TIN ALLOY ELECTROPLATING

RANDHIR KUMAR SINGH ASST PROFESSOR OPJIT

CONTENT

Characteristics of tin Applications of electroplated tin alloys Tin alloys used for electroplating Tin alloy electroplating in fluoborate solutions Tin alloy electroplating in methane sulfonic solutions Tin electroplating in sulfate solutions Tin electroplating in stannate solutions

Characteristics of tin
Symbol
Atomic number Atomic weight

: Sn
: 50 : 118.71

Classification Crystal structure

: Metal : Tetragonal

Tin is soft ductile silver white metal.

Characteristic properties of tin and tin alloys:

Excellent corrosion and tarnish resistance; Excellent cosmetic appearance; Excellent solderability; Very good ductility (malleability); Non-Toxicity; Good anti-friction properties (low friction, high galling resistance).

Applications of electroplated tin alloys

Electronics and semiconductors industry Tin Electroplating is widely used in manufacturing printed circuit boards (PCBs), printed wiring boards (PWBs), electronic components. Food containers and packages Many food and beverage cans, food storage containers, food handling equipment are tin plated. Engine bearings Tin-copper and lead-tin-copper alloys are used in tri-metal sliding bearings as anti-friction coating of 0.0005-0.001 (0.012-0.025 mm) thick. In addition to this very thin (0.04 inch / 1m) pure tin coating over the bearing surface is used for better cosmetic appearance and corrosion protection.

Tin alloys used for electroplating

Most tin base alloys have been developed as non-toxic lead-free alternatives of the traditional tin-lead solder 63Sn-37Pb. Electroplating process of tin base lead-free alloys requires strict control of the electrolyte composition and other process parameters. Small deviations in the deposited alloy composition may result in large changes in the melting point. Another disadvantage of most tin base lead-free alloys is their proneness to form tin whiskers - mono-crystal tin filaments growing on the surface of tin base alloy. Long whiskers formed on a lead extend to other leads and may bridge across them causing catastrophic shorts of the circuit. The following measures reduce the risk of whiskers formation: low brighteners plating solutions, annealing immediately after plating at 300340F (150-170C) for 3-1 hours, reflow after the plating, nickel barrier preventing diffusion of copper from the substrate to the tin coating.

Tin alloys used for electroplating

Pure tin There are two types of electroplated pure tin: bright tin and matte tin. Bright tin is coated in electroplating solutions containing brighteners organic additives causing formation of fine Grain structure deposit. Bright tin coating have excellent cosmetic appearance, however they are characterized by high internal stresses and contain increased amount of organics. Matte tin coatings are made in electrolytes without additions of brighteners. Matte tin has dull appearance but the level of internal stresses in matte tin depositions is much less than in that of bright tin. Pure tin has been used in food package applications and as cosmetic overlay. Recently pure tin has been introduced as non-toxic replacement of lead containing solders. Maximum service temperature of pure tin solders is higher due to higher melting temperature of tin (450F / 232C). Matte tin (in contrast to bright tin) is characterized by low whiskers growing therefore it is used in electronics.

Tin "Whisker" shown above growing between pure tin-plated hook terminals of an electromagnetic relay similar to MIL-R-6106 (LDC 8913)

"Dendrites" shown above are NOT the same phenomenon as "whiskers"

Tin alloys used for electroplating

Tin-lead Tin-lead alloys (eg.63Sn-37Pb) were very popular for electroplating of electronic components. The composition 63Sn37Pb is eutectic point of the binary Sn-Pb system therefore the melting point of the alloy is lowest of all Sn-Pb alloys: 361F (183C). Now toxic lead containing alloys have been replaced by leadfree alternatives. Lead-tin-copper Alloys 87Pb-10Sn-3Cu, 83Pb-14Sn-3Cu, 82Pb-10Sn-8Cu are used for deposition of anti-friction layer on sliding engine bearings. Lead provides good anti-friction properties of the coating, tin imparts corrosion resistance, copper increases hardness and fatigue strength.

Tin alloys used for electroplating

Tin-copper Eutectic composition Sn-0.7Cu with the melting point 441F (227C) is the most popular non-toxic Sn-Cu alloy. The presence of copper increases the alloy strength but makes it brittle. Other disadvantages of the alloy are its poor wetting and proneness to form whiskers. Tin-silver Sn-3.5Ag, Sn-3Ag are typical tin-silver lead-free alloys possessing good solderability, high maximum service temperature and mechanical strength. The alloy disadvantages are relatively high cost and proneness to form whiskers. Tin-silver-copper Eutectic composition Sn-3.5Ag-0.7Cu has relatively low melting point 423F (217C), moderate wettability, good strength and fatigue strength. Sometimes up to 3% of bismuth is added to the alloy to improve wettability and decrease the melting point.

Tin alloys used for electroplating

Tin-bismuth Eutectic composition 42Sn-58Bi having very low melting point 280F (138C) is used in some low temperature applications. The alloy has good wettability and low proneness to whiskers however it is brittle. Sn-Bi alloys are incompatible with lead containing materials because of formation of ternary eutectic with extremely low melting point 204F (96C). The eutectic locating along the grain boundaries causes drop of mechanical properties. Tin-zinc The alloy Sn-9Zn has a melting point 388F (198C). The alloy strength and fatigue strength are higher than those of tin-lead alloy. The disadvantages of the alloy are poor wettability and low corrosion resistance.

Tin alloy electroplating in fluoborate solutions

Bath ingredients: Tin fluoborate Sn(BF4)2 Lead fluoborate Pb(BF4)2 Copper fluoborate Cu(BF4)2 Fluoboric acid HBF4 Boric acid H3BO3 Organic brighteners (additives) Deionized (DI) water

Tin alloy electroplating in fluoborate solutions

Operating conditions: : 70-100F (21-38C) : Solution and/or cathode rod, no air agitation Anodes composition : similar to the coating composition Anode/Cathode surface areas ratio : 1 Filtration : continuous with minimum 2 bath turnovers per hour, no carbon Cathode current density : 20-70 A/ft (2.2-7.6 A/dm) Temperature Agitation

Bath formulations Tin alloy electroplating in fluoborate solutions Tin Lead Coating oz/gal g/l oz/gal g/l

Copper oz/gal g/l

Fluoboric acid oz/gal g/l 26 200

Boric acid oz/gal g/l 4 30

Pure tin (100Sn) 90Sn-10Pb

60Sn-40Pb 10Sn-87Pb-3Cu

37

10
7 1.3

75
52 10

1.3
4 9

10
30 68 0.33 2.5

23
17 17

175
128 128

4
4 4

30
30 30

Problems and troubleshooting

Problem Burning at high current densities Treeing at high current densities Cause 1. Low metals concentration 2. Too high current density 1. Low additive concentration 2. Low acid concentration 1. Foreign particles in bath 2. Stannic tin 3. Sulfate/chloride contaminations 1. Low acid concentration 2. Metallic contaminations 1. Organic contaminations 2. Metallic contaminations Poor substrate cleaning 1. Organic contaminations 2. Metallic contaminations 1. Organic contaminations 2. Low additive 3. Low temperature Corrective action 1. Adjust metals concentrations 2. Adjust current density 1. Ad additive 2. Ad acid

Roughness

Poor throwing power

Poor solderability
Poor adhesion Brittle deposit

Dark deposit

1. Filter 2. Filter 3. Increase rinsing and filter the bath 1. Ad acid 2. Dummy bath at 1-2 A/ft (0.10.2 A/dm) 1. Carbon treat 2. Dummy bath at 1-2 A/ft (0.10.2 A/dm) Improve cleaning 1. Carbon treat 2. Dummy bath at 1-2 A/ft (0.10.2 A/dm) 1. Carbon treat 2. Ad additive 3. Increase temperature

Tin alloy electroplating in methane sulfonic solutions

Electroplating in methane sulfonic acid solutions is more controllable process than deposition in fluoborate solutions. It allows to obtain high quality tin base coatings of consistent chemical composition.
Bath ingredients Stannous methane sulfonate Lead methane sulfonate Copper methane sulfonate Methane sulfonic acid (MSA) Organic brighteners (additives) Deionized (DI) water

Tin alloy electroplating in methane sulfonic solutions

Operating conditions:
: 70-100F (21-38C) : Solution and/or cathode rod, no air agitation Anodes composition : similar to the coating composition Filtration : continuous with minimum 2 bath turnovers per hour, no carbon Cathode current density : 10-40 A/ft (1.1-4.3 A/dm) Temperature Agitation

Bath formulations
Tin alloy electroplating in Methane sulfonic acid solutions Tin Lead Copper Coating
Pure tin (100Sn) 90Sn-10Cu MSA

oz/gal 6
6.7

g/l 45
50

oz/gal

g/l

oz/gal g/l oz/gal 26

0.67 5 26

g/l 200
200

90Sn-10Pb
60Sn-40Pb

3
2

22
15

0.4
1

3
7.5

26
26

200
200

Problems and troubleshooting

Problem Burning at high current densities Cause Corrective action 1. Adjust metals 1. Low metals concentrations concentration 2. Adjust current 2. Too high current density density
1. Low additive concentration 2. Low acid concentration 1. Ad additive 2. Ad acid

Treeing at high current densities

Roughness Poor adhesion

1. Foreign particles in bath 1. Filter 2. Stannic tin 2. Filter

Poor substrate cleaning

Improve cleaning

Tin electroplating in sulfate solutions

Bath ingredients:
Stannous sulfate SnSO4 Sulfuric acid H2SO4 Organic brighteners (additives) Deionized (DI) water Operating conditions: Temperature : 70-100F (21-38C) Agitation : Solution and/or cathode rod, no air agitation Anodes composition : pure tin Filtration : continuous with minimum 2 bath turnovers per hour, no carbon Cathode current density : 10-40 A/ft (1.1-4.3 A/dm)

Bath formulations
Tin 6 oz/gal (45 g/l) Sulfuric acid 16 oz/gal (120 g/l)

Problems and troubleshooting

Problem Burning at high current densities Treeing at high current densities Cause 1. Low metals concentration 2. Too high current density 1. Low additive concentration 2. Low acid concentration 1. Foreign solid particles in bath 2. Stannic tin 1. Low acid concentration 2. Low tin concentration Corrective action 1. Adjust metals concentrations 2. Adjust current density 1. Ad additive 2. Ad acid 1. Filter 2. Filter 1. Ad acid 2. Add stannous sulfate 1. Carbon treat 2. Dummy bath at 1-2 A/ft (0.10.2 A/dm) Improve cleaning 1. Carbon treat 2. Dummy bath at 1-2 A/ft (0.10.2 A/dm) 1. Carbon treat 2. Ad additive 3. Increase temperature

Roughness
Poor throwing power

Poor solderability Poor adhesion

Brittle deposit

1. Organic contaminations 2. Metallic contaminations Poor substrate cleaning

1. Organic contaminations 2. Metallic contaminations 1. Organic contaminations 2. Low additive 3. Low temperature

Dark deposit

Tin electroplating in stannate solutions

Bath ingredients: Potassium stannate K2SnO33H2O Free potassium hydroxide KOH No additives are required Deionized (DI) water
Operating conditions: Temperature : 150-180F (66-82C) Agitation : Solution and/or cathode rod Anodes composition : pure tin, steel, stainless steel Filtration : continuous with minimum 2 bath turnovers per hour Cathode current density : 30-100 A/ft (3.2-11 A/dm) Bath formulations Potassium stannate 13.5 oz/gal (100 g/l) Free potassium hydroxide 2 oz/gal (15 g/l)

Problems and troubleshooting

Problem Low cathode efficiency Cause Corrective action

1. Low tin concentration 2. Low temperature 3. High current density

1. Low free potassium hydroxide 2. Low temperature 3. High current density 1. Low temperature 2. Low free potassium hydroxide 3. Low tin concentration Stannous tin formation

1. Ad potassium stannate 2. Increase temperature 3. Adjust current density

1. Ad potassium hydroxide 2. Increase temperature 3. Adjust current density or increase anode area 1. Increase temperature 2. Ad potassium hydroxide 3. Ad potassium stannate Add hydrogen peroxide

Low anode efficiency

Low conductivity

Spongy dark deposit

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