Electroplating andElectroless Plating ofCopper & its Alloys

Table of Content

1 Introducing Copper 
1.1 PROPERTIES I
1.1.1 Chemical Properties I

1.1.1.1 Copper(I) Compounds 2
1.1.1.2 Copper(II) Compounds 3
1.1.1.3 Acid Resistance 5
1.1.1.4. Atmospheric Corrosion 7
1.1.2 Toxicity of Copper 9
1.1.3 Physical Properties 10
1.1.3.1 Electrical Conductivity 10
1.1.3.2 Thermal Conductivity 12
1.1.4. Mechanical Properties 12
1.1.4.1 Crystalline Structure 12
1.1.4.2 Plastic Behaviour 13
1.1.4.3 Heat Treatment 16
2 Electrodeposition of Copper and its Alloys 21
2.1 PRINCIPLES 21
2.1.1 General 21
2.1.2 Electrodeposition from Alkaline Cyanide Copper Plating
Baths 22
2.1.3 Electrodeposition from Acid Sulphate Copper Plating
Baths 23
2.2 PROCESSES 24
2.2.1 Alkaline Cyanide Electrolytes 24
2.2.1.1 Basic Composition 24
2.2.1.2 Constituents of the Electrolyte 26
2.2.1.3 Operating Conditions 28
2.2.1.4 Impurities 30
2.2.1.5 Practical Guidelines 32
2.2.1.6 Defects and Their Correction 32
TABLE OF CONTENTS
2.2.2 Acid Sulphate Copper Plating Baths 34
2.2.2.1 Basic Composition 35
2.2.2.2 Constituentsof the Electrolyte 36
2.2.2.3 Operating Conditions 38
2.2.2.4 Contmninants 39
2.2.2.5 Practical Guidelines 40
2.2.2.6 Faults and Remedies 41
2.2.3 Other Copper Plating Baths 42
2.2.3.1 Copper Fluoroborate Plating Baths 42
2.2.3.2 Copper Pyrophosphate Plating Baths 42
2.2.3.3 Copper Sulphamate, Copper Phosphate and Copper
Alkylsulphonate Plating Baths 43
2.3 THE DEPOSITION OF COPPER ALLOYS 43
2.3.1 Brass plating 43
2.3.1.1 Principles 43
2.3.1.2 The Brass Plating Bath 45
2.3.1.3 Operating Conditions And Maintenance 46
2.3.2 Bronze Plating 47
2.3.2.1 Principles 47
2.3.2.2 The Bronze Plating Bath 48
2.3.3 Other Alloy Plating Solutions 49
2.4 ALKALINE COPPER PLATING BATHS 49
3 The Technology of Electrodeposition of Copper and
Copper Alloys 51
3.1 INTRODUCTION 51
3.2 CYANIDE PLATING BATHS 52
3.2.1 Make-up of Cyanide Copper Plating Baths 54
3.2.2 Maintenance of Cyanide Copper Plating Baths 55
3.3 ACID SULPHATE COPPER PLATING BATHS 56
3.3.1 Make-up of Acid Sulphate Copper Plating Baths 57
3.3.2 Maintenance of Acid Sulphate Copper Plating Baths 58
3.4 OTHER COPPER PLATING BATHS 58
3.4.1 Pyrophosphate Copper Plating Solutions 58
3.4.2 Fluoroborate Copper Plating Solutions 59
3.5 BARREL COPPER PLATING 60
3.5.1 Copper Cyanide barrel plating solutions 60
TABLE OF CONTENTS iii
3.5.2 Acid Sulphate Barrel Plating Solution 61
3.5.3 Pyrophosphate Barrel Plating Solution 62
3.5.4 Phosponate Barrel Plating Solution 62
3.6 RACK PLATING 63
3.6.1 Acid Sulphate Solutions 63
3.6.2 Cyanide Solutions 64
3.7 CONTINUOUS COPPER PLATING 64
3.8 COPPER-ZINC ALLOY (BRASS) PLATING 66
3.9 COPPER-TIN ALLOY (BRONZE) PLATING 67
3.9.1 Red-Bronzes 68
3.9.1 White Bronzes 68
3. I0 COPPER PLATING SOLUTIONS for SURFACE PRE-treatment 69
3. 10.I Surface Preparation of Zinc-Base Diecastings 69
3.10.2 Electroplating of Plastics 70
3.11 ELECTROFORMING 71
3.11.1 Copper Plating of Cylinders 72
3.11.2 Manufacture of Metal Sieves 73
4 The Properties of Copper and Copper Alloy Coatings 75
4.1 COPPER COATINGS 75
4.1.1 Texture and Structure 75
4.1.2 Internal stresses 78
4.1.3 Adhesion 78
4.1.4 Hardness 79
4.1.5 Ductility 79
4.1.6 Electrical Properties and Contacts 80
4.1.7 Corrosion behaviour 81
4.2 COPPER ALLOY COATING 81
4.2.1 Brass (Copper-Zinc) 82
4.2.1.1 Texture and structure 82
4.2.1.2 Internal stress 83
4.2.1.3 Adhesion 83
4.2.1.4 Hardness 83
4.2.1.5 Ductility 83
4.2.1.6 Electrical Properties and Contacts 83
4.2.1.7 Corrosion Characteristics 83
iv TABLE OF CONTENTS
4.2.2 Bronze (copper-tin) 84
4.2.2.1 Texture and Structure 84
4.2.2.2 Internal Stresses 84
4.2.2.3 Adhesion 85
4.2.2.4 Hardness 85
4.2.2.5 Ductility 85
4.2.2.6 Electrical Properties and Contacts 85
4.2.2.7 Corrosion Behaviour 86
5 The Applications of Electrodeposited Copper and Copper
Alloy Coatings 89
5.1 INTRODUCTION 89
5.2 DECORATIVE APPLICATIONS 90
5.2.1 Copper Coatings 90
5.2.2 Copper Alloy Coatings 94
5.2.2.1 Bronze 94
5.2.3 Brass 99
5.3 FUNCTIONAL APPLICATIONS 100
5.3.1 Corrosion protection 100
5.3.2 Electroforming and Electrotyping 104
5.3.3 Printing industry 105
5.3.4 Coating of Strip, Wires and Tubes 108
5.3.5 Masking for Heat Treatment 109
5.4 COLOURING OF COPPER AND COPPER ALLOY COATINGS 109
5.4.1 Surface Preparation Before Colouring 110
5.4.2 Colouring Solutions III
5.4.2.1 Patina Colouring I I I
5.4.2.2 Colouring with Liver Of Sulphur 112
5.4.2.3 Colouring with Aqueous Permanganate Solution 113
5.4.2.4 Black Colouring 114
5.4.2.5 Lustre Colouring 114
5.4.2.6 Colouring with Chlorate Solutions 115
5.4.2.7 “Gold Sulphur” Colouring 115
5.4.2.8 Persulphate Colouring 116
5.4.3 General Guidelines on Colouring 116
5.5 BLACK COLOURING (BLACK OXIDE) IN THE PRINTED
CIRCUIT BOARD INDUSTRy 117
5.6 ELECTRICAL AND ELECTRONICS INDUSTRIES 118
TABLE OF CONTENTS v
6 Electrolessly Deposited Copper Coatings 123
6.1 HISTORICALREVIEW 123
6.2 PROCESSES 124
6.2.1 Exchange Processes (Cementation or Displacement
Reactions) 124
6.2.2 Sputtering Processes, Evaporation Processes 124
6.2.3 Laser Induced Copper Deposition 124
6.3 ELECTRO LESS COPPER PLATING BY CHEMICAL
REDUCTION 125
6.3.1 Reducing agents and Their Chemistry 126
6.3.2 Initiation of Copper Deposition 127
6.3.3 Stabilisers and Their Influence 128
6.3.4 Complexing Agents 129
6.3.5 The Composition of Chemical Copper Plating Baths 130
6.3.6 On-line-Control of Chemical Copper Plating Baths 131
6.3.6.1 Copper ions 131
6.3.6.2 Alkali content 131
6.3.6.3 Formaldehyde 132
6.3.6.4 Stabilizer 132
6.4 PRE-TREATMENT 133
6.4.1 Metallization of Plastics 140
6.4.2 Metallizing of Inorganic Materials 145
6.5 APPLICATIONS 146
6.5.1 Shielding 147
6.5.2 Electronic Applications 148
6.5.2.1 Subtractive Technology 152
6.5.2.2 Semi-additive Technology 152
6.5.2.3 Additive Technology 153
6.6 COPPER PLATING BATHS FOR PRINTED CIRCUIT
BOARD MANUFACTURE 154
6.7 OUTLOOK 156
7 Properties of Electroless Copper Coatings 159
7.1 INTRODUCTION 159
7.2 COPPER COATINGS 159
7.2. I Copper Electrolytes 159
vi TABLE OF CONTENTS
7.3 SURFACE MORPHOLOGY 162
7.3.1 Scanning Electron Microscopy 162
7.4 SURFACE ROUGHNESS 163
7.4.1 Profilometer 163
7.5 DEGREE OF PURITY 163
7.5.1 ESCA Investigations 163
7.5.2 Auger electron Spectroscopy 165
7.5.3 Energy-Dispersive X-Ray Analysis 167
7.5.4 Electron-beam Microanalysis 168
7.6 MICROSTRUCTURES 169
7.6.1 Optical Microscopy 169
7.6.2 Transmission-Electron Microscopy 171
7.6.3 Electron Diffraction Experiments 172
7.7 INTERNAL STRESS 174
7.7.1 X-Ray Fine-Structure Investigation 174
7.8 DUCTILITY 175
7.8.1 Hydraulic Bulge Test 175
7.8.2 Tensile Test 177
7.9 TENSILE STRENGTH 178
7.9.1 Tensile Test 178
7.10 HARDNESS 180
7.10.1 Vickers Microhardness 180
7.11 ELECTRICAL RESISTANCE 181
7.11.1 Four-Probe Current-potential Method 181
8 Quality Assurance, Analysis and Process Optimization in
Copper Deposition … 185
8.1 INTRODUCTION 185
8.2 MONITORING AND ANALYSIS OF SOLUTIONS 186
8.2.1 Analytical Control of the Metal Content 187
8.2.1.1 Volumetric Methods 187
8.2.1.1 Gravimetric Methods 188
8.2.1.3 Spectroscopic methods 189
8.2.1.4 Potentiometry 192
TABLE OF CONTENTS vii
8.2.2 Control of Additive Concentrations 193
8.2.2.1 High-performance Liquid-chromatography 193
8.2.2.2 Tensiometry (Surface or Interfacial Tension) 195
8.2.3 Indirect Electrochemical Methods 196
8.2.3.1 Cyclic Voltammetry (CVS, Cyclic Voltammetric
Stripping) 196
8.2.3.2 Chronoamperometry 198
8.2.3.3 Capacity Measurement 199
8.2.4 Optical Methods 20 I
8.2.4.1 Scattered Light Patterns of Laser Beams 20 I
8.2.4.2 Raman Spectroscopy 20 I
8.3 PROCESS OPTIMIZATION 201
8.3.1 Factors Influencing the Process 202
8.3.1.1 The Workpiece 202
8.3.1.2 Composition of the Electrolyte 202
8.3.1.3 Current Density/Potential 203
8.3.1.4 Temperature and Hydrodynamic Conditions 204
8.3.2 Throwing Power and Current Distribution 205
8.3.2.1 The Primary Current Distribution 205
8.3.2.2 Secondary Current Distribution: Macro-throwing
Power 206
8.3.2.3 Tertiary Current Distribution (Micro-Throwing
Power and Levelling) 207
8.3.3 Taguchi Statistical Experiment Design 208
9 Stripping of Copper and Copper Alloy Coatings 211
9.1 GENERAL 211
9.2 COPPER STRIPPING PROCESSES 212
9.2.1 Mechanical Processes 213
9.2.2 Wet-Chemical Processes 213
9.2.2.1 Chemical Processes 214
9.2.2.2 Electrochemical Processes 214
9.3 SURFACE PREPARATION BEFORE FURTHER
ELECTROPLATING 217
9.4 WASTE DISPOSAL METHODS FOR COPPER STRIPPING
SOLUTIONS 218
viii TABLE OF CONTENTS
10 Recycling And Effluent Treatment 221
10.1 THE PROBLEM 221
10.2 PROCESSES IN RECYCLING TECHNOLOGy 223
10.2.1 Reduction in Water Volume 223
10.2.1.1 Water Saving Measures 223
10.2.1.2 Rinsing Techniques 223
10.2.2 The Technology of Ion Exchange 225
10.2.3 Retardation Processes 228
10.2.4 Membrane Filtration 229
10.2.5 Electrolytic Processes 231
10.2.5.1 Electrolysis 231
10.2.5.2 Electrodialysis 232
10.2.6 Evaporation and Vaporization 233
10.2.6.1 Evaporation 233
10.2.6.2 Vaporization 234
10.3 EFFLUENT TREATMENT 235
10.3.1 The Main Process 235
10.3.1.1 Neutralization for Precipitation 235
10.3.1.2 Precipitation of Anionic Contaminants 236
10.3.1.3 Treatment of Complex Metal Compounds 237
10.3.1.4 Removal of Toxic Material 238
10.3.1.5 Removal of Ammonia 239
10.3.1.6 Removal of Halogenated Hydrocarbons 240
10.3.1.7 Elimination of Materials that Cause COD 241
10.3.2 Dewatering Processes 242
10.3.3 After-treatment Processes 244
11 Copper In Microtechnology 247
11.1 Introduction 247
11.2 Electrodeposition of Metallic Microstructures 249
11.3 Electrolytes and Plant Technology 250
11.3.1 Acid copper Electrolytes 250
11.3.2 The Copper Tetratluoroborate Electrolyte 252
11.3.3 Methane Sulphonate Electrolytes 253
11.3.4 Cyanide and Pyrophosphate Electrolytes 254
11.3.4.1 Cyanide Electrolytes 254
11.3.4.2 Pyrophosphate Electrolytes 255
TABLE OF CONTENTS ix
11.4 Plant Technology 255
11.5 The Influence of the Basis Material 256
11.6 Applications 257
11.6.1 Micro-relays 257
11.6.2 Sacrificial Layer Technique for Movable
Microstructures 258
11.6.3 Electrodes for Micro Spark Erosion 259
11.6.4 Mould Inserts with Copper Backfilling 260
11.7 Outlook 262
12 Copper In Printed Circuit Board Technology 263
12.1 Introduction 264
12.2 Printed Circuit Board Construction 264
12.2.1 Resin Systems for Printed Circuit Boards 265
12.2.2 Electrochemical Production of Copper Foils 266
12.3 Possible Methods of Constructing of Printed Circuit Boards.
Subtractive, Semi-Additive, and Fully-Additive Processes 269
12.3.1 Subtractive Processes 269
12.3.2 Additive Processes 271
12.4 Electrodeposition of Planar High-Ductility Copper Coatings 273
12.4.1 Organic Additives and their Mechanism in Copper …………….
Electrolytes 276
12.4.2 Reverse-pulse Plating 277
12.4.3 Plant Technology 280
12.4.3.1 Vertical Technique 280
12.4.3.2 Horizontal Technique 283
12.5 Chemical Copper Plating 285
12.6 Printed Circuit Boards with Micro-Holes – High Density
Interconnection (HDI) 287
12.7 Outlook 290
Appendix 291
Index 299

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