Acid Copper

Acid copper baths are simple formulations, containing copper ions, additives, and either sulfate or
fluoborate ions, along with the corresponding acids. Because of their acidity they cannot be plated
directly onto active metals such as zinc die castings and steel for they will produce non-adhering
immersion deposits.

The chemical cost of acid-copper baths is low and their compositions are not very critical. When
compared with cyanide and alkaline non-cyanide baths, their effluent control is simpler, they are
easier to control, and they are more stable.

Their anode and cathode efficiencies are high (close to or equal to 100 pct), and they
can tolerate high current densities. However, because of their low cathode polarization,
the acid baths do not have a throwing power as good as that of alkaline solutions,
making them poor strike baths.

TABLE IV—Typical Acid Copper Sulfate Baths

General-Purpose Printed-Circuit
Bath
High-Throw
High-
(Concentrations in
Speed
g/liter)
Copper sulfate 190-250 60-90 80-135
Sulfuric acid 45-90 150-225 185-260
Chloride ion (ppm) 20-80 30-80 40-80
Temperature (F) 70-100 70-90 70-110
Cathode current density
(depending on degree of agitation) 20-200 15-50 50-200
(asf)
Anode CD 20-40 7-25 20-100
Anode: cathode ratio At least 1:1 2:1 2-3:1
Anode & cathode efficiency (pct) »100 »100 »100
Voltage 5-12 5-12 5-12
Agitation Air or mechanical Air or mechanical Vigorous air
or solution
Filtration Continuous, 1-2 turnovers per hr, 5 micron polypropylene or Dynel.
Diatomaceous-earth type filter aid can also be used.
Rectifier 5 pct or less ripple at all load levels.
Cooling Lead or titanium coils when needed.
Proprietary additive As recommended by supplier
Anodes Bagged phosphorized copper (0.02-0.08 pct.P)

Chemistry of Acid Copper Sulfate

Table IV shows the chemical makeup and operating conditions of typical acid-copper-sulfate baths.
General-purpose baths are used for decorative plating, while high-throw and high-speed baths are
for special applications such as for printed-circuit-board and strip plating. A high-throw bath can
plate almost as much copper in the holes of printed-circuit boards, where current density is very
low, as it plates on the surfaces of the boards. A high-speed bath can plate about twice as fast as
conventional baths while retaining all the desired deposit properties.

The concentration of copper sulfate helps determine the properties of the baths. At higher
concentrations, the resistivity of the bath is greater, and the anode and cathode polarization are
slightly reduced. At lower copper sulfate concentrations, the throwing power increases. A
concentration of less than 60 g/liter of copper sulfate decreases cathode efficiency. The solubility
of copper sulfate decreases with increasing sulfuric acid concentration.

Sulfuric acid gives the bath its high conductivity, reduces anode and cathode polarization, and
prevents precipitation of basic copper salts. A practical minimum sulfuric acid concentration is
about 45 g/liter.

Agitation, Anodes. To ensure brightness and to prevent high-current-density burning, agitation

of acid copper baths is essential. Air agitation from an oil-free blower is best for decorative copper
plating. For PC boards, mechanical agitation, in which the PC board's movement forces solution
through the board's holes is good to obtain the maximum throwing power. For high-speed copper
plating at high current density, high-velocity solution flow and/or part movement, perpendicular to
the cathode, has been successful.

A necessary black cupric oxide film forms on the anodes. If it is disturbed, brightener
consumption will increase, deposit ductility will decrease and leveling of deposits will
be reduced. If the anodes have either a pink or a light gray appearance, too-low anode
phosphorus content or electrical problems may be the cause. Low-current-density
electrolysis, starting at five and building up to 25 asf, should develop the desired film if
the correct anode material is used.

TABLE V—Acid-Copper Troubleshooting Guide

A: General-Purpose Baths
Problem: Copper deposit is burned.
Causes: 1) Insufficient agitation; 2) solution temperature is less then 70F; 3) copper content of solution is too low; 4) brightener
concentration too low; 5) maximum current density has been exceeded; 6) anodes too long or too many; 7) chloride content is out of
normal range.

Problem: Poor throwing power.

Causes: 1) Copper content of solution is too high; 2) sulfuric acid content of solution is too low; 3) solution temperature too high; 4)
metallic contamination of solution.

Problem: Poor leveling.

Causes: 1) Low brightener content; 2) chloride content too low; 3) cathode current density too low; 4) brightener concentration
excessively high; 5) organic contamination;

Problem: Roughness.
Causes: 1) Particulate matter in bath; 2) too-low or too-high anode-to-cathode ratio (ratio typically 2:1); 3) low-phosphorus-content
anode; 4) substrate rough before plating; 5) excessive current density; 6) insufficient acid; 7) high rectifier ripple.

Problem: Pitting.
Causes: 1) Grease or oil contamination in plating bath; 2) particulate matter in bath; 3) excessive and/or non-uniform air agitation; 4)
pitting in substrate before plating; 5) poor cleaning of substrate.

Problem: Streaking of deposit.

Causes: 1) Excessive brightener additions; 2) organic contamination; 3) cleaners and/or rinses prior to copper plating are contaminated.

Problem: Lack of response to brightener additions.

Causes: 1) Too low anode-to-cathode area; 2) metallic contamination; 3) high chloride content for brightener system; 4) anode
polarization; 5) sulfuric acid content too high; 6) solution temperature too high; 7) excessive organic contamination.

Problem: Step plating.

Causes: Chloride content too low.

Problem: Copper deposit peels from basis metal.

Causes: 1) Poor cleaning of basis metal; 2) rinses after cleaning are contaminated; 3) Immersion layer on zinc or iron (steel) substrates.

Problem: Enlarged grain structure of copper deposit.

Causes: 1) Brightener content too low; 2) chloride content too low (low chloride will also cause treeing and nodulation of the deposit).

Problem: Anodes off-color.

 Causes: 1) If anodes are very bright and crystalline, acid is in excess; 2) if anodes are dark, acid is deficient; 3) if anodes are green,
solution is contaminated with hydrochloric acid.

Problem: Deposit too soft.

Causes: 1) Low acid content; 2) slow rate of deposition; 3) high temperature of bath.

Problem: Deposit very hard.

Causes: 1) Excessive acidity; 2) low temperature of bath; 3) organic contamination in solution; 4) heavy contamination of iron.

B: Specialty Processes (Printed Circuit)

Problem: Brittle deposit, resulting in cracks in copper on plating board's walls after solder-float test.
Causes: 1) Brightener level in excess; 2) organic contamination; 3) metallic impurities.

Problem: Poor tensile properties of deposit.

Causes: 1) Particulate matter in bath, causing discontinuities in the plating, leading to low tensile strength; 2) metallic or organic
contamination in the plating solution.

Problem: Matte or dull deposit around opening of plated-through-hole (also referred to as dishing or fisheye).
Causes: 1) Excess brightener or organic contamination (from brightener-breakdown products, cleaner dragin, and resist-leach products);
2) incorrect or excessive air agitation; 3) use of dirty compressed air instead of clean blower air.

Problem: Nodules in copper deposit on walls of plated-through-hole.

Causes: 1) Poor drilling; 2) solution temperature out of range; 3) brightener level in excess; 4) particles in solution.

Contamination. Nickel, cobalt, chromium and iron will not readily co-deposit with copper, but will
reduce the solution's conductivity when about 1,000 ppm are present. These metals cannot be
removed.

Iron will also cause the copper concentration in the bath to increase by a reaction with the anode
during idle periods.

Calcium and lead will precipitate as sulfates and cause roughness if not removed, but they do not
affect the deposit.

Tin can codeposit to cause rough dark deposits if present above 60 ppm. Lead and tin are usually
introduced into the bath by carry-over on solder plated racks. Stripping the racks after solder
plating will minimize this. Medium-current-dummying (15-20 asf) will remove tin.

Antimony will codeposit if it is in the 20- to 100-ppm range, causing brittle deposits. Antimony is
usually introduced as an impurity in the copper anodes. It can be removed by low-current-density
dummying. Aluminum in amounts greater than 50 ppm may cause dullness in recesses.
 Troubleshooting,
TABLE VI—Typical Carbon/Hydrogen Peroxide purification. Acid-copper-
Treatment for Acid Copper sulfate baths are easy to
maintain. Use wet analysis
1. Transfer the entire plating solution into a properly leached treatment tank. to control copper, sulfuric
acid, and chloride. Add
2. Raise the temperature to approximately 110F. proprietary addition agents,
which control brightness,
3. While stirring, add one quart of 30-35 pct hydrogen peroxide for every 100 gallons of plating ductility, and leveling, on
solution. Agitate for two hours at 110F. the basis of amp hours. You
can also regulate their
4. Raise the temperature to 140F and continue to agitate for two more hr. addition by using Hull Cells
and a copper analysis.
5. Add four pounds of a finely powdered activated plating grade carbon per 100 gallons of plating
solution. Maintain the temperature at 140F. After a two-hour mixing period, turn off the heat and
agitation. Permit the solution to settle. Table V lists some typical
problems that might be
6. Cool a sample to operating temperature and Hull Cell test to insure that the deposit is matte encountered. If an additive
across the entire Hull Cell panel. If the deposit is still bright, a longer treatment time and/or more system is used, consult the
carbon will be needed.
supplier's troubleshooting
guide, too.
7. Once the Hull Cell panel is matte in appearance, pump the treated solution through a filter
packed with diatomaceous-earth filter aid into a clean plating tank. Be careful that the powdered
carbon does not pass through the filter. Even though acid-copper
baths are very tolerant to
8. Add normal make-up additives to the treated solution and dummy the solution for one to two contamination, they must
hours at 10-15 asf.
be purified occasionally.
Organic contaminants are
9. Hull Cell test to insure that the bath is at its desired level before resuming plating.
probably the most common,
since they are easily
Note: If enough carbon can be placed in a filter, the treatment can be conducted in the plating introduced into the bath
tank. One disadvantage of this is that the plating tank cannot be cleaned out and inspected during
the treatment. This is also a good opportunity to inspect the anode bags and replace if necessary. from cleaners, oils, greases,
brightener-breakdown
Follow steps two through four, then pack the filter with 8-10 lb granular carbon per 100 gal products and brightener
plating solution. Use granular carbon to help insure that carbon does not get through the filter overloads.
and into the plating tank. Circulate the solution through the filter until a matte deposit is obtained
in a Hull Cell test. If after six to eight turnovers the deposit is not matte, repack the filter with a
fresh charge of carbon. Repeat this procedure until the matte is obtained. Most proprietary systems
can tolerate an overdose of
After carbon treating, cool the solution and add a normal make-up quantity of additives. Next, additives for short periods
dummy the solution for one to two hours at 10-15 asf. Run a Hull Cell to insure a bright deposit is of time, but if overdosing
obtainable, and resume plating.
continues, a light carbon
treatment might be necessary. Pack the filter with activated carbon and circulate the solution
through the carbon for about three or four turnovers. This should remove enough organics to
permit the bath to continue to operate satisfactorily.

Most acid-copper baths will eventually require a carbon/hydrogen peroxide treatment to remove
organics that cannot be removed by a light carbon treatment. The organic contaminants will
eventually cause the bath to have a narrow bright plating range and to produce a dull and burned
copper deposit. Table VI describes a typical full carbon treatment.

Acid Fluoborate Copper Processes

Copper fluoborate is much more soluble than copper sulfate. Therefore for high-current-density
and high-speed processes, the copper-ion concentration can be more than double that obtainable
in the sulfate baths. The fluoborate ion also helps provide solubility and conductivity. But when
compared with sulfate baths, the fluoborate bath has less throwing power.

The copper sulfate bath is more widely used than the fluoborate because it is less expensive. Also,
many more additive systems have been developed for copper-sulfate formulations.
Copper fluoborate baths are more hazardous to use and harder to waste treat than sulfate baths.
And as with the sulfate baths, the fluoborate solutions are very corrosive, making careful design of
plating equipment important.