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Copper Plating

By Dr. Donald L. Snyder


World Wide Technical Marketing Manager
Atotech USA Inc.
Rock Hill, South Carolina

Excluding the specialty and continuous-strip-plating industries, more copper is plated than any Visit PF's
other metal except for nickel. There are several reasons for this.
Plating Zone
•Copper is an excellent undercoat for subsequent deposits, since it is a good metal to cover
substrate defects such as holes and splinters. Buffing copper, which is very easy to do, even PF's Tools
improves upon its ability to be an excellent substrate. Copper, and especially buffed copper, can
provide an easy-to-plate, highly level and bright substrate.

•Copper is among the less expensive metals and is in relatively stable supply. More leveling can
be obtained for the cost of the metal electroplated than for any other metal.

•Copper has a high plating efficiency and many copper plating processes offer good coverage and throwing power.

•Although the EPA limits the discharge of copper and copper plating solutions, copper metal is less environmentally
hazardous than many other plated metals. The waste-treatment processes for copper plating solutions and copper-
containing rinse waters are well known, and in most cases easy to accomplish. Also, many times the copper metal and
even the plating bath can be recycled.

•Copper's high electrical conductivity is exceeded only by silver, making it an excellent and inexpensive coating for
products such as printed-circuit (PC) boards. Used as a topcoat on steel wire, it produces high-strength, conductive
electrical cable.

Types of Processes

Three basic types of processes are commerically available based upon the complexing system utilized. They are
alkaline-(several modifications of cyanide and non-cyanide); acid-(sulfate and fluoborate); and mildly alkaline-(pyro
phosphate) complexed baths.

Alkaline Cyanide Solutions

Alkaline-copper solutions have better throwing power (uniform deposit thickness) than acid-copper solutions. However, it
cannot be plated at as high a current density as acid copper. It is also relatively more difficult to control than acid-sulfate
solutions. Also, cyanide involves special handling and treatment procedures because of its acute health hazards and
waste-disposal problems. But, the procedures are well understood, and cyanide can, with care, be handled safely.

Types of cyanide copper baths. A cyanide TABLE I—Typical Cyanide Copper Baths
copper solution can be used in either rack or
Strike Rochelle High-efficiency
barrel plating. The processes can be generally
classified as the low-efficiency or "strike" (Concentrations in g/liter)
process; the medium-efficiency "Rochelle" CuCN 15 45 75
process; and the high-metal, high-efficiency or NaCN 28 56 100*
"high-speed" process. Typical plating-bath
or KCN** - - 133*
compositions and operating characteristics are
shown in Table I. NaOH - - 30*
or KOH** - - 42*
A cyanide-copper strike bath is typically used to
Na2CO3 15 30 -
deposit a thin, adherent layer that can
completely cover an active metal surface such Rochelle salt by analysis - 45 optional
as zinc or steel prior to further plating Cu as metal 10.5 31.5 53
operations. Because of the bath's low plating "Free" NaCN*** 11 6 19*
efficiency, the plating time, and thus the

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deposit's thickness, is often determined by the or "Free" KCN - - 25*


time needed to just obtain complete coverage.
Operation
The maximum practical deposit thickness is Cathode CD, A/m2 100- 150- 100-
typically in the range of 0.05 to 0.10 mil. The
300 600 1000
copper strike serves only as a protective layer
Anode Cd,
for further plating, typically with copper or 100 300 500
nickel. It also improves adhesion and in some limiting, A/m2
cases acts as "insurance" in the preplate cycle. Temperature, F 120-145 130-160 145-175
Limiting thickness 2.5 um 13 um >25 um
The low metal and high cyanide levels in the
Cathode efficiency, pct 30-60 30-50 90-99
copper strike are responsible for the low
efficiency, but these same properties ensure Proprietary additives As recommended by supplier
against a non-adhering immersion layer of Agitation Solution movement only Mechanical, mild air,
copper forming on the surface being plated. solution flow
This formulation also produces the desired Filtration Continuous; one turnover per hr.
excellent covering (plating in recesses/holes) * Values given are for all-sodium or all-potassium baths; solutions with equal molar
and throwing (uniform deposit thickness) concentrations of sodium and potassium are also being used.
powers. ** Potassium salts produce baths with greater cathode efficiencies and greater
tolerance to contamination.
*** "Free" cyanide prevents CuCN from forming insoluble fine particles on the
The Rochelle-salt bath is often used for similar
anodes and in solution, and promotes anode corrosion.
purposes. But it may also be used to deposit
thicker deposits than can be obtained with cyanide-strike baths.

The high-efficiency formulation, with its higher temperature and copper concentration, plates faster and can produce
thicker deposits. However, it has lower covering power. Therefore a cyanide strike must be used prior to use of this bath
when parts with low-current-density areas are plated. Today the trend is to use cyanide copper baths just for strikes and
to use other processes such as acid sulfate copper to increase deposit thickness.

Carbonate Chemistry. Carbonate, typically as sodium carbonate, is added to strike- and Rochelle-salt processes at bath
makeup. It controls pH by acting as a buffer and reduces anode polarization.

Carbonate is not added to high-efficiency baths. However, carbonate forms naturally during operation, in all cyanide
baths. This is a result of the decomposition of free cyanide through hydrolysis and cyanide oxidation at the anode.
Carbonate also builds up in the bath by the absorption of carbon dioxide from the atmosphere, an effect promoted by air
agitation.

If carbonate concentration reaches 75 to 100 g/liter, some should be removed since it reduces the bright plating range.
Remove carbonates by precipitation, through the addition of calcium (lime) or barium hydroxide to form insoluble calcium
or barium salts. Barium cyanide, which also lowers carbonate content, prevents an increase in the hydroxide level of the
bath.

Another approach is to chill the sodium-based bath to form sodium carbonate, which is much less soluble at lower
temperatures. If the temperature is reduced below 32F, copper salts also will precipitate. Carbonates cannot be chilled out
of a potassium-based bath, since potassium carbonate is too soluble.

For both the precipitation and chilling procedures, use a treatment tank other than the plating tank. This allows the
carbonate to settle out before pumping the plating solution through a filter into a cleaned plating tank.

Anodes, Current. Use high-purity, oxide-free anodes for high-efficiency decorative copper plating. Lower-quality anodes
can be used in strike and medium-efficiency Rochelle salt-cyanide copper plating baths (provided that anode current
density is kept low). Intermingle plain steel anodes with the copper anodes to control the build-up of copper in the bath.
Keep the anode/cathode ratio between 1:1 and 2:1. It's also a good idea to bag the anodes, in order to contain insoluble
particles coming from the anodes.

Current interruption and periodic reverse (PR) are beneficial in high-efficiency processes, since they help provide brighter
and smoother deposits. Current-interruption cycles are typically 10 seconds on and one second off. Typical PR cycles
require 10 to 60 seconds direct current followed by two to 20 seconds of reverse current.

TABLE II—Cyanide Copper Troubleshooting Troubleshooting, Purification. Table II lists some of the common
Guide problems and causes encountered in cyanide plating. Chemical
analysis and frequent Hull-Cell testing will avoid some of these
Problem: Anode polarized (black or green film on
problems. The best method, however, is to prevent the problem in the
anodes)
Causes: 1) Low free cyanide; 2) anode current density first place. Eliminate the source of the problem so that purification or
too high; 3) solution temperature too low; 4) insufficient other corrective measures will not need to be conducted as often.
solution agitation; 5) high organic contamination.
All cyanide copper plating baths, especially the high-efficiency baths,
Problem: Plated copper peels from basis metal or has
are sensitive to contaminants. Organic residues from buffing
blistered appearance.
Causes: 1) Insufficient cleaning of basis metal; 2) over compounds, cleaners, tank and rack materials and other organics also
cleaning of basis metal; 3) contaminated rinses prior to can contaminate the bath.
plating; 4) hexavalent chromium contamination of plating

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solution.
Continuously filtering the plating solution through a filter chamber
Problem: Dull deposit. packed with approximately 0.1 ounce of activated plating-grade
Causes: 1) Organic contamination from dragin of cleaning carbon per gallon of plating solution will remove small amounts of
and buffing compounds or oils and greases; 2) chromium
contamination; 3) insufficient brightener additions.
some organics. Change the carbon frequently and properly dispose of
the carbon. Once the carbon has been in contact with the copper
Problem: Roughness of plated part. electrolyte, it is contaminated with organics and cyanide and must be
Causes: 1) Excessive current on anode; 2) particulate treated as hazardous.
matter in bath; 3) poor quality of anode; 4) rough
substrate; 5) organic contamination.
If a carbon-packed filter is not available or if the organic
Problem: Brassy deposits. contamination is too severe, a batch carbon/peroxide treatment may
Cause: Zinc contaminated from zinc die castings. be necessary. Since this is best accomplished in a different tank than
the plating tank, chilling the solution to remove carbonates may be
Problem: Reduction of bright plating range.
Causes: 1) Excessive carbonate; 2) "free" cyanide done at the same time. Table III gives the directions for a typical
content too high. batch carbon/peroxide treatment.

Problem: Non-adherent spongy copper. Even low concentrations of hexavalent chromium, which can be
Causes: 1) Low "free"-cyanide concentration; 2) low
dragged into the bath on the racks, will produce dull and spotty
Rochelle-salt concentration (for medium-efficiency bath).
deposits. Chromium can be reduced quickly to the trivalent form and
Problem: Anodes bright and crystalline in appearance. precipitated by the addition of proprietary reducing agents directly to
Cause: 1) Excess of "free" cyanide. the plating bath. Hexavalent chromium also can be converted to the
inactive trivalent state by means of high-current-density electrolysis,
or by adding sodium hydrosulfite or sodium stannite. There is evidence however, that trivalent chromium left in the
plating bath can be reoxidized by air back to hexavalent chromium. The best procedure is to precipitate the chromium and
remove it by filtering.

TABLE III—Batch Carbon/Peroxide Treatment of Cyanide Copper Plating Baths

1. Transfer the entire plating solution to a separate clean treatment tank of equal or greater volume.

2. Heat to approximately 130-140F.

3. Add one pint of 35 pct by weight hydrogen peroxide per 100 gal of plating solution and mechanically mix
for approximately two hrs.

4. With continued agitation, add four to six lb activated carbon for each 100 gal of solution.

5. Continue mixing the solution at the elevated temperature for two or more hr.

6. Cool a sample to its operating temperature and run a Hull-Cell test to determine if the contamination has
been removed. Repeat Steps 3 through 5 if necessary.

7. When the treatment is complete, filter the solution back into the plating tank, analyze, and make the
necessary chemical, additive, and volume adjustments.

Zinc contaminants will plate out simultaneously with the copper, causing brittle and brassy looking deposits. You can
remove zinc by dummying the bath at two to four asf. Dummying also removes many other metallic contaminants.

Sulfur and its compounds cause dull, red deposits in low-current-density areas. These usually appear in deposits from new
baths, as a result of the use of impure cyanides or leaching out contaminants from tank and rack linings.

Alkaline, Non-Cyanide Copper

The growing concern for worker safety and the government regulations on cyanide have made the use of non-cyanide
copper desirable. However, they cannot yet replace cyanide processes in all applications, especially for barrel plating zinc
die castings due to the formation of a non-adhering immersion copper deposit.

Many non-cyanide copper processes operate between the same plating properties as cyanide-copper baths. A proprietary
non-hazardous, easier-to-waste-treat complexer replaces cyanide. A typical bath formulation requires 11 g/liter of copper
metal at a pH of around 9.0. Cyanide copper solutions have a pH of at least 11.

Non-cyanide processes operate between 130 and 150F, with air agitation. Use an anode-to-cathode ratio of 2:1 and the
same anodes used in cyanide solutions.

Analysis and routine additions of the complexer are all that are typically needed to maintain the bath. However, the
removal of metallic impurities might be a major problem. Due to deficiencies within many non-cyanide copper processes,
they should only be used after extensive testing on the actual parts to be plated produced under production conditions.

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.

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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
(Concentrations in High-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.

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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.

TABLE VI—Typical Carbon/Hydrogen Peroxide Treatment for Troubleshooting, purification. Acid-copper-sulfate

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Acid Copper baths are easy to maintain. Use wet analysis to


control copper, sulfuric acid, and chloride. Add
1. Transfer the entire plating solution into a properly leached treatment tank. proprietary addition agents, which control
2. Raise the temperature to approximately 110F. brightness, ductility, and leveling, on the basis of
amp hours. You can also regulate their addition by
3. While stirring, add one quart of 30-35 pct hydrogen peroxide for every 100 using Hull Cells and a copper analysis.
gallons of plating solution. Agitate for two hours at 110F.
Table V lists some typical problems that might be
4. Raise the temperature to 140F and continue to agitate for two more hr.
encountered. If an additive system is used, consult
5. Add four pounds of a finely powdered activated plating grade carbon per the supplier's troubleshooting guide, too.
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 Even though acid-copper baths are very tolerant to
settle.
contamination, they must be purified occasionally.
6. Cool a sample to operating temperature and Hull Cell test to insure that the Organic contaminants are probably the most
deposit is matte across the entire Hull Cell panel. If the deposit is still bright, a common, since they are easily introduced into the
longer treatment time and/or more carbon will be needed. bath from cleaners, oils, greases, brightener-
7. Once the Hull Cell panel is matte in appearance, pump the treated solution breakdown products and brightener overloads.
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. Most proprietary systems can tolerate an overdose of
additives for short periods of time, but if overdosing
8. Add normal make-up additives to the treated solution and dummy the continues, a light carbon treatment might be
solution for one to two hours at 10-15 asf.
necessary. Pack the filter with activated carbon and
9. Hull Cell test to insure that the bath is at its desired level before resuming circulate the solution through the carbon for about
plating. three or four turnovers. This should remove enough
Note: If enough carbon can be placed in a filter, the treatment can be
organics to permit the bath to continue to operate
conducted in the plating tank. One disadvantage of this is that the plating tank satisfactorily.
cannot be cleaned out and inspected during the treatment. This is also a good
opportunity to inspect the anode bags and replace if necessary. Most acid-copper baths will eventually require a
carbon/hydrogen peroxide treatment to remove
Follow steps two through four, then pack the filter with 8-10 lb granular carbon
per 100 gal plating solution. Use granular carbon to help insure that carbon
organics that cannot be removed by a light carbon
does not get through the filter and into the plating tank. Circulate the solution treatment. The organic contaminants will eventually
through the filter until a matte deposit is obtained in a Hull Cell test. If after cause the bath to have a narrow bright plating range
six to eight turnovers the deposit is not matte, repack the filter with a fresh and to produce a dull and burned copper deposit.
charge of carbon. Repeat this procedure until the matte is obtained.
Table VI describes a typical full carbon treatment.
After carbon treating, cool the solution and add a normal make-up quantity of
additives. Next, dummy the solution for one to two hours at 10-15 asf. Run a Acid Fluoborate Copper Processes
Hull Cell to insure a bright deposit is obtainable, and resume plating.
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.

Chemistry of copper fluoborate baths. Table VII shows the TABLE VII—Typical Acid Copper Fluoborate Bath
composition of a typical acid copper fluoborate bath. If the
Component Concentration
fluoboric acid concentration is too low (pH above 1.7), the deposit
may be dull, dark, and brittle. Add boric acid to stabilize the bath Low High
and to prevent the decomposition of the fluoborate to fluoride. The (Concentrations in g/liter)
anode film and its care in a fluoborate bath are very similar to the Copper fluoborate 225 450
requirements described for the copper sulfate bath.
Copper metal 60 120
Contamination, purification. Lead is the only metallic impurity Fluoboric acid 15 30
known to interfere with the deposition of ductile copper from a Boric acid 15 30
fluoborate bath. Addition of small amounts of sulfuric acid will pH 1.2-1.7 0.2-0.6
remove the lead by precipitation.
Cathode CD, asf Up to 2,000 under special conditions
Organic impurities originating from the decomposition of addition Anode CD, asf Up to 550 with agitation
agents, solution dragin, or the leaching of tank linings and racks Agitation Air or mechanical
can embrittle the copper deposit and affect the deposit's
Temperature, F 65-140
appearance and mechanical properties. A batch carbon treatment,
Anode and cathode efficiency, pct» 100
Table VI, followed by filtration or continuous carbon filtration will
remove most organics from the bath. Anode bags Polypropylene or Dynel
Anodes OFHC, oxygen free high conductivity copper
Pyrophosphate Copper

The main use of pyro copper is plating of printed circuit boards. The bath has good throwing power, obtaining surface-

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to-hole ratios of 1:1 on many PC boards. Some Federal agencies specify pyro copper where ductility of the deposit is very
important. It is also used for general plating, electroforming, and plating on plastics. Even here though, sulfate acid
copper has the largest market share.

Pyrophosphate copper baths are mildly alkaline, making them less corrosive than acid baths. They are essentially
non-toxic. They are easy to waste treat, but the phosphate ion is beginning to be considered a pollution problem, which
might make the waste treatment of this bath more difficult.

As with sulfate acid copper baths, pyrophosphate plating baths form immersion coatings on active metals such as steel
and zinc die castings and thus strike layers such as cyanide copper must be used.

TABLE VIII—Typical Pyrophosphate Copper Plating Chemistry of pyrophosphate baths. Copper


Baths pyrophosphate, Cu2P2O7.3H2 O, dissolved in potassium
pyrophosphate, K4P2O7 solution, forms the stable complex
(Concentrations in g/liter)
ion Cu(P2O7) 26- , from which copper plates. Potassium is
General-Purpose Printed-Circuit
used instead of sodium because it is more soluble and has a
Copper 22-38 27-33 higher electrical conductivity. Any pyrophosphate in excess
Pyrophosphate 150-250 155-250 of this ratio is called "free" pyrophosphate. Free
Nitrate 5-10 5-10 pyrophosphate is essential for the operation of the bath,
Ammonia 1-3 1-3 providing conductivity and anode corrosion. Table VIII shows
typical general-purpose and printed-circuit bath
Oxalate 15-30 15-30
formulations.
Orthophosphate <115 <40
Additives As Recommended The presence of nitrate increases maximum allowable current
pH 8-9 8-9
density and reduces cathode polarization. The use of
ammonium nitrate improves the quality of the deposit over
P2O7/Cu ratio 7:1-8:1 7:1-8:1
that obtained if potassium nitrate is used. Ammonium is
Temperature (F) 120-140 125-135 added on a regular basis to produce uniform and lustrous
Anode/Cathode deposits and to improve anode corrosion. Excess ammonium
2:1 2:1
Ratio can cause copper (I) to form, which hinders adhesion, but
Anodes, not Oxygen-free; high conductivity; no lead, nickel, ammonium is easily lost by evaporation. Oxalate is a buffer.
bagged silver or tin.
Filtration Five micron; 1-3 turnovers per hr. Operation. Copper pyrophosphate baths are difficult to
control. They require more control and maintenance than
cyanide and acid-copper baths.

Orthophosphate. Orthophosphate (HPO42- ), which is formed by the hydrolysis of pyrophosphate, promotes anode
corrosion and acts as a buffer. At about 100 g/liter of orthophosphate, the conductivity and bright plating range of the
bath decrease and it produces banded deposits.

A pH below seven, a high P2O7/Cu ratio, and a bath temperature greater than 140F will increase the formation of
orthophosphate. Orthophosphate cannot be chemically removed from pyrophosphate solutions. Therefore some or all of
the bath must be discarded, to reduce its concentration.

For printed-circuit-board plating, the orthophosphate concentration should not exceed 40 to 60 g/liter. The bath will lose
its throwing power and the deposit will be less ductile.

pH. A low pH will precipitate copper pyrophosphate TABLE IX—Troubleshooting Pyrophosphate Copper
and decrease the throwing power of the bath. A high
pH will precipitate copper hydroxide and the anode Problem: Rough deposit.
Causes: 1) Particulate matter; 2) metallic contamination.
cor-rosion will decrease. Potassium hydroxide and
pyrophosphoric acid are used for pH adjustments. Problem: Brittle deposits. (Barrel cracking during solder shock test for PC
boards.)
Current density. The cathode current density is a Causes: 1) Organic contamination; 2) excessive brightener.
function of operating temperature and agitation. The
Problem: Step-plating or dishing (high-current-density areas are unplated).
typical range is between 10 and 90 asf. Throwing Causes: 1) Excessive brightener; 2) too much agitation.
power and current efficiency drop sharply with
increasing current density. Problem: Pitted deposit.
Causes: 1) Grease and oil/contamination; 2) poor cleaning prior to plating.
The anode current density is fairly critical and should
Problem: Poor throwing power.
be kept between 20 and 40 asf. If it is too high an Causes: 1)Organic contamination; 2) orthophosphates too high; 3) copper
insoluble oxide tends to form. If too low the anode metal too high; 4) temperature too high; 5) copper/pyrophosphate ratio too
efficiency exceeds 100 pct, causing a buildup of low.
copper in the bath. Permissible current density can Problem: Streaky and/or hazy deposit.
be increased by ultrasonic agitation. Current Cause: Lead contamination.
interruption, current reversal or increasing the
copper concentration also will increase the Problem: Dull deposit overall.
Causes: 1) Ammonia content too low; 2) low brightener content; 3) organic
permissible current density range. contamination; 4) cyanide contamination

Agitation. Agitate vigorously to maintain deposit Problem: Dull deposit in low-current-density areas.

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brightness and uniformity. Without agitation the Causes: 1) Temperature too high; 2) excess ammonia content; 3) low
electrodeposit is brownish and the operating current pyrophosphate content.
density is drastically lowered. Air, mechanical, or
Problem: Deposit has "folded-over" appearance in plated-through-hole of
ultrasonic agitation can be used alone or in circuit board.
combination. Cause: Brightener content too low.

Contamination, purification. The key to successful Problem: Copper deposit is burned.


operation of a copper pyrophosphate solution is Causes: 1) Copper content too low; 2) solution temperature too low; 3)
insufficient agitation; 4) limiting cathode current density exceeded; 5) low
careful control of the additives. The solutions are pyrophosphate content.
considerably more sensitive than acid copper
solutions to organic contamination such as oils, Problem: Plated copper peels from basis metal.
Causes: Poor cleaning and/or rinsing of basis metal.
cleaning and buffing compounds, organics leached
out of PC boards, and breakdown products of organic Problem: Mottled plating.
addition agents. Cause: Hexavalent chromium contamination over 60 ppm.

Organic, cyanide, and lead contamination can cause Problem: Brassy looking deposit.
Cause: Zinc contamination.
dull, streaked deposits and produce a lower effective
current density range.

Filtering through sulfur-free plating-grade carbon will remove most organic contamination. Treating with hydrogen
peroxide or potassium permanganate before carbon treatment will remove cyanide and severe organic contamination.
Dummying will remove lead. Even on solution makeup, the bath should be dummied at three to five asf to remove
metallic impurities. Sodium bisulfite will reduce hexavalent chromium and allow precipitation as chromium hydroxide.

Zinc will produce brassy looking deposits and so should be dummied out at medium-to-low current density.

Troubleshooting. Chemical analysis for copper, pyrophosphate, and ammonia is the starting point for good bath
operation. The Hull Cell can be used to evaluate the additives. Table IX lists some of the typical problems and possible
causes. PFD

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