TECHNICAL DATA SHEET

Cupracid® ULTRA
Acid Copper Plating Process
Issue 3 of 14.01.2004
Replaces Issue 2 of 16.07.2002

INTRODUCTION

Cupracid® ULTRA is a sulfuric acid-based copper plating process that produces low-
stressed, ductile, and bright copper deposits. The additives are designed to operate at
bath temperatures up to 86o F (30o C) without any noticeable loss in quality. It can be
used on both properly prepared metals and plastic substrates.

The outstanding features of the Cupracid ULTRA bright acid copper process are:

! High deposit brightness with exceptional rates of brightening and leveling with no
loss of ductility

! Easily buffable surface

! Ease of bath maintenance and control under production conditions

! Addition agents are added on an ampere-hour basis and controlled by Hull Cell
tests.

Atotech India Limited,

For Industrial Use Only 66 KM Stone, NH 8, Delhi – Jaipur Highway,
Atotech India gives no warenty, express or implied, and all products are sold upon condition that
Village Sidhrawali, Distt. Gurgaon – 123413
purchasers will make their own tests to determine the quality and suitability of the product. Atotech shall in
Haryana, India.
no way be responsible for the proper use and service of the product. Any information or suggestions given
are without warranty of any kind and purchasers are solely responsible for any loss or damage arising
Tel: (+91) 1274 – 267190, 267191
from the use of such information or suggestions. No information or suggestions given by us shall be
Fax: (+91) 1274 – 267189
deemed to be a recommandation to use any product or process in conflict with any existing patent rights
Email: [email protected]
www.atotech.com
Atotech India Limited is ISO 9001 : 2000, ISO 14001 : 1996 and OHSAS 18001 : 1999 certified
 Cupracid ULTRA Page 2 / 11

SOLUTION COMPOSITION

Bath Component Optimum Range

Copper Sulfate (CuSO4 5H2O) 28 oz/gal (210 g/l) 26 - 34 oz/gal (195 - 255 g/l)

Sulfuric Acid (66o Baumé) - 8 oz/gal (60 g/l) 6.7 - 9.3 oz/gal (50 - 70 g/l)

Chloride - 100 ppm (100 mg/l) 80 - 150 ppm (80 - 150 mg/l)

Cupracid ULTRA Make-up - 1.0% by vol. (10 ml/l)

Cupracid ULTRA Part A - 0.05% by vol. (0.5 ml/l) 0.04 - 0.06% by vol. (0.4 -
0.6 ml/l)

Cupracid ULTRA Part B - 0.05% by vol. (0.5 ml/l) 0.04 - 0.06% by vol. (0.4 -
0.6 ml/l)

OPERATING CONDITIONS

Operating Variable Optimum Range

Temperature - 75 - 82o F (24 - 28o C) 68 - 86o F (20 - 30o C).

Cathode Current Density - 30 Amps/ft2 10 - 55 Amps/ft2

(3.0 Amps/dm2) (1.0 – 6.0 Amps/dm2)

Anode Current Density - >5 Amps/ft2 (0.5 Amps/dm2) 5 - 25 Amps/ft2

to form and maintain a solid, (0.5-2.5 Amps/dm2)
black anode film.

Voltage - 1.0-4.0 volts. Some baths may require up to 6 volts

depending on the current density and bath loading.
Maximum ripple from the rectifier at the operating current
should not exceed 10%.

Agitation - Cathode rod movement and/or air from a low-pressure

blower. Compressed air, no matter how well filtered, is
unacceptable. A suitable material for the air sparging system
is PVC.

Filtration - Continuous filtration through 5-micron media is

recommended. The filter turnover rate should be 2 - 3 times
per hour.
 Cupracid ULTRA Page 3 / 11

Anodes - Copper anodes with a phosphorus content of 0.03-0.06% are

recommended. Phosphorized copper nuggets or balls in
titanium baskets are preferred.

Ventilation - Required. Refer to local standards for design requirements.

EQUIPMENT

Tanks - Mild steel with a hard rubber lining, or PVC/polyester reinforced

material. If lined steel is used, the tank should be spark-tested to
assure that the linings are continuous.

Heating/Cooling- Graphite, Titanium, PTFE, PVC, or Polyethylene. If metal is used, it

must be grounded or made anodic to prevent bipolarity on plated
parts.

Anode Bags - The anodes should be enclosed in bags made of acid-resistant, fully
synthetic material such as dynel or polypropylene. Typically, with dye-
based acid copper systems, a loosely woven bag is preferred to
reduce the risk of anode polarization if the bags plug up.

Filter Aid - Diatomaceous earth.

MAKE-UP PROCEDURE

1. In a separate storage or mixing container made of PVC or polyethylene, dissolve

the required amount of copper sulfate in half the total volume of deionized water
required. To accelerate dissolution, the water may be heated to 104 - 122o F (40 -
50o C).

2. When the copper sulfate has dissolved, add 1.7-lbs/100 gallons (0.2 kg/100 liters)
of low iron, low sulfur, plating grade activated granular or powdered carbon. It
should be added and allowed to react for about one hour while stirring
continuously.

3. Filter the solution into the clean tank and make up to about 90 - 92% of the final
volume with deionized water. The filtration process must be performed with
extreme care, since particles of carbon in the plating bath can cause matte or
rough copper deposits. When using the filter for continuous filtration, it should be
carefully cleaned of carbon particles. Filter cartridges and/or filter paper must also
be replaced.

4. Carefully add the required amount of sulfuric acid carefully while stirring vigorously.
(CAUTION! SAFETY GLASSES AND PROTECTIVE CLOTHING MUST BE
WORN!) During this step care must be taken if the temperature does not rise above
140o F (60o C).
 Cupracid ULTRA Page 4 / 11
5. After cooling to about 77o F (25o C), add the required amounts of hydrochloric acid
(2.2 ml HCl/1000 L for 1 ppm Chloride), Cupracid Ultra Make-up, Part A and Part B.

6. Electrolyze the solution for 7.6 amp-hours/gallon (2 amp-hour/liter) to achieve a

level of optimal brightness. PROCESS CONTROL AND SOLUTION
REPLENISHMENT

Copper Sulfate is the source of copper metal plated out onto the work. It is important that
the concentration of copper sulfate be maintained within the recommended limits. The
required amount of copper sulfate pentahydrate crystals should first be dissolved in an
adequate volume of warm water. After the solution has cooled to room temperature, it
should be added to the bath through the filter. Low concentrations will cause high current
density burning. High concentrations can cause two types of problems. First, air agitation
sparger pipes may become plugged with insoluble crystals. Second, the anodes may
become coated with copper sulfate crystals and then polarize.

Sulfuric Acid increases solution conductivity and lowers the voltage required to plate at a
particular current density. The addition of 0.4 gallons per 100 gallons (0.4 liters per 100
liters) of bath, increases the sulfuric acid content by 1 oz/gal (7.5 g/l). Low concentrations
will cause an increase in the operating voltage required to attain a given current density.
High concentrations can lead to anode polarization and/or precipitation of copper sulfate
crystals.

Chloride works in combination with the Cupracid ULTRA additives to give bright, highly
leveled copper deposits. Careful control of chloride content is essential to optimum bath
performance. Chloride concentration can be adjusted by using C. P. grade hydrochloric
acid (100 ml/1,000 gal. = 10 ppm) (2.2 ml HCl/1000 L for 1 ppm Chloride) or sodium
chloride (63 g/1,000 gal. = 10 ppm). Low chloride levels can result in striated deposits and
low current density dullness. High chloride levels can cause anode polarization.

Cupracid ULTRA Additives - In order to achieve optimal brightness and leveling

characteristics, Cupracid ULTRA Part A and Cupracid ULTRA Part B must be present in
the bath in a certain ratio. This ratio must be carefully observed, since the two materials
have a mutual influence on each other (i.e., an excess of one additive has the same effect
as a deficiency of the other). The Cupracid ULTRA addition agents can be controlled by
plating 2 amp., 10 min. air agitated Hull Cell panels. Please refer to the attached charts
showing the appearances of typical Hull Cell panels. Cupracid ULTRA Part A should
never be mixed with Part B. The Cupracid ULTRA additives can be added directly to the
bath according to the following schedule, with vigorous stirring.

Addition Agent Additions Per 10,000 Ampere Hours

Cupracid ULTRA Part A - 0.18 gal. 0.7 liters

Cupracid ULTRA Part B - 0.13 gal. 0.5 liters

The consumption of Cupracid ULTRA Parts A and B depends on the degree of brightness
and leveling required. If copper bar anodes are used, consumption of Part B may
decrease. In some cases where dragout and evaporation losses are high, periodic
additions of Cupracid ULTRA Make-up Solution (100 ml per 10,000 Ampere-hours) may
be required.
 Cupracid ULTRA Page 5 / 11

Deficiency of Cupracid ULTRA Part A or Excess of Cupracid ULTRA Part B

A deficiency of Cupracid ULTRA Part A or an excess of Part B causes reduced leveling

and hazy deposits in medium to low current density areas. In such a case, Cupracid
ULTRA Part A should be added in increments of 10 ml per 100 liters of copper bath. If
required, the addition of Cupracid ULTRA Part B should then be reduced and/or the
additions of Cupracid ULTRA Part A, increased.

Deficiency of Cupracid ULTRA Part B or Excess of Cupracid ULTRA Part A

A deficiency of Cupracid ULTRA Part B or an excess of Cupracid ULTRA Part A results in

high current density nodular plating. If this is noted, Cupracid ULTRA Part B should be
added in increments of 10 ml per 100 liters of plating bath. In order to prevent haze
formation, Cupracid ULTRA Part A must be added at the same time, in a quantity
corresponding to 20% of the Cupracid ULTRA Part B being added.

ANALYSIS PROCEDURES

Determination of Copper Sulfate

Reagents Required:

Murexide Indicator - Weigh 100 grams of sugar and transfer about 85 grams to a plastic-
capped jar. Grind 0.25 grams of murexide powder (ammonium purpurate) with the
remaining 15 grams of sugar and transfer the powdered mixture to the jar. Shake the jar
until all the sugar granules have been uniformly coated with murexide.

Ammonium Hydroxide - Reagent grade, 28%

0.1 Molar EDTA Solution

Ammonium Buffer - Dissolve 68 grams of ammonium chloride in about 300 ml of water

and wash into a liter bottle. Add 570 ml of fresh ammonium hydroxide and dilute to one
liter. Store in a polyethylene bottle or NO-Sol-Vit glass bottle using a rubber stopper
instead of a cap.

Procedure:

1. Pipette a 2.0 ml sample of bath into a 600 ml beaker.

2. Add 5 ml of ammonium buffer and dilute to 450 ml with water.

3. If solution is not a deep clear blue color, add the ammonium buffer dropwise until it
is clear blue.

4. Add about 0.5 grams of murexide indicator (1 Coor's No. 1A scoop) and stir until
dissolved.

5. Titrate with 0.1Molar EDTA solution until the greenish color turns to an intense
purple.
 Cupracid ULTRA Page 6 / 11

6. Calculate the copper sulfate content:

CuSO4 • 5H2O (oz/gal) = ml EDTA x M EDTA x 16.66

CuSO4 • 5H2O (g/l) = ml EDTA x M EDTA x 124.95

Determination of Sulfuric Acid

Reagents Required:

1 N NaOH Solution
Bromphenol Blue Indicator

Procedure:

1. Pipette a 2 ml sample of the bath into a 400 ml tall beaker.

2. Add 75 ml of deionized water, 4-6 drops of bromphenol blue indicator solution.

3. Titrate with 0.1 N NaOH to a deep blue color. Use a magnetic stirrer. (Note: with
iron present, titrate to a slight turbidity.)

4. Calculate the sulfuric acid content:

H2SO4 (oz/gal) = ml NaOH x Normality of NaOH x 3.259

H2SO4 (g/l) = ml NaOH x N x 24.4

Determination of Chloride

Reagents Required:

1:1 Nitric Acid

0.1 N Silver Nitrate
N Mercuric Nitrate - Dissolve 1.083 grams of mercuric oxide (HgO) in 5 ml of 1:1 HNO3
and dilute to one liter with deionized water. This solution need not be standardized.
Procedure:

1. Pipette a 25 ml sample of the bath into a 150 ml beaker containing a magnetic stir
bar.

2. Add 30 ml of deionized water and 20 ml of 1:1 nitric acid.

3. Add 3 drops of 0.1 N silver nitrate solution to produce turbidity.

4. Titrate with 0.01 N mercuric nitrate solution stirring constantly until the turbidity just
clears.

5. Calculate the chloride concentration using the following equation:

 Cupracid ULTRA Page 7 / 11

Cl (mg/l or ppm) = ml of 0.01 N mercuric nitrate x 355

ml of sample

BATH TROUBLESHOOTING

The Cupracid ULTRA solution can be monitored using an air-agitated, 267 ml. Hull Cell.
The anode is a phosphorized copper bar and the cathode, a brass panel scratched with
type "0000" emery paper. An aquarium pump is used to supply clean air to the test cell.
Plating is done at 2 amps. for 10 minutes.

Examination of the test panel will reveal overall brightness and leveling, LCD coverage,
and the presence or absence of HCD noduling. Test panels should be compared with
panels plated in an optimized Cupracid ULTRA solution.

If pitting is observed on the work and it is not due to porosity in the substrate (e.g.,
aluminum), the bath chemistry may be checked by plating a V-shaped, recessed brass
panel. One liter of plating solution is placed in a glass beaker along with a phosphorized
copper anode and air sparger. The properly cleaned recessed panel is plated at 2 amps.
for 15 minutes with air agitation and the deposit evaluated. There should be no signs of
pitting on the surface or shelf areas on the face side of the panel. If pitting is present, it
can be categorized as (1) fine pitting; (2) crater pitting; or (3) cluster pitting. Additions of
Cupracid GM Plus Wetting Agent will normally reduce or eliminate #1 or #2. If this does
not eliminate the problem, contact your Atotech technical service representative for
assistance. The third type, cluster pitting, is usually a sign of excessive wetting agent
content.

The addition rates of Cupracid GM Plus Wetting Agent are:

Initial -20 ml of Cupracid GM Plus Wetting Agent per 100 liters of bath

Continuous - 100 - 200 ml of Cupracid GM Plus Wetting Agent every 10,000

Ampere Hours

Cupracid GM Plus Wetting Agent is a foam-producing product. It will be extensively

removed by treatment with activated carbon.

WASTE DISPOSAL

This material must be disposed of in accordance with all applicable federal, state, and
local regulations and permits. Consult the MSDS for additional regulatory information. The
information contained herein is general in nature and may not apply to each application.

GENERAL SAFETY PRECAUTIONS

When working with this product(s), ensure that all health, environmental, and safety
regulations and standards are met. Avoid direct contact with this material. Do not inhale
associated mist, vapors, and/or dust. Maintain and limit exposure as recommended by
OSHA, ACGIH, and other state and local regulations. Wash contaminated clothing before
 Cupracid ULTRA Page 8 / 11
reuse. Always comply with the Hazard Communication Standard, 29 CFR 1910.1200.
Emergency showers and eyewashes must be readily available.

It is recommended that the plating chemistry product(s) referred to in this Technical

Information Sheet be used: (a) in accordance with the information provided in product
specific MSDS; and (b) in compliance with all applicable requirements and guidelines
established by OSHA, NIOSH, ACGIH, NFPA, and others.
NOTE: A Material Safety Data Sheet (MSDS) for this product(s) is available upon
request from Atotech India Ltd.

REVIEW MSDS BEFORE USING THIS PLATING CHEMISTRY AND FOR SPECIFIC
INFORMATION. A precautionary approach should be used when there is potential for
chemical exposure -- this includes minimizing exposure potential, rapid decontamination,
and medical follow-up.
 Cupracid ULTRA Page 9 / 11

CUPRACID ULTRA HULL CELL CHART

Optimum Panel Recommendations

None

HCD, MCD, LCD

Bright Levelled Deposit

High Cupracid Ultra Part A

Bright Deposit, Add Cupracid Ultra Part B in

Reduced Levelling 0.1 ml/l increments
Uniform, Bright
Levelled Deposit

Low Cupracid Ultra Part A

Uniform, Bright Smoky, Dark Add Cupracid Ultra Part A in

Levelled Deposit Copper Deposit 0.1 ml/l increments
 Cupracid ULTRA Page 10 / 11

CUPRACID ULTRA HULL CELL CHART

No Cupracid Ultra Part A Recommendations

Add 0.5 ml/l Cupracid Ultra Part A

Bright Semi bright
Non levelled Non leveled
Deposit Deposit

High Cupracid Ultra Part B

Smpky dark Add Cupracid Ultra Part A in

Copper Deposit 0.1 ml/l increments
Uniform, Bright
Levelled Deposit

Low Cupracid Ultra Part B

Uniform, Bright Bright Deposit Add Cupracid Ultra Part B in

Levelled Deposit Reduced Levelling 0.1 ml/l increments
 Cupracid ULTRA Page 11 / 11

CUPRACID ULTRA HULL CELL CHART

No Cupracid Ultra Part A Recommendations

Add 0.5 ml/l Cupracid Ultra Part A

Matte Semi bright
Striated Deposit
Deposit 10 ml/l Make Up solution

Test Conditions:

Current – 2 amps.
Time – 10 min.
Agitation – Air from an aquarium pump
Anode – Phosphorised copper
Substrate – Polished brass panel