United States Patent (19) (11) 4,238,300

Yoshida 45 Dec. 9, 1980

54 GOLD ELECTROPLATING PROCESS OTHER PUBLICATIONS
75 Inventor: Kei Yoshida, Reading, Pa. E. D. Winters, Plating, pp. 213-218, Mar. 1972.
(73) Assignee: Bell Telephone Laboratories, Primary Examiner-G. L. Kaplan
Incorporated, Murray Hill, N.J. Attorney, Agent, or Firm-Peter V. D. Wilde; Michael J.
21 Appl. No.: 42,456 Urbano
22 Filed: May 25, 1979 57 ABSTRACT
Electrolytic deposition of gold results in the formation
51) int. Cl. ................................................ C25D 3/48 of undesirable reducible gold III species in the electro
52 U.S. C. .................................................. 204/46 G plating bath which interfere with the current efficiency
58) Field of Search .................. 204/46 G, 43 G, 109, and make the prediction of gold thickness based on
204/DIG. 13; 423/316 applied current impossible. Addition of a small quantity
(56) References Cited of hypophosphorous acid to the plating bath when the
current efficiency has dropped below a certain mini
U.S. PATENT DOCUMENTS mum, chemically reduces accumulated gold III species
2,812,299 11/1957 Volk et al. ......................... 204/43 G and scavenges dissolved oxygen. Thus, the current
3,423,295 1/1969 Greenspan ......................... 204/43 G efficiency is restored to about 100%. The hypophos
4,067,783 1/1978 Okinaka et al. ................... 204/43 G phorous acid treatment is particularly advantageous in a
FOREIGN PATENT DOCUMENTS phosphate buffered bath because no foreign ions are
introduced into the solution.
1331064 5/1963 France ................................... 204/46 G
928.088 6/1963 United Kingdom .................. 204/46 G 5 Claims, No Drawings
 4,238,300
2
reduces the dissolved oxygen to sulphate. However,
GOLD ELECTROPLATING PROCESS sulfite can not be used where the pH of the bath is less
than 7.
BACKGROUND OF THE INVENTION
1. Field of the Invention
SUMMARY OF THE INVENTION
This invention relates to the electrodeposition of I have discovered that treating the electroplating
gold, and more particularly to a method for improving bath with hypophosphorous acid, followed by heating
the current efficiency of an electroplating bath. for a brief period of time, effectively reduces gold III
2. Description of the Prior Art species and scavenges oxygen so that the current effi
O ciency returns to about 100%. Basically, the technique
Gold electroplating has been used in a variety of
applications ranging from purely decorative to indus involves monitoring the current efficiency until it drops
trial. Recently, the expanding electronics industry has below a predetermined minimum, typically below about
created a great demand for gold electroplating pro 80%. At that point, addition of about 0.06–0.10M (bath
cesses. The chemical and physical stability, good con vol.) hypophosphorous acid followed by heating the
ductivity, and corrosion resistance of gold makes it 15 bath to a temperature of at least about 70 degrees C for
ideally suited for use in electronic devices. Gold has about 3 hours or more has been found to restore the
been used in integrated circuits for bonding pads, current efficiency to its original value. The treatment is
contacts, and current conductors. It has also been useful particularly compatible with phosphate buffered baths
in making ohmic and rectifying contacts in semiconduc since no foreign ions which could adversely affect bath
tor devices since it forms an eutectic with silicon and properties are introduced into solution.
germanium. Other electronic applications include plat
ing of copper headers and housings for semiconductor DETAILED DESCRIPTION
diodes where, for example, copper ions would contami Conventional plating baths generally contain gold I
nate the device. as the source of gold. The typical industrially-used pure
Unfortunately, a major problem with gold plating is 25
gold electroplating solution contains an alkali-metal
that the current efficiency (amount of gold plated per gold-cyanide complex such as potassium aurocyanide,
quantity of electricity applied) decreases with time. KAu(CN)2 and conducting salts of organic or inorganic
Therefore, the length of time for plating must be in reagents such as citrate or phosphate as buffers. Com
creased to ensure a predetermined minimum thickness. mon additives to the pure gold baths include complex
This may lead to overplating and consequent waste of 30 ing agents, grain refiners, and hardening agents. In such
gold. Furthermore, the lower plating efficiency may solutions, dicyanoaurate (gold I) is cathodically re
have an effect on the porosity and quality of the deposit.
Therefore, when the current efficiency of the bath falls duced to elemental gold as follows:
below a certain minimum, the bath must be replaced. Au(CN)2 -e=2CN -- Au (Base)
Frequent replacement of the bath is wasteful not only of 35
gold, but also of personnel time. Au(CN)2 --2H -- es2HCN--Au (Acid)
Accordingly, some research has been done to ascer
tain the cause of the drop in current efficiency with In the conventional dicyanoaurate bath, tetracyanoau
electrolysis time. Conventional plating baths typically rate ions (gold III) accumulate as anodic electrolysis
use gold I species as the source of gold. Polarographic proceeds. Formation of tetracyanoaurate results in a
studies have demonstrated that gold III species accumu decrease in current efficiency as reduction of the triva
late in these solutions with time and have a deleterious
effect on the current efficiency. The prior art has pro lent gold
gold takes three electrons while the monovalent
requires only one electron.
posed the reduction of gold III by chemical reducing Furthermore, with an open container, oxygen from
agents. Generally, hydrazine has been used. U.S. Pat. the air dissolves into
45
the plating solution, particularly if
No. 4,067,783 suggests a treatment of 0.25 ml 85% hy the solution is agitated.
drazine per 100 ml of bath solution accompanied by I reduction according toThe the
oxyten competes with gold
overall reactions:
heating for a period of time. The problem with hydra
zine is that it is a noxious, carcinogenic chemical. Fur
thermore, excessive hydrazine should be avoided due to 50
its adverse effect on the chemical and physical proper
ties of the gold plating solution. Active charcoal has
also been used to restore current efficiency by absorb The most notable effect due to oxygen is at low current
ing certain impurities, but it is not as effective as hydra density, e.g., less than 5 mA/cm2.
zine treatment and also absorbs gold species. 55 Eventually, the accumulations of tetracyanoaurate
In addition to a build-up of gold III species, E. D. and dissolved oxygen effectively compete with the
Winters, Plating, Vol. 72, 213 (1972) demonstrated that desired reduction of dicyanoaurate to elemental gold.
oxygen from the atmosphere dissolves into the bath and The uniformity of deposition thickness and smoothness
also decreases the current efficiency as the reduction of of the deposit become hard to control. At this point, the
the oxygen competes with the reduction of gold I into 60 bath should be treated with hypophosphorous acid. One
elemental gold. The prior art suggests inert gas purging method for determining when to add the hypophospho
or chemical oxygen scavengers for removing the dis rous acid is by monitoring the current efficiency until it
solved oxygen. In particular, nitrogen sweeping of the reaches a predetermined minimum. For maximum con
plating solution before and during plating has been trol, the current efficiency should not go below about
suggested. However, this technique may not always be 65 80%. At about 75% the deposits are nonuniform and
practical. Chemical reducing agents such as hydrazine rough. Current efficiency which is defined as the
have been employed. Addition of a complex which will amount of gold plated per quantity of electricity applied
yield a sulfite ion has also been suggested since sulfite can be measured by plating a preweighed substrate for
 3
4,238,300
4.
a fixed time at a fixed current density. Then, the sub
strate is weighed. The following Nernst equation deter EXAMPLE 1.
mines the current efficiency from the weight gain data
on the basis of the reduction of gold I: Soft Gold, Phosphate Buffered
Potassium gold cyanide, KAu(CN)2 20g/
% current efficiency = (100 x Wt. gain X n) / ( I F
196.97 Xt ) Potassium monohydrogen phosphate 40g/1
Potassium dihydrogen phosphate 10g/
pH 6-10
where I= current in amps, t = electrolysis time in sec temperature 40–75 degrees C.
onds, F = the Faraday (96,500 coulombs per gram continuous agitation current density
10 anode 5-20mA/in2
platinized
equivalent), and n = number of electrons involved in the titanium
reaction, in this case, n = 1.
Another means for determining when to add the
hypophosphorous acid is by use of polarographic mea EXAMPLE 2
suring techniques. The concentration of accumulated 15
gold III species can be estimated by using solutions of Soft Gold, Citrate Buffered
known concentrations of dicyanoaurate and tet
racyanoaurate as described in U.S. Pat. No. 4,067,783 Potassium gold cyanide 8g/
issued to Y. Okinaka et all on Jan. 10, 1978 at Col. 3, line Citric acid 40g/1
20 Sodium citrate 40g/l
47-;l Col. 4, line 17. When the concentration of tet pH 3-6
racyanoaurate reaches a certain maximum, treatment is temperature room temp.
warranted.
After addition of the hypophosphorous acid, the bath The citrate based or phosphate based baths as exem
temperature should be raised above normal to speed up plified in Examples 1 and 2 would be amenable to hypo
the gold III reduction reaction. In a neutral solution, 25 phosphorous acid treatment. There are a few known
reduction of tetracyanoaurate Au(CN)4 may be slow sodium gold sulfite baths, but sulfite based baths do not
due to the disproportionation reaction: accumulate gold III species so there would be no need
for the hypophosphorous acid reducing agent. The
30 hypophosphorous acid treatment works well with baths
Caution should be taken not to excessively heat the bath having neutral pH. The pH of hypophosphorous acid is
since the heat could adversely affect the properties of about 4. Therefore, it would also be useful in an acidic
the gold plating bath. Bath temperatures typically range bath, such as Example 2. In an alkaline bath, it could
between room temperature and about 80 degrees C.; the cause a pH shift which would have to be compensated
most common range being between about 50-75 de 35 for.
grees C. Treatment at a temperature of about 70-85 EXAMPLE 3
degrees C. for about three hours or more is sufficient.
Hypophosphorous acid treatment has been found to
restore the current efficiency to about 100%. The over Hard Gold, Phosphate Buffered
all chemical equations are: Potassium gold cyanide 4-46g/1
Phosphoric acid to adjust pH to about 4.2
Cobalt citrate 20-200ppm

45 EXAMPLE 4

Hard Gold, Citrate Buffered

Potassium gold cyanide 4g/
Citric acid 120g/
50 Tetraethylene pentamine 20g/l
The hypophosphorous acid is readily oxidized to a Ni3(C6H5O)2 2.5g/l
higher oxidation state as: pH 4.
temperature 40 degrees C.

55 Examples 3 and 4 are hard gold baths. Common hard

The PO4)3 ion is the primary electrolyte of a phos ners, such as Co and Ni additives, would precipitate the
phate buffered bath. Thus, no foreign ions are added to phosphate complex in a citrate buffered bath when
such a solution which could adversely affect the bath hypophosphorous acid is added. However, if a com
properties. plexing agent for Co or Niis present, such as tetraethyl
Although maximum advantage is gained by use of the 60 ene pentamine as in Example 4 or an organophospho
hypophosphorous acid treatment in conjunction with a nate, there will be no phosphate precipitation and the
phosphate buffered bath, the treatment is compatible hypophosphorous acid treatment can be used.
with other baths as well. It can be employed in deposi
tion of pure gold or alloy, both hard and soft. Some EXAMPLE 5
examples are set forth below. Other bath formulations 65 The hypophosphorous acid treatment has been found
may be found in the literature. A well-known source is to produce excellent results in the standard aqueous
Gold Plating Technology by F. H. Reid and W. Goldie, alkali metal-gold-cyanide bath which is buffered by
Electrochemical Publications Limited, 1974. alkali metal and alkaline earth metal primary and sec
 4,238,300
5 6
ondary phosphates. The following bath was used in embodiments which can be devised to represent appli
conventional rack plating using metal pieces and metal cation of the principles of this invention. Numerous and
lized wafers as the cathodes. varied arrangements can be devised with these princi
ples by those skilled in the art without departing from
Electroplating Bath the spirit and scope of the invention. In particular, the
KAu(CN)2 32.5g/
hypophosphorous acid treatment is applicable to nu
K2HPO4.3H2O 280g/1 merous types of gold plating baths.
I claim:
Pb+2 0.5 - 0.3 ppm 1. A method of manufacturing an article by steps
pH 1-8 10 comprising electrolytically depositing gold from a gold
temperature 70 - 2 degrees C.
continuous agitation 15 Amin plating bath onto said article,
characterized by adding hypophosphorous acid to
The anode was a platinized-titanium electrode avail said bath, with the pH of said bath being in the
able commercially from Sel-Rex Corporation (Nutley, 15
range of 6 to 10.
2. The method of claim 1 further characterized in that
N.J.). An electrical source supplied current at a current about 0.06–0.10 M (Vol.) hypophosphorous acid is
density of 5-80 mA/in2. added and said bath is heated to a temperature of at least
The current density was monitored by the weight 70 degrees C. for at least three hours.
gain technique. When the current efficiency dropped to
a value between 75%-80%, the bath was treated with 20 said3. bath
The method of claim 1 further characterized in that
comprises an aqueous solution of a gold alkali
the hypophosphorous acid. I have found that about 0.08 metal cyanide and at least one buffer selected from the
M, calculated by bath volume, is an appropriate quan group of alkali metal and alkaline earth metal primary
tity under these conditions. After addition of the hypo and secondary phosphates.
phosphorous acid, the temperature of the bath was
raised to about 80 degrees C for at least three hours. 25 4. The method of claims 1, 2, or 3 further character
After treatment, the current efficiency increased to ized by monitoring the accumulation of gold III species
101.5% from 75.5%. A value greater than 100% is pos and adding said hypophosphorous acid when said accu
sible since some gold III species is reduced to elemental mulation reaches a predetermined value.
gold. After two months of continuous usage, the cur 5. The method of claims 1, 2, or 3 further character
rent efficiency was still 98.5%. The deposits are bright 30 ized by monitoring the current efficiency of said bath
and smooth with a hardness of 97.5 knoop as plated and and adding said hypophosphorous acid when said cur
45 knoop as annealed. rent efficiency reaches a predetermined minimum
It is to be understood that the above-described exam value.
ples are merely illustrative of the many possible specific se k c k

35

45

50

55

60

65