HANDBOOK OF

SEMICONDUCTOR WAFER
CLEANING TECHNOLOGY

Science, Technology,
and Applications

Edited by

Werner Kern

Werner Kern Associates

East Windsor, New Jersey

NOYES PUBLICATIONS
WeStwOOd,New Jersey, U.S.A.
Contents

Part I. Introduction and Overview

1 Overview and Evolution of Semiconductor

Wafer Contamination and Cleaning Technology ... .3
Werner Kern
1 .O INTRODUCTION ................................................................. 3
1 .l Importance of Clean Wafer Surfaces ......................... 3
1.2 Wafer Cleaning Technology ....................................... 4
1.3 Scope and Organization of this Chapter ..................... 4
2.0 OVERVIEW OF WAFER CONTAMINATION ASPECTS.. .. .5
2.1 Types and Origins of Contaminants.. .......................... 5
2.2 Types of Semiconductor Wafers ................................ 7
2.3 Effects of Contaminants on Semiconductor Devices . 8
2.4 Prevention of Contamination from Equipment
and Processing.. ....................................................... IO
2.5 Purity of Chemicals .................................................. 11
2.6 Analytical Methods ................................................... 14
3.0 OVERVIEW OF WAFER CLEANING TECHNOLOGY.. ..... 15
3.1 Approaches for Attaining Clean Semiconductor
Wafers ................................................................. 15
3.2 Liquid Cleaning Methods .......................................... 15
3.3 Wet-Chemical Cleaning Processes .......................... 17
3.4 Implementation of Wet-Chemical Cleaning
Processes ................................................................ 22

xi
xii Contents

3.5 Wafer Rinsing, Drying, and Storing .......................... 24

3.6 Vapor-Phase Cleaning Methods ............................... 25
4.0 EVOLUTION OF WAFER CLEANING SCIENCE AND
TECHNOLOGY ................................................................. 28
4.1 Period from 1950 to 1960 ......................................... 28
4.2 Period from 1961 to 1971 ......................................... 29
4.3 Period from 1972 to 1989 ......................................... 44
4.4 Period of October 1989 to Mid-1992 ......................... 48
5.0 SUMMARY AND CONCLUSIONS ..................................... 55
REFERENCES ................................................................. 57

2 Trace Chemical Contamination on

Silicon Surfaces ............................................... . ....... 68
Don To/liver
1 .O INTRODUCTION ............................................................... 68
1 .I Horizontal and Vertical Dimensions .......................... 71
1.2 A Manufacturing Issue, Not a Device Design
Specification ............................................................ 72
1.3 Cleaning Technology in the United States ................ 72
1 .4 Visibility of the Problem.. .......................................... 73
1.5 Management of Surface Contamination in
Manufacturing .......................................................... 74
1.6 Gallium Arsenide and other Ill-V Compound
Semiconductors ....................................................... 74
2.0 SOURCES OF CHEMICAL CONTAMINATION ................. 75
2.1 Cleanroom Air .......................................................... 76
2.2 Cleanroom Personnel ............................................... 76
2.3 Liquid Sources and Photolithographic Resists .......... 76
2.4 Materials, Components, and Systems for
Process Liquids ........................................................ 83
2.5 Storage and Transport of Liquids and Chemicals ...... 84
2.6 High-Purity Process Gases in the Semiconductor
Fab as a Source of Surface Contamination .............. 85
2.7 Chemical Contamination from Thermal Process
Tools and Systems ................................................... 91
2.8 Plasma Etch, Strip, and RIE Processing Tools ......... 91
2.9 Wet Etching, Wet Cleaning, and Drying Equipment.. 94
2.10 Vacuum Processing Equipment.. .............................. 99
2.11 Wafer Handling and Storage Systems .................... 100
3.0 KILLER CONTAMINANTS ............................................... 101
3.1 Particle Concentrations .......................................... 101
3.2 Trace Metal Concentrations.. .................................. 103
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_._

3.3 Killers Other than Particles and Metallics ............... 103

4.0FUTURE DIRECTIONS AND NEEDS.. ............................ 103
4.1 Equipment Design .................................................. 103
4.2 Material Specifications ........................................... 104
4.3 Fabrication and Installation.. ................................... 104
4.4 Characterization and Evaluation ............................. 104
4.5 Safety and Environmental Requirements ............... 104
4.6 Directions in Research and Development ............... 105
REFERENCES ............................................................... 106

Part II. Wet-Chemical Processes

3 Aqueous Cleaning Processes ............................... 111

Don C. Burkman, Donald Deal,
Donald C. Grant, and Charlie A. Peterson
1 .O INTRODUCTION TO AQUEOUS CLEANING.. ................ 111
1 .l Advantages of Aqueous Cleaning: .......................... 112
1.2 Disadvantages of Aqueous Cleaning: ..................... 112
2.0 CONSIDERATIONS OF CONTAMINANTS AND
SUBSTRATES ............................................................... 113
2.1 Surface Effects--Forces Holding the Contaminants 114
2.2 Chemical Adsorption .............................................. 115
2.3 Physical Adsorption ................................................ 115
3.0 FACTORS AFFECTING AQUEOUS CLEANING ............. 118
3.1 Predicting and Enhancing Contaminant Solubility ... 118
3.2 Etching as a Means of Contaminant Removal ........ 119
4.0 CLEANING CHEMISTRIES ............................................. 120
5.0 AN EXAMPLE OF AN AQUEOUS CHEMICAL
CLEANING PROCESS .................................................... 122
5.1 Organic Removal ................................................... 122
5.2 Native Oxide Removal ........................................... 122
5.3 Particle Removal With Simultaneous Oxide
Regrowth ............................................................... 123
5.4 Metal Removal ....................................................... 123
6.0 EFFECTS OF PROCESS VARIABLES ON AQUEOUS
CHEMICAL CLEANING ................................................... 124
6.1 The Effect of Changing the Sequence of the
Chemical Cleaning Steps ...................................... 124
6.2 The Effect of Concentration.. .................................. 127
6.3 The Effect of Temperature ..................................... 127
6.4 Wetting ............................................................... 128
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6.5 The Effect of Solution Degradation.. ....................... 130

6.6 Carrier Effects ........................................................ 131
7.0 SEMICONDUCTOR WAFER DRYING ............................ 131
7.1 Centrifugal Drying .................................................. 131
7.2 Vapor Drying .......................................................... 133
7.3 Hot Water Drying Techniques ................................ 134
8.0 EQUIPMENT USED FOR AQUEOUS CLEANING .......... 134
8.1 General Design Considerations .............................. 134
8.2 Immersion Processors.. .......................................... 136
8.3 Spray Processors ................................................... 137
8.4 Ultrasonics and Megasonics ................................... 141
8.5 Liquid Displacement Processors.. ........................... 142
8.6 Point of Use Chemicals .......................................... 143
8.7 Single-Wafer Cleaners ........................................... 143
8.8 Alternative Cleaning Techniques ............................ 144
8.9 Combined Wet/Dry Systems .................................. 144
8.10 Rinsing and Drying ................................................. 145
9.0 CONCLUSION ............................................................... 146
REFERENCES ............................................................... 147

4 Particle Deposition and Adhesion ........................ 152

Robert P. Donovan and Venu B. Menon
1 .O INTRODUCTION ............................................................. 152
2.0 AEROSOL PARTICLE DEPOSITION .............................. 153
2.1 Thermal Effects.. .................................................... 164
3.0 PARTICLE DEPOSITION FROM A LIQUID BATH .......... 167
3.1 Comparison of Hydrosol and Aerosol Particle
Deposition Mechanisms ......................................... 168
3.2 Concepts of Colloid Chemistry ............................... 170
3.3 Zeta Potential and Particle Deposition .................... 175
3.4 Effect of Ionic Strength on Electric Double Layer
Repulsion ............................................................... 180
3.5 Van der Waals Attraction.. ...................................... 181
4.0 DLVO THEORY.. ............................................................. 182
4.1 The Effect of Solution pH on Colloid Deposition ..... 184
4.2 Hydrophobic Surfaces ............................................ 187
4.3 EDR Effects in the Filtration of Colloids.. ................ 188
5.0 PARTICLE ADHESION ................................................... 190
5.1 Other Adhesive Forces.. ......................................... 194
6.0 SUMMARY ............................................................... 195
REFERENCES ............................................................... 196
 Contents xv

Part III. Dry Cleaning Processes

5 Overview of Dty Wafer Cleaning

Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..~..... 201
Jetzy Ruzyllo
1.0 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . 201
2.0 LIMITATIONS OF WET WAFER CLEANING
PROCESSES . . . . . . . .. . .. . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . 202
3.0 ANTICIPATED ROLE OF DRY WAFER CLEANING
IN IC FABRICATION . . . . . .. .. . . . .. .. . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
4.0 REQUIREMENTS OF DRY WAFER CLEANING
TECHNOLOGY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
5.0 MECHANISMS OF DRY WAFER CLEANING . . . . . . . . . . . . . . . . . 206
6.0 GENERAL OUTLINE OF DRY WAFER CLEANING
METHODS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . 210
7.0 REVIEW OF EXPERIMENTAL RESULTS . . . . . . . . .. . . . .. . . . . . . . . 213
7.1 Cleaning Through Physical Interactions . . . . . . . . . . . . . . . . . . 213
7.2 Thermally Enhanced Cleaning . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . 214
7.3 Vapor Phase Cleaning . . . . . . . . . . . . . . . .. . .. . . . . . . . . . . . . . . . . . . .. . . . . 216
7.4 Photochemically-Enhanced Cleaning . . . . . . . . . . . . . . . . . . . . . 219
7.5 Plasma-Enhanced Cleaning . . .. . . . . . . . . . . . . . . .. . . . . . . . . .. . . . 224
6.0 SUMMARY . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . .. .. . 227
REFERENCES ............................................................... 226

6 Ultraviolet-Ozone Cleaning Of
Semiconductor Surfaces ....................................... 233
John R. Vig
1 .O INTRODUCTION ............................................................. 233
2.0 HISTORY OF UV/OZONE CLEANING ............................ 233
3.0 VARIABLES OF UVIOZONE CLEANING ........................ 237
3.1 Wavelengths Emitted by the UV Sources ............... 237
3.2 Distance Between the Sample and UV Source ....... 240
3.3 Contaminants.. ....................................................... 241
3.4 Precleaning ............................................................ 242
3.5 Substrate ............................................................... 243
3.6 Rate Enhancement Techniques.. ............................ 244
4.0 MECHANISM OF UV/OZONE CLEANING ...................... 246
5.0 UV/OZONE CLEANING IN VACUUM SYSTEMS ........... .248
6.0 SAFETY CONSIDERATIONS.. ........................................ 249
7.0 CONSTRUCTION OF A UVIOZONE CLEANING
FACILITY ............................................................... 251
xvi Contents

8.0 APPLICATIONS .............................................................. 253

8.1 Cleaning of Silicon Surfaces .................................. 253
8.2 Cleaning of Other Semiconductor Surfaces.. .......... 256
8.3 Other Applications .................................................. 257
9.0 EFFECTS OTHER THAN CLEANING ............................. 260
9.1 Oxidation ............................................................... 260
9.2 UV-Enhanced Outgassing ...................................... 261
9.3 Other Surface/Interface Effects .............................. 261
9.4 Etching ............................................................... 262
10.0 SUMMARY AND CONCLUSIONS ................................... 262
REFERENCES ............................................................... 263

7 Vapor Phase Wafer Cleaning Technology .......... .274

Bruce E. Deal and C. Robert Helms
1 .O INTRODUCTION AND BACKGROUND.. ......................... 274
1 .I General ............................................................... 274
1.2 Aqueous Cleaning Processes ................................. 276
1.3 “Dry” Cleaning Processes ...................................... 276
1.4 Other Types of Cleaning Processes ....................... 277
2.0 VAPOR CLEANING ......................................................... 277
2.1 Historical ............................................................... 277
2.2 Advantages of Vapor Cleaning ............................... 280
2.3 Current Vapor Cleaning Systems ........................... 282
3.0 OXIDE ETCHING ............................................................ 288
3.1 Thermal Oxides.. .................................................... 288
3.2 Native/Chemical Oxides.. ....................................... 293
3.3 Deposited Oxides ................................................... 296
4.0 MECHANISM OF OXIDE ETCHING ................................ 296
4.1 Background ............................................................ 296
4.2 Important Aqueous Chemistry ................................ 298
4.3 Vapor Phase Mechanisms ...................................... 303
4.4 Summary ............................................................... 309
5.0 IMPURITY REMOVAL ..................................................... 310
5.1 Types of Contamination ......................................... 310
5.2 Evaluation Techniques ........................................... 310
5.3 Particles and Residues ........................................... 311
5.4 Organic Contaminants.. .......................................... 313
5.5 Metallic Contaminants ............................................ 314
5.6 Mechanisms of Metal Impurity Removal ................. 316
6.0 DEVICE APPLICATIONS ................................................ 318
6.1 General Effects of Impurities on Device Properties 318
6.2 Junction Characteristics ......................................... 318
 Contents xvii

6.3
Contact/Interface Properties ................................... 318
6.4 Gate Oxide Properties.. .......................................... 321
7.0 INTEGRATED PROCESSING ......................................... 324
7.1 Concept ............................................................... 324
7.2 Advantages and Disadvantages of integrated
Processing ............................................................. 325
7.3 Requirements/Considerations of Integrated
Processing ............................................................. 326
7.4 Applications Involving Vapor Cleaning ................... 327
8.0 CONCLUSIONS AND SUMMARY ................................... 329
REFERENCES ............................................................... 330

8 Remote Plasma Processing for Silicon

Wafer Cleaning . . . . . . . . . . . . . . .. . .. . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . 340
Ronald A. Rudder, Raymond E. Thomas,
and Robert J. Nemanich
1 .O INTRODUCTION . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
2.0 PLASMA CLEANING CRITERIA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
2.1 Cleaning for Low-Temperature Epitaxial Growth . . . 344
2.2 Cleaning for Interface Formation with
Deposited-SiO, on Silicon . . . . . . . . . . . . . . ... 345
3.0 MECHANISMS . . . . . . . . . . . . . . .. .. . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . .. . 346
4.0 PROCESSING EQUIPMENT . . . . . . . . . . . . . . . . . . . . . .._................... 351
5.0 WAFER PROCESSING . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
5.1 Ex Situ Processing . . . . . . . . . . . . . . . . . . . . 356
5.2 In Situ Processing: Remote RF Sources . . . . 358
5.3 In Situ Processing: ECR Sources . . . . . . . .._................. 366
5.4 In Situ Processing: Remote Microwave Sources..... 369
6.0 CONCLUSIONS . . . . . . . ..____........._.__......_............................. 371
REFERENCES . .. . . ... . . . . . . . . 372

Part IV. Analytical and Control Aspects

9 Measurement and Control of Particulate

Contaminants ..................................................... 379
Venu B. Menon and Robert P. Donovan
1 .O INTRODUCTION ............................................................. 379
1.1 Scope ............................................................... 380
1.2 Chapter Organization ............................................. 380
2.0 PARTICLE MEASUREMENT IN LIQUIDS ....................... 380
xviii Contents

2.1 Optical Light Scattering .......................................... 381

2.2 Nonvolatile Residue Monitor.. ................................. 383
2.3 Microscopy ............................................................. 384
2.4 Particles on Wafers.. .............................................. 385
3.0 PARTICLE CONTROL IN CHEMICALS ........................... 386
3.1 Incoming Chemical Quality .................................... 387
3.2 DI Water Quality .................................................... 390
3.3 Chemical Distribution System.. ............................... 394
3.4 Point Of Use Filtration ............................................ 397
3.5 Chemical Reprocessing.. ........................................ 399
4.0 PARTICLE CONTROL DURING PROCESSING ............. 400
4.1 Effect of Process Chemistry ................................... 400
4.2 Process System Configuration ............................... 405
4.3 Rinsing and Drying ................................................. 410
4.4 GasNapor Phase Cleaning .................................... 414
5.0 POST-PROCESSING PARTICLE REMOVAL
TECHNOLOGIES ............................................................ 415
5.1 Brush Scrubbing ..................................................... 418
5.2 Hydrodynamic Cleaning ......................................... 418
5.3 Ultrasonic Cleaning ................................................ 420
5.4 Megasonic Cleaning ............................................... 421
5.5 Other Techniques.. ................................................. 424
6.0 PARTICLE MONITORING PRACTICES .......................... 425
7.0 CONCLUSIONS .............................................................. 427
REFERENCES ............................................................... 428

10 Silicon Surface Chemical Composition

and Morphology ..................................................... 433
Gregg S. Higashi and Yves J. Chabal
1 .O INTRODUCTION ............................................................. 433
2.0 OXIDE-TERMINATED SURFACES ................................. 435
2.1 Introduction ............................................................ 435
2.2 Chemical Composition ........................................... 436
2.3 Structure and Morphology ...................................... 441
2.4 Contamination Issues ............................................. 445
3.0 HYDROGEN-TERMINATED SURFACES.. ...................... 446
3.1 Chemical Composition of HF Treated
Surfaces (Wet) ....................................................... 446
3.2 Structure and Morphology ...................................... 458
3.3 Contamination Issues ............................................. 484
4.0 SUMMARY AND FUTURE DIRECTIONS ........................ 487
REFERENCES ............................................................... 490
 Contents xix

11 Analysis and Control of Electrically Active

Contaminants by Surface Charge Analysis ........ .497
Emil Kamieniecki and G. (John) Foggiato
1.O INTRODUCTION TO SURFACE CHARGE ANALYSIS
TECHNIQUE ............................................................... 497
2.0 PRINCIPLES OF OPERATION ....................................... 498
2.1 Basic Relationships ................................................ 500
2.2 Overview of Measured Parameters ........................ 510
3.0 SURFACE CHARGE CHARACTERIZATION OF
CLEANING PROCESSES .............................................. 516
3.1 HF Etch ............................................................... 519
3.2 RCA Standard Clean 1 (SC-l). ............................... 522
3.3 RCA Standard Clean 2 (SC-2) ................................ 525
3.4 Effects of Metallic Contaminants ............................ 527
3.5 Rinsing and Drying ................................................. 529
4.0 INCOMING WAFER SURFACE QUALITY
MONITORING ............................................................... 531
5.0 SUMMARY ............................................................... 533
REFERENCES ............................................................... 534

12 Ultratrace Impurity Analysis of Silicon Surfaces

by SIMS and TXRF Methods .................................. 537
Richard S. Hackett
1.O INTRODUCTION ............................................................. 537
2.0 ANALYTICAL PROBLEM ................................................ 537
2.1 Relevant Contamination Levels.. ............................ 537
2.2 Analysis Depth and Number of Atoms .................... 540
2.3 Quantification ......................................................... 540
2.4 Composition of Clean Native Oxide.. ...................... 540
3.0 AVAILABLE ANALYTICAL TECHNIQUES.. ..................... 540
3.1 Electron Spectroscopy for Chemical Analysis.. ....... 541
3.2 Auger Electron Spectroscopy ................................. 543
3.3 Rutherford Backscattering Spectrometry ................ 545
3.4 Laser Ionization Mass Spectrometry ....................... 546
3.5 X-Ray Fluorescence Spectroscopy ......................... 547
3.6 High-Resolution Electron Energy Loss
Spectroscopy ......................................................... 547
3.7 Infrared Spectroscopy ............................................ 547
3.8 VPDJAAS ............................................................... 548
3.9 Secondary Ion Mass Spectrometry ......................... 551
3.10 Total Reflection X-Ray Fluorescence Spectroscopy 551
xx Contents

4.0PRINCIPLES AND METHODOLOGY OF

SIMS ANALYSIS ............................................................. 552
4.1 Principles of SIMS.. ................................................ 552
4.2 Static SIMS ............................................................ 553
4.3 Dynamic SIMS ....................................................... 558
4.4 PolyencapsulationKIMS.. ....................................... 560
5.0 TXRF ANALYSIS.. ........................................................... 564
5.1 Principles of TXRF ................................................. 564
5.2 Quantification ......................................................... 569
5.3 Quantitative Comparisons ...................................... 572
5.4 Angle Properties.. ................................................... 572
5.5 Monochromatic TXRF ............................................ 575
5.6 Characterization of Cleaning Processes by TXRF . . 577
6.0 FUTURE ANALYTICAL TECHNOLOGY.. ........................ 583
6.1 VPD Chemistries .................................................... 584
6.2 VPD ICP/MS .......................................................... 585
6.3 VPD/TXRF ............................................................. 585
6.4 VPD/SIMS.. ............................................................ 586
6.5 TOF-SIMS.. ............................................................ 587
7.0 CONCLUSIONS .............................................................. 588
REFERENCES ............................................................... 588

Part V. Conclusions and Future Directions

13 Future Directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . .. . . . . . .. 595

Werner Kern
1 .O INTRODUCTION . . . . . . .._.................................................... 595
2.0 PURITY REQUIREMENTS FOR ULTRACLEAN
SILICON WAFERS . . . . . . . . . . . . .. . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 596
3.0 FUTURE OF LIQUID-PHASE WAFER CLEANING
PROCESSES . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
4.0 FUTURE OF GAS-PHASE WAFER CLEANING
PROCESSES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . 598
5.0 FUTURE NEEDS OF PROCESSING CHEMICALS . . .. .. . . . 599
6.0 WAFER CLEANING EQUIPMENT . . . .. . . .. . . . . . . . . . . . . . . . .. . . .. . . . . 602
7.0 CONTROL OF MICROCONTAMINATION . . . . . . . . . . . . . . . . . . . . . . . 603
8.0 SUMMARY AND CONCLUSIONS . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . 606
REFERENCES (July through December 1992) . . . . . . . . . . . . . . . . . . . . . . . . 607

Index ,...,.......................,......................~...................~.. 611