COPPER ELECTROPLATING

RANDHIR KUMAR SINGH

ASST PROFESSOR

OPJIT

Copper plating
Copper plating is a process of copper deposition over a part immersed into

an electrolyte solution and used as a cathode, when the copper anode is being dissolved into the electrolyte in form of the copper ions traveling through the solution and depositing on the cathode surface.
Phosphorized copper (0.04-0.08% P)is recommended for the anodes in Copper plating [Acid copper sulfate bath] and Acid copper fluoborate bath.
High purity oxygen-free copper is used for the anodes in Cyanide copper

bath and Copper pyrophosphate bath. Less pure anodes form sludges on their surfaces.
The

sludge particles may increase the deposit roughness. Anode-to-cathode area ratio is kept within the range between 1 and 2.
oil-free air or by the oscillating cathodes.

The copper electrolyte solutions are normally agtated by the solution flow, The solutions are continuously filtered through a 1-5 m filters at a flow 1-3

turnovers/hour (at least).

Discuss:
Properties of copper deposites
Cyanide copper bath Copper pyrophosphate bath

Acid copper sulfate bath

Acid copper fluoborate bath

Properties of copper deposites

High electrical conductivity. The most popular application of the

electroplated copper is copper plating of Printed Circuit Boards (PCB). Copper substrate is easy to plate therefore copper deposit is widely used as an undercoat for over-deposits. High thermal conductivity. Copper deposits are used as thermal conductors. Copper deposit over steel surface may serve as a diffusion barrier. Copper coatings are used as stop-off preventing diffusion of carbon or/and Nitrogen during selective Case hardening. There are numerous elctrolyte solutions and electro-deposition techniques for copper plating. Copper deposits possess excellent decorative appearance. Copper is relatively inexpensive metal.

Cyanide copper bath

Cyanide copper (particularly strike bath) provides excellent adhesion of the copper deposit. Cyanide baths are used for applying strike adhesion coatings and for wire plating Compositions of cyanide copper baths
CuCN NaCN KCN Na2CO3 NaOH KOH Rochelle salt Cu Free cyanide

Bath Strike Rochelle salt

oz/gal

g/l

oz/gal

g/l

oz/gal

g/l

oz/gal

g/l

oz/gal

g/l

oz/gal

g/l

oz/gal

g/l

oz/gal

g/l

oz/gal

g/l

2.0 3.5

15 26

3.7 4.6

28 35

2.0 4

15 30 to PH=12.3 6 45

1.4 2.5

10.5 19

1.5 0.8

11 6

High speed

60

12.5

94

15

5.6

42

5.6

42

1.0

7.5

Operation conditions of cyanide copper baths Cathode current Anode current density density (max.) A/ft2 Cathode efficiency Max.deposit thickness mil 0.1 m 2.5 Solution flow Continuous

Temperature Bath Strike F C 49-63

Agitation

Filtration

A/dm2 A/ft2 A/dm2 % 10 1 30-60

120145

10-30 1-3

Rochelle salt

130160

54-71

20-40 2-4

30

50

0.2

5.0

Solution flow

Continuous

High speed

170180

77-82

30-60 3-6

50

100

0.3-2.0 7.5-50

Solution flow, Continuous mechanical, air

Cyanide copper bath troubleshooting guide

Problem: Poor adhesion (blistering or peeling) Possible causes: 1.Poor cleaning treatment (Surface preparation) 2.Contaminated rinsing water Problem: Low current efficiency due to the anode polarization (black or green deposit on anodes) Possible causes: 1. Low free cyanide 2.Insufficient agitation 3.High anode current density 4.High operation temperature 5.Organic contamination Problems: Roughness Possible causes: 1.Suspended solid particles in the solution 2.Rough substrate surface 3.High current density 4.Organic contamination

Cyanide copper bath troubleshooting guide

Problem: Turbide solution

Possible causes:

1.Low free cyanide 2.Insoluble particles in the solution Problem: Dull deposit

Possible causes:

1.Low brightner 2.Organic contamination Problem: Dark deposit with yellow tarnish

Possible causes:
1.Low copper 2.High free cyanide

Problem: Spongy deposit

Possible causes:
1.Low free cyanide 2.Low Rochelle salt

Copper pyrophosphate bath

Copper pyrophosphate baths provide high throwing power and ductile copper deposition. They are used in electroforming, plating on plastics, printed circuit boards, and as stop-off in selective Case hardening of steel. Copper pyrophosphate is a weak alkaline process.
Composition of copper pyrophosphate bath
Copper Pyrophosphate Nitrate Ammonia
Weight ratio P2O7/Cu

oz/gal 3.5

g/l 26

oz/gal 25

g/l 188

oz/gal 1.5

g/l 11

oz/gal 0.13

g/l 1 7-8.5

Operation conditions of acid copper pyrophosphate bath

Temperature
F C Cathode current density A/ft2 A/dm2 Cathode efficiency %

Voltage
V

PH

Filtration

Agitation

100-140 38-60 10-70

1-7

95-100

2-5

8-8.5

Vigorous air

Continuous 1 turnover/hr

Copper pyrophosphate bath troubleshooting guide

Problem: Poor adhesion (blistering or peeling)

Possible causes:

1.Poor cleaning treatment (Surface preparation); 2.Contaminated rinsing water

Problem: Poor throwing power

Possible causes:

1.High copper metal; 2.Insufficient agitation; 3.Low copper/pyrophosphate ratio; 4.High operation temperature; 5.Organic contamination
Problems: Roughness

Possible causes:

1.Suspended solid particles in the solution; 2.Rough substrate surface; 3.High current density; 4.Metallic contamination

Copper pyrophosphate bath troubleshooting guide

Problem: Brittle deposit Possible causes: 1.High brightner content; 2.Organic contamination; 3.Excessive ammonia
Problem: Dull deposit Possible causes:

1.Low brightner; 2.Organic contamination; 3.Low ammonia

Problem: Burnt copper deposit Possible causes: 1.Low copper; 2.Insufficient agitation;

3.Low operation temperature; 4.low pyrophosphate

Problem: Buildup of orthophosphate in solution. Possible causes: 1.High operation temperature; 2.Low copper/pyrophosphate ratio

Acid copper sulfate bath

Copper sulfate baths provide high throwing power. The plating process and the waste treatment are relatively inexpensive. Copper sulfate copper plating is widely used in electronics (printed circuit boards, semiconductors), electroforming and for application undercoats. Compositions of acid copper sulfate baths
Bath General High throw High speed Copper sulfate CuSO4*5H2O oz/gal g/l 27 200 10 75 50 375 Sulfuric acid H2SO4 oz/gal g/l 9.3 70 25 188 8 60 Chloride ion Clppm 75 60

Operation conditions of acid copper sulfate baths

Temperature Bath
General High throw Cathode current density Anode current density (max.) Anode/ cathode area ratio (min.)

Agitation

Filtration

F
70-100

C
21-38

A/ft2
40

A/dm2
4

A/ft2
40

A/dm2
4 1 Vigorous air Continuous 3 turnover/hr

70-90
64-113

21-32
18-45

15-50
50-200

1.5-5
5-20

7-25
20-100

0.7-2.5
2-10

2
2

High speed

Air or Continuous mechanical 2 turnover/hr Vigorous air Continuous or 2 turnover/hr mechanical

Acid copper sulfate bath troubleshooting guide

Problem: Poor adhesion (blistering or peeling)

Possible causes:

1.Poor cleaning treatment (Surface preparation); 2.Contaminated rinsing water

Problem: Poor throwing power

Possible causes:

1.High copper metal; 2.Low acid; 3.Low brightner content

Problems: Roughness

Possible causes:

1.Suspended solid particles in the solution; 2.Rough substrate surface; 3.High chloride; 4.Low brightner content; 5.High rectifier ripple

Acid copper sulfate bath troubleshooting guide

Problem: Anode polarization

Possible causes:

1.High chloride; 2.Insufficient anode area; 3.Organic contamination 4.Low temperature; 5.High acid; 6.Low copper
Problem: Burnt deposit

Possible causes:

1.Low copper; 2.High acid; 3.Low chloride; 4.Insufficient agitation; 5.Organic contamination

Problem: Pitting Possible causes:

1.Low chloride; 2.Organic contamination

Acid copper fluoborate bath

Copper fluoborate baths provide high plating speed. They are used in printed circuit boards, electroforming, plating on plastic.

Compositions of acid copper fluoborate baths

Bath Low concentrat ion High concentrat ion Copper fluoborate Cu(BF4)2 oz/gal g/l 30 225

Copper metal
oz/gal 8 g/l 60

Fluoboric acid HBF4 oz/gal g/l 2 15

Boric acid H3BO3 oz/gal g/l 2 15

60

450

16

120

30

30

Operation conditions of acid copper fluoborate baths

Cathode current density A/ft2 A/dm2 75-125 125-350 7.5-12.5 12.5-35 Cathode efficiency % 95-100 95-100

Temperature Bath Low concentration High concentration F 80-170 80-170 C 27-77 27-77

Agitation Air or mechanical Air or mechanical

Filtration Continuous carbon Continuous carbon

Acid copper fluoborate bath troubleshooting guide

Problem: Poor adhesion (blistering or peeling)

Possible causes:

1.Poor cleaning treatment (Surface preparation); 2.Contaminated rinsing water

Problem: Poor throwing power

Possible causes:

1.High copper metal; 2.Low acid; 3.Low operation temperature; 4.High current density
Problems: Roughness

Possible causes:

1.Suspended solid particles in the solution; 2.Rough substrate surface; 3.Low brightner content; 4.High rectifier ripple

Acid copper fluoborate bath troubleshooting guide

Problem: Low deposit hardness

Possible causes:

1.High temperature; 2.High acid; 3.Low current density

Problem: Brittle deposit

Possible causes:

1.Chloride contamination; 2.Organic contamination

Problem: Coarse deposit Grain structure

Possible causes:

1.Low grain refiner; 2.High hardener content