U.S. patent number 3,754,939 [Application Number 05/256,049] was granted by the patent office on 1973-08-28 for electroless deposition of palladium alloys.
This patent grant is currently assigned to The United States of America as represented by the Secretary of the Army. Invention is credited to Fred Pearlstein, Robert F. Weightman.
United States Patent |
3,754,939 |
Pearlstein , et al. |
August 28, 1973 |
ELECTROLESS DEPOSITION OF PALLADIUM ALLOYS
Abstract
A plating solution for providing an electroless deposit of
palladium alloys wherein palladium predominates, with a minor
amount of nickel, cobalt, or zinc. The electroless palladium alloys
contain up to about 6% nickel, or 10% cobalt, or 36% zinc, each
with phosphorus. Preferred bath compositions comprise 29.6 g/l
NiSO.sub.4.sup.. 6H.sub.2 O, or 29.6 g/l CoSO.sub.4.sup.. 6H.sub.2
O, or 36.0 g/l ZnSO.sub.4.sup.. 8H.sub.2 O, with: PdCl.sub.2 --2
g/l Hcl (38%)--4 ml/l Nh.sub.4 oh (28%)--160 ml/l Nh.sub.4 cl--27
g/l NaH.sub.2 PO.sub.2.sup.. H.sub.2 O--10 g/l
Inventors: |
Pearlstein; Fred (Philadelphia,
PA), Weightman; Robert F. (Philadelphia, PA) |
Assignee: |
The United States of America as
represented by the Secretary of the Army (Washington,
DC)
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Family
ID: |
22970913 |
Appl.
No.: |
05/256,049 |
Filed: |
May 23, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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74038 |
Sep 21, 1970 |
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Current U.S.
Class: |
106/1.24;
106/1.22 |
Current CPC
Class: |
C23C
18/48 (20130101) |
Current International
Class: |
C23C
18/16 (20060101); C23C 18/48 (20060101); C23c
003/02 () |
Field of
Search: |
;106/1
;117/130,13E,47A |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Koretzky, "Electroless Deposition of Ferromagnetic Alloys," I.B.M.
Tech. closure Bulletin, Vol. 5, No. 2, 1962, p. 59..
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Primary Examiner: Hayes; Lorenzo B.
Parent Case Text
This application is a continuation-in-part of our copending
application, Ser. No. 74,038, filed Sept. 21, 1970, now abandoned,
for "Electroless Deposition of Palladium and Palladium Alloys", and
assigned to the same assignee hereof.
Claims
1. A bath composition for the electroless deposition of alloys of
palladium phosphorous wherein palladium predominates, said alloy
including a minor amount of a member of the group consisting of
nickel, cobalt, or zinc, said bath comprising:
0.5 to 4 g/l PdCl.sub.2,
1.0 to 8 ml/l 38% HCl,
80 to 320 ml/l 28% NH.sub.4 OH,
10 to 54 g/l NH.sub.4 Cl, and
5 to 20 g/l NaH.sub.2 PO.sub.2.sup.. H.sub.2 O,
said bath composition including a member of the group consisting of
NiSO.sub.4.sup.. 6H.sub.2 O, CoSO.sub.4.sup.. 6H.sub.2 O, and
ZnSO.sub.4.sup.. 8H.sub.2 O for forming an alloy of Pd-Ni-P,
Pd-Co-P, and Pd-Zn-P respectively.
2. The composition as described in claim 1 wherein said PdCl.sub.2
is present in an amount of 2 g/l, said HCl is present in an amount
of 4 ml/l, said NH.sub.4 OH is present in an amount of 160 ml/l,
said NH.sub.4 Cl is present in an amount of 27 g/l, and said
NaH.sub.2 PO.sub.2.sup.. H.sub.2 O is present in an amount of 10
g/l.
3. The bath composition as described in claim 1 wherein said
NiSO.sub.4.sup.. 6H.sub.2 O is present in an amount between about 1
to 40 g/l.
4. The bath composition as described in claim 1 wherein said
CoSO.sub.4.sup.. 6H.sub.2 O is present in an amount between about 1
to 40 g/l.
5. The bath composition as described in claim 1 wherein said
ZnSO.sub.4.sup.. 8H.sub.2 O is present in an amount between about 1
to 40 g/l.
6. The bath composition as described in claim 1 wherein said
NiSO.sub.4.sup.. 6H.sub.2 O is present in an amount of 29.6
g/l.
7. The bath composition as described in claim 1 wherein said
CoSO.sub.4.sup.. 6H.sub.2 O is present in an amount of 29.6
g/l.
8. The bath composition as described in claim 1 wherein said
ZnSO.sub.4.sup.. 8H.sub.2 O is present in an amount of 36.0 g/l.
Description
The invention described herein may be manufactured, used, and
licensed by or for the Government for governmental purposes without
the payment to us of any royalty thereon.
The present invention relates to the electroless deposition of
palladium alloys and improved bath compositions therefor.
Electroless deposition (autocatalytic chemical reduction) of
palladium has been accomplished through the use of hydrazine-based
baths which, however, have a short shelf life and deposition rates
decrease rapidly after initial use but prior to significant
depletion. These deficiences have been substantially minimized by
our electroless plating bath which provides binary alloys of Pd-P
and ternary alloys of Pd-P and an additional metal such as nickel,
cobalt, or zinc.
Electrolessly deposited palladium alloys are most useful metals
having diverse and important commercial and military applications.
They may be used on electrical contacts for communications systems
and to provide reliable and substantially noise-free transmission
in voice circuits. Electroless palladium alloy deposits should find
broad application to electronic components such as connectors,
terminals, slip rings and electrical brushes where low contact
resistance and high wear resistance is required. Electroless
palladium alloy deposits may be applied directly to non-conductive
substrates for use in catalytic chemical processing and for fuel
cell electrodes. Electroless deposition of the palladium alloys
will provide certain advantages over electroplated palladium. In
general an electroless palladium alloy deposit
A. IS MORE UNIFORM RESULTING IN A MINIMUM AMOUNT OF METAL REQUIRED
FOR A GIVEN APPLICATION.
B. YIELDS LESS PORUS DEPOSITS AND HENCE THINNER DEPOSITS MAY BE FOR
A GIVEN APPLICATION.
C. IS MORE VERSATILE, PROVIDING A VARIETY OF CONTROLLABLE
PROPERTIES SUCH AS HARDNESS, WEAR RESISTANCE, AND CATALYTIC
ACTIVITY CHANGE WITH ALLOY COMPOSITION.
Accordingly, it is an object of this invention to provide an
improved bath composition for permitting the electroless deposition
of high quality palladium alloy deposits.
Another object of the invention is to provide improved bath
compositions as above discussed having a shelf life of at least
seven months and yet with deposition rates that are relatively
constant so long as bath replenishment is accomplished.
Still another object of the invention is to provide improved bath
compositions which yield palladium phosphorus alloys or having
codeposited therewith, nickel or cobalt, or zinc.
The exact nature of this invention as well as other objects and
advantages thereof will be apparent from consideration of the
following description and drawings wherein:
FIG. 1 graphically represents effect of temperature on electroless
palladium phosphorus alloy deposition rates, and
FIG. 2 is a graphical representation showing effects of depletion
and replenishment on electroless deposition rates.
In accordance with the above objects, we have discovered that
excellent electroless deposits of palladium alloys may be obtained
through the use of our invention. When palladium ions and
hypophosphite ions are present in solution, homogeneous chemical
reduction occurs such that palladium metal is formed throughout the
solution as well as on the desired surface. The nuclei of metal
thus formed in the solution provide a large surface area for
catalytic oxidation of hypophosphite and reduction of palladium
ions thereby resulting in rapid and wasteful depletion of the
reacting chemicals. A stable hypophosphite-based electroless
palladium plating solution was developed wherein the acidified
palladium chloride stock solution utilized for solution preparation
consisted of 20 g/l PdCl.sub.2 -- 40 ml/l HCl (38%). All solutions
hereinafter described will thus be understood to contain 2 ml/l HCl
(38%) for each g/l PdCl.sub.2 present. The appropriate quantity of
acidified PdCl.sub.2 solution was added to the NH.sub.4 OH
solution, allowed to stand 20 hours and filtered before addition of
other test solution constituents.
Test solutions for electroless palladium phosphorus alloy
deposition were prepared and heated in a constant temperature bath.
An activated tantalum panel of 10 cm.sup.2 area was immersed into
200 ml of test solution. The deposit weight was found by difference
after stripping the deposit for 10 minutes in aqua regia.
Activation of the panel comprised immersing it in 5 g/l of
SnCl.sub.2 -5 ml/l HCl solution for 2 minutes; rinse; then in 0.2
g/l PdCl.sub.2 -1 ml/l HCl solution for 2 more minutes; and
rinse.
Test electroless palladium alloy plating solutions were prepared of
1 g/l PdCl.sub.2, 160 ml/l NH.sub.4 OH (28%) and varying
concentrations of hypophosphite. Increasing NaH.sub.2
PO.sub.2.sup.. H.sub.2 O resulted in increased deposition rate at
40.degree.C to a maximum at about 20 g/l. At 60.degree.C, the
solutions containing 20 or 40 g/l NaH.sub.2 PO.sub.2.sup.. H.sub.2
O were unstable and rapid solution decomposition occurred before
deposition tests could be conducted. 10 g/l NaH.sub.2
PO.sub.2.sup.. H.sub.2 O yielded optimum results.
Solutions were prepared with 0.5, 1.0, 2.0 and 4.0 g/l PdCl.sub.2,
160 m/l NH.sub.4 OH (28%) and 10 g/l NaH.sub.2 PO.sub.2.sup..
H.sub.2 O. The deposition rates from the solutions at 40.degree.C
increased with increasing palladium content but there was
relatively little benefit from concentrations above 2.0 g/l
PdCl.sub.2.
Additional deposition rate determinations were made using solutions
containing 2.0 g/l PdCl.sub.2, 10 g/l NaH.sub.2 PO.sub.2.sup..
H.sub.2 O and various concentrations of ammonium hydroxide. The
solution containing 40 ml/l NH.sub.4 OH (28 percent) was unstable
at 60.degree.C. There was otherwise little effect on deposition
rate or stability of solutions containing 80 to 320 ml/l NH.sub.4
OH.
The effect of NH.sub.4 Cl additions on electroless palladium
phosphorus alloy deposition rates was determined from solutions
containing 2 g/l PdCl.sub.2, 160 m/l NH.sub.4 OH (28%) and 10 g/l
NaH.sub.2 PO.sub.2.sup.. H.sub.2 O. Increasing concentration of
NH.sub.4 Cl resulted in marked decrease in deposition rates
presumably by more effectively complexing the palladium. The
stability of the electroless solutions on extended use were
improved with increasing NH.sub.4 Cl concentration. It is thus
considered very desirable to include NH.sub.4 Cl in the electroless
palladium phosphorus alloy plating solution.
Bath compositions are presented in the following Tables for
providing electroless deposits of palladium-phosphorus alloy or
palladium-phosphorus alloys additionally containing nickel, cobalt
or zinc:
TABLE I
Bath composition For Electroless Deposition Of Pd-P
Alloy Preferred Compound Concentration Effective Range PdCl.sub.2 2
g/l 0.5 to 4 g/l HCl (38%) 4 ml/l 1.0 to 8 ml/l NH.sub.4 OH (28%)
160 m/l 80 to 320 ml/l NH.sub.4 Cl 27 g/l 10 to 54 g/l NaH.sub.2
PO.sub.2.sup.. H.sub.2 O 10 g/l 5 to 20 g/l
TABLE II
Bath Composition for Electroless Deposition of Pd-Ni-P Alloy
Compound Preferred Concentration Effective Range PdCl.sub.2 2 g/l
0.5 to 4 g/l HCl (38%) 4 ml/l 1.0 to 8 ml/l NH.sub.4 OH (28%) 160
ml/l 80 to 320 ml/l NH.sub.4 Cl 27 g/l 50 to 54 g/l NaH.sub.2
PO.sub.2.sup.. H.sub.2 O 10 g/l 5 to 20 g/l NiSO.sub.4.sup..
6H.sub.2 O 29.6 g/l 1 to 40 g/l
TABLE III
Bath Composition for Electroless Deposition of Pd-Co-P Alloy
Compound Preferred Concentration Effective Range PdCl.sub.2 2 g/l
0.5 to 4 g/l HCl (38%) 4 ml/l 1.0 to 8 ml/l NH.sub.4 OH (28%) 160
ml/l 80 to 320 ml/l NH.sub.4 Cl 27 g/l 10 to 54 g/l NaH.sub.2
PO.sub.2.sup.. H.sub.2 O 10 g/l 5 to 20 g/l CoSO.sub.4.sup..
6H.sub.2 O 29.6 g/l 1 to 40 g/l
TABLE IV
Bath Composition For Electroless Deposition of Pd-Zn-P Alloy
Compound Preferred Concentration Effective Range PdCl.sub.2 2 g/l
0.5 to 4 g/l HCl (38%) 4 ml/l 1.0 to 8 ml/l NH.sub.4 OH (28%) 160
ml/l 80 to 320 ml/l NH.sub.4 Cl 27 g/l 10 to 54 g/l NaH.sub.2
PO.sub.2.sup.. H.sub.2 O 10 g/l 5 to 20 g/l ZnSO.sub.4.sup..
8H.sub.2 O 36.0 g/l 1 to 40 g/l
The preferred pH of our preferred concentration baths is about 9.8
.+-. 0.2.
The bath of preferred composition (Table I) for providing
electroless palladium-phosphorus alloy deposition was studied for
effect of temperature on deposition rate and stability. The results
are shown in FIG. 1. The deposition rate increased with increasing
temperature. However, at 80.degree.C, solution decomposition ensued
before the deposition test was completed and at 90.degree.C
deposition tests could not be conducted because of premature
decomposition. The solution may be used at 70.degree. or lower.
However, deposition at 50.degree. to 60.degree.C is advisable with
deposition rates of over 2.5 .mu.m/hr. (0.1 mil/hr) (3 mg/cm.sup.2
/hr).
The electroless palladium phosphorus alloy plating solution was
prepared and filtered, and left in a glass stoppered bottle at room
conditions (22.degree. to 28.degree.C) for seven months without
evidence of solution decomposition and without reduced
effectiveness of decomposition. Poor shelf life was characteristic
of prior art electroless palladium plating solutions. However,
during use of the palladium plating solution, entrance of
particulate matter may affect solution stability by providing
nuclei for catalytic reduction of palladium. Filtration into a new
container is advisable if gassing is evident in the solution or on
the container bottom indicating presence of catalytic nuclei.
A number of consecutive one hour deposition tests on 10 cm.sup.2
activated tantalum were conducted using a single 200 ml solution at
40.degree.C. The deposition rates were determined as shown in FIG.
2. The deposition rate decreased as the solution became depleted.
After 19 consecutive one hour deposition tests, the deposition rate
decreased from about 1.7 to 0.3 mg/cm.sup.2 and over 90 percent of
the palladium originally present in the solution was plated out.
When the palladium content was restored to the original value by
addition as the amine complex in NH.sub.4 OH, the deposition rate
was restored to almost the original value even without
hypophosphite replenishment. Prior art palladium plating baths were
drastically reduced in plating rate after very short usage and
replenishment procedures were ineffective.
Hydrogen gas is evolved on the surface during electroless palladium
alloy deposition as it is during electroless deposition of other
metals when hypophosphite reducing agent is utilized. Of course,
hydrogen gas formation represents inefficient use of reducing
agent. The efficiency of hypophosphite utilization was determined
by analysis of hypophosphite consumed during electroless deposition
of 59.4 mg palladium phosphorus alloy at 40.degree.C. Approximately
188 mg NaH.sub.2 PO.sub.2.sup.. H.sub.2 O was consumed. This
represents a utilization of efficiency of approximately 31
percent.
A 150 .mu.m electroless palladium phosphorus alloy deposit was
produced by immersion in the plating solution at 40.degree.C for an
extended period. The deposit was cross-sectioned and tested for
microhardness which was found to be approximately 165 kg/mm.sup.2
on the Vickers scale. Microscopic examination of the deposit cross
section revealed a crack pattern probably owing to stresses in the
deposit.
After alkaline cleaning and immersion in 10 percent (volume)
sulfuric acid at 25.degree.C, copper, brass and gold specimens were
immersed into the electroless palladium phosphorus alloy plating
solution at 55.degree.C. Electroless deposit coverage was achieved
on copper after about 3 minutes, on brass after about 1.5 minutes
and on gold after about 20 seconds. Immersion of the metal for 30
seconds in 0.1 g/l PdCl.sub.2 --0.5 ml/l HCl (38% ) at 25.degree.C,
and rinsing prior to immersion in the electroless palladium
phosphorus alloy plating solution, resulted in deposit coverage on
all of the metals within about 20 seconds. Electroless palladium
phosphorus alloy was also spontaneously deposited on steel or
electroless nickel plated steel shortly after immersion in the
plating solution.
The tests described above were repeated except that the
hypophosphite reducing agent was omitted from the plating solution.
No visible deposits were produced on any of the metal surfaces. It
is thus evident that the aforementioned deposits were produced by a
truly electroless mechanism rather than by electrochemical
displacement.
Glass or plastics, activated by stannous chloride and palladium
chloride immersions are readily coated with palladium phosphorus
alloy from the electroless plating solution.
Production of electroless palladium phosphorus alloys with nickel,
cobalt or zinc are presented below.
The possibility of producing the ternary electroless palladium
alloys was determined by addition of metal salts to the electroless
palladium phosphorous alloy plating solution. Deposits were
produced on activated tantalum over a period of 5 hours at
60.degree.C. The deposits were analyzed for constituent elements by
wet chemical procedures. The results are shown in Table V
below:
TABLE V
ELECTROLESS PALLADIUM ALLOY DEPOSITION
Metal Salt Addition to Deposit Composition, % by Weight Preferred
Bath Salt Conc, g/l Metal Phosphorus Palladium NONE 1.52 Balance
NiSO.sub.4.sup.. 6H.sub.2 O 29.6 (Nickel) 2.68 Balance 5.99
CoSo.sub.4.sup.. 6H.sub.2 O 29.6 (Cobalt) 2.77 Balance 9.82
Na.sub.2 WO.sub.4.sup.. 2H.sub.2 O 37.2 (Tungsten) 2.69 Balance
0.00 ZnSO.sub.4.sup.. 8H.sub.2 O 36.0 (Zinc) 1.24 61.43 35.99
KReO.sub.4 3.3 (Rhenium) 2.56 Balance Trace
Both nickel and cobalt are capable of independent electroless
deposition and were employed in the electroless palladium solutions
at 10 times the molar concentration of palladium salt, yet less
than 10% cobalt or 6 % nickel was codeposited with palladium. The
preferential deposition of palladium is thus evident. However, when
zinc sulfate was added to the electroless palladium bath, about 36%
zinc was produced in deposits. The palladium content was directly
analyzed to be 61.43 percent indicating that the zinc is present in
elemental form since the metallic elements account for virtually
the entire deposit. The induced chemical reduction of zinc with
palladium is significant since the high electronegativity of zinc
would be expected to preclude the possibility of alloy formation
with palladium. Palladium alloys with tungsten or rhenium were not
produced from the electroless palladium solution to which tungstate
or perrhenate was added.
It is recognized that by reducing the palladium ion concentration
in our alloy plating solution, an increase of the concentration of
alloying element in the deposit would be expected.
We wish it to be understood that we do not desire to be limited to
the exact details shown and described, for obvious modifications
will occur to a person skilled in the art.
* * * * *