates

2.6. The Growth of Crystal Surfaces

2.6.1. Introduction

2.6.2. The Equilibrium Structure of Surfaces and Steps

2.6.3. The Equilibrium Structure and Formation Energy of Two-dimensional Nuclei

2.6.4. Two-dimensional Nucleation and Growth

2.6.5. Screw Dislocation Growth

2.6.6. Application to Vapor, Melt, and Solution Growth

2.7. Simulated Crystal Growth

2.7.1. The Scope and Objectives of Simulation Studies

2.7.2. Equilibrium Surface Structure

2.7.3. Nucleation and Growth

2.8. Material and Heat Flow in Crystal Growth

2.8.1. Growth from Solution

2.8.2. Growth from the Melt

2.8.3. Growth from the Vapor

2.9. The Kinetic Generation of Crystal Forms

2.9.1. Whiskers

2.9.2. Needles and Platelets

2.9.3. Flat Faces

2.9.4. Equilibrium and Characteristic Habits

2.9.5. Dendrites

3. Hydrodynamics of Crystal Growth Processes

3.1. Introduction

3.2. Fundamentals

3.2.1. Flowfields

3.2.2. The Flownet

3.2.3. Navier-Stokes Equations

3.2.4. The Vorticity Transport Equation

3.2.5. Transport Coefficients

3.3. Flow over Crystals in Solution

3.3.1. Stokes Flow

3.3.2. Flow around Asymmetric Crystals in Solutions

3.3.3. Flow Separation

3.4. Boundary Layer Phenomena

3.4.1. Boundary Layers

3.4.2. Boundary Layer Flow over a Flat Surface

3.5. Flow in Rotating Fluids

3.5.1. Flow to a Rotating Disk Substrate

3.5.2. Flow to a Rotating Fluid

3.5.3. Flow between Two Rotating Plane Surfaces

3.5.4. Accelerated Crucible Crystal Growth

3.5.5. Detached Shear Layers

3.5.6. Flow in Czochralski Crystal Growth

3.6. Flow in Gas Phase Epitaxial Reactors

3.6.1. Flow in a Straight Channel

3.6.2. Flow in Vertical Cylinder Reactors

3.6.3. Stagnation Flow Reactors

3.7. Thermally Driven Flow

3.7.1. Convective Flow on Vertical Surfaces

3.7.2. Convective Flow in Fluids Heated from below

3.7.3. Horizontal Normal Freezing

3.7.4. Convective Instabilities in Vapor Phase Crystal Growth

3.8. Flow-Assisted Mass Transfer

3.8.1. Mass Transfer Equations

3.8.2. Growth Rate of Crystals in Stokes Flow

3.8.3. Growth Rate on a Rotating Surface

3.8.4. Mass Transfer through Boundary Layers

3.8.5. Growth Rates in Epitaxial Reactors

3.9. Conclusions

4. Environment For Crystal Growth

4.1. Introduction

4.1.1. General Remarks on Instrumentation

4.1.2. Definitions in Measurement

4.2. Temperature

4.2.1. Methods of Heating

4.2.2. Temperature Measurement

4.2.3. Temperature Control

4.3. Atmosphere

4.3.1. Vacuum Techniques

4.3.2. High Pressure Techniques

4.3.3. Dynamic Atmospheres

4.4. Container Materials

4.4.1. General Considerations

4.4.2. Maintenance of Containers

4.5. Growth Velocity

4.5.1. Macroscopic Growth Velocity

4.5.2. Microgrowth Fluctuations

4.6. Conclusion

5. Vapor Phase Growth

5.1. Introduction

5.2. Thermodynamics

5.2.1. SiCl4 Growth of Si

5.2.2. Composition of III V Alloys

5.3. Mass Transport

5.3.1. Closed Tube Systems

5.3.2. Horizontal Reactor

5.3.3. Vertical Reactor

5.4. Interface Kinetics

5.4.1. Si Growth from SiH4

5.4.2. GaAs Growth Kinetics

5.5. Defect Generation

5.5.1. Sources of Defects

5.5.2. Si/Si:B

5.5.3. III-V Alloy Systems

5.5.4. Si on Sapphire

5.6. Conclusions

6. MBE—Molecular Beam Epitaxial Evaporative Growth

6.1. Introduction

6.1.1. Evaporative Methods Other than MBE

6.2. Apparatus and Instrumentation

6.2.1. General

6.2.2. Vacuum Systems

6.2.3. Evaporation Sources

6.2.4. Substrate Holders and Heaters and Sample Manipulators

6.2.5. Instrumentation

6.3. MBE—Crystal Growth

6.3.1. Phase Equilibria and Stoichiometry—GaAs

6.3.2. Stoichiometry

6.3.3. Deposition

6.4. Substrate Preparation

6.5. Surface Structures

6.6. Adsorption and Desorption

6.6.1. Interaction of As, Ga and Al on GaAs

6.6.2. Doping and Stoichiometry in MBE

6.6.3. Oxidation

6.7. Specific Materials and Specialized Structures

6.7.1. Silicon

6.7.2. GaAs-GaAlAs and Other III-V's

6.7.3. IV-VI's: PbSnTe

6.7.4. ZnSe and Other II-VI's

7. Crystal Pulling

7.1. Introduction

7.2. Material Considerations

7.2.1. Liquid Material Limitations

7.2.2. Crucible Selection

7.2.3. Heat Sources

7.2.4. Furnace Construction

7.3. Crystal Growth

7.3.1. Growth Rate

7.3.2. Thermal Gradients

7.3.3. Thermal Effects

7.3.4. Growth Striations

7.4. Solid Solutions and Impurities

7.5. Growth Control

7.5.1. Temperature Control

7.5.2. Diameter Control

7.6. Special Techniques

7.6.1. Silicon Growth

7.6.2. Liquid Encapsulation Czochralski (LEC)

7.6.3. Flux Pulling

7.6.4. Shaped Growth

8. Zone Refining and Its Applications

8.1. Introduction

8.1.1. Brief Description

8.1.2. Brief History

8.2. Theoretical Aspects of Zone Melting

8.2.1. The Distribution Coefficients

8.2.2. Solute Distribution in Normal Freezing Processes

8.2.3. Solute Distribution in Zone Melting

8.3. Factors Affecting the Practice of Zone Melting

8.3.1. The Zone Length

8.3.2. Zone Traverse Velocity

8.3.3. Temperature Gradient at the Solid-Liquid Interface

8.3.4. The Degree of Mixing in the Liquid

8.3.5. Matter Transport in Zone Melting

8.4. Design and Choice of Zoning Equipment

8.4.1. Zoning in a Container

8.4.2. Zone Refining Without Containers

8.4.3. Traverse Mechanisms

8.4.4. Design Considerations For "Ideal Zones"

8.4.5. Stirring

8.5. Modifications of Zone Refining

8.5.1. Liquid Encapsulation

8.5.2. Microscale Zone Melting

8.5.3. Direct Current Effects and Zone Melting

8.6. Allied Techniques

8.6.1. Thin Alloy Zone Techniques

8.7. Conclusions

9. Methods of Growing Crystals under Pressure

9.1. Introduction: Explanation of the Decomposition Tendency of Compounds Having Mixed Bonding

9.2. Resistance Heater Methods

9.2.1. Bridgman Growth Under High Inert Gas Pressure

9.2.2. The Capillary-Tipped Ampoule Method for ZnTe

9.2.3. The "Soft Ampoule" Method

9.2.4. Preparing II-VI Compounds from the Pure Elements

9.3. Induction Heater Methods

9.3.1. Vertical and Horizontal Bridgman Method in Unsupported Quartz Ampoules

9.3.2. Vertical Bridgman Growth in Pressure-Relieved Ampoules

9.3.3. Czochralski-Type Pulling under Pressure

9.4. Crystal Growth Using Liquid Encapsulation (LE)

9.4.1. Czochralski Pulling

9.4.2. Liquid Encapsulation Bridgman Growth

9.4.3. Liquid Encapsulation Zone Leveling

9.5. Outlook: New Methods

9.5.1. Issuing Phosphorus Vapor into the Melt

9.5.2. Continuous Liquid-Phase Epitaxy Growth

9.6. Summary and Conclusions

10. Crystallization from Solution at Low Temperatures

10.1. Introduction

10.2. Basic Requirements

10.2.1. Choice of Solvent

10.3. Crystallization Apparatus

10.3.1. A General Purpose Laboratory Crystallizer

10.4. Saturation and Seeding

10.4.1. Saturation

10.4.2. Seed Selection and Mounting

10.5. Factors That Influence the Perfection of the Final Crystal

10.6. Control of Crystal Morphology

11. Liquid Phase Epitaxy

11.1. Introduction

11.2. Apparatus

11.3. Phase Diagrams

11.4. Growth Kinetics

11.4.1. Modes of LPE Growth

11.4.2. Diffusion Equations Used to Describe LPE Growth

11.4.3. Semi-Infinite Solutions without Interfacial Kinetics

11.4.4. Semi-Infinite Solutions with Interfacial Kinetics

11.5. Surface Morphology and Lattice Mismatch

11.5.1. Surface Morphologies

11.5.2. Supercooling and Substrate Misorientation Effects

11.5.3. Stresses and Surface Changes as a Result of Mismatch

11.5.4. Changes in Growth Rate and Segregation Coefficients Resulting from Mismatch

11.6. Outlook For LPE

11.7. Appendixes

11.8. Symbols

12. High-Temperature Solution Growth

12.1. Introduction

12.2. Choice of a Solvent

12.3. Experimental Techniques

12.3.1. General Requirements

12.3.2. Growth Stability

12.3.3. Slow Cooling

12.3.4. Evaporation

12.3.5. Gradient Transport

12.3.6. Thin Solvent Zone Methods

12.3.7. Electrocrystallization

12.3.8. Stirring

12.3.9. Liquid Phase Epitaxy

12.4. Studies of the Growth Mechanism

12.5. Summary

13 Dendritic Growth

13.1. Introduction

13.2. Consequences of Dendritic Growth

13.2.1. Morphology

13.2.2. Crystal Defects

13.2.3. Solute Segregation

13.2.4. Void Formation

13.2.5. Crystal Multiplication

13.2.6. Importance and Origin of Dendritic Growth

13.3. Instabilities That Cause Dendritic Growth

13.4. Steady-State Dendritic Growth Velocity

13.4.1. Elementary Treatment

13.4.2. Improvements to This Elementary Treatment

13.5. Experimental Observations of Dendritic Growth Velocities

13.6. Other Studies of Dendritic Growth

13.6.1. Dendrite Arm Spacing

13.6.2. Influence of Fluid Flow on Dendritic Growth Phenomenon

13.7. Appendix

14 Bulk Crystallization

14.1. Supersaturation

14.1.1. Supersaturation and Metastability

14.1.2. Measurement of Supersaturation

14.2. Nucleation

14.3. Crystal Growth

14.3.1. Overall Growth Rates

14.3.2. Face Growth Rates

14.3.3. Size-Dependent Growth

14.3.4. Expression of Crystal Growth Rates

14.3.5. Mass Transfer Correlations

14.3.6. "Films" and "Boundary Layers"

14.4. Habit Modification

14.4.1. Industrial Importance

14.5. Crystallization Methods and Equipment

14.5.1. Cooling Crystallizers

14.5.2. Controlled Crystallization

14.5.3. Direct Contact Cooling

14.5.4. Classifying Crystallizers

14.5.5. Evaporating and Vacuum Crystallizers

14.5.6. Forced Circulation Evaporators

14.5.7. Vacuum Operation

14.5.8. Salting-out Crystallization

14.5.9. Reaction Crystallization

14.5.10. Spray Crystallization

14.5.11. Melt Crystallization

14.6. Design and Operation of Crystallizers

14.6.1. Crystallizer Selection

14.6.2. Information For Design

14.6.3. Crystal Yield

14.6.4. Scale-up and Operating Problems

14.6.5. Modes of Operation

14.6.6. Concept of the Population Balance

14.6.7. Crystal Size Distributions

14.6.8. Applications of the Population Balance

15. Assessment of Crystalline Perfection

15.1. Introduction

15.2. Volume, Area, Line, and Point Defects

15.3. Threshold Concentrations of Defects in Crystals

15.4. Methods for Detecting Structural Imperfections

15.4.1. Optical Methods

15.4.2. Transmission Electron Microscopy

15.4.3. X-Ray Topography

15.4.4. Scanning Electron Microscopy

Subject Index

Organic Compounds Index

Inorganic Compounds Index

Table of Fundamental Physico-Chemical Constants

Table of Useful Conversions of Units

Table of Energy Conversion Factors

Periodic Table


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Brian R. Pamplin

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