U.S. patent number 3,650,777 [Application Number 05/114,695] was granted by the patent office on 1972-03-21 for electroless copper plating.
This patent grant is currently assigned to Photocircuits Division of Kollmorgen Corporation. Invention is credited to John F. McCormack, Frederick W. Schneble, Jr., John Duff Williamson, Rudolph J. Zeblisky.
United States Patent |
3,650,777 |
Schneble, Jr. , et
al. |
March 21, 1972 |
ELECTROLESS COPPER PLATING
Abstract
An improved aqueous autocatalytic copper deposition solution is
provided which comprises maintaining in a solution, containing
complexing and reducing agents for the copper ion and a pH
adjuster, a small effective amount of a compound providing a metal
value selected from the group consisting of molybdenum, niobium,
tungsten, rhenium, rare earths of the actinide series, rare earths
of the lanthanide series, and mixtures of the foregoing.
Additionally, an improved method of depositing electroless copper
is provided which comprises employing the solution hereinabove
defined.
Inventors: |
Schneble, Jr.; Frederick W.
(Oyster Bay, NY), Zeblisky; Rudolph J. (Hauppauge, NY),
McCormack; John F. (Roslyn Heights, NY), Williamson; John
Duff (Miller Place, NY) |
Assignee: |
Photocircuits Division of
Kollmorgen Corporation (Hartford, CT)
|
Family
ID: |
22356860 |
Appl.
No.: |
05/114,695 |
Filed: |
February 11, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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9062 |
Feb 5, 1970 |
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772061 |
Oct 18, 1968 |
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451335 |
Apr 27, 1965 |
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Current U.S.
Class: |
427/443.1;
106/1.23; 427/437 |
Current CPC
Class: |
C23C
18/40 (20130101) |
Current International
Class: |
C23C
18/40 (20060101); C23C 18/31 (20060101); C23c
003/02 () |
Field of
Search: |
;106/1
;117/13R,13E,13B,47A |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Hayes; Lorenzo B.
Parent Case Text
REFERENCE TO COPENDING APPLICATIONS
This application is a continuation-in-part of copending
application, Ser. No. 9,062, filed Feb. 5, 1970, which, in turn, is
a continuation-in-part of copending application Ser. No. 772,061,
filed Oct. 18, 1968, which, in turn is a streamlined continuation
of application Ser. No. 451,335, filed Apr. 27, 1965, all now
abandoned.
Claims
We claim:
1. In an autocatalytic copper deposition solution which consists
essentially of:
water;
a water soluble copper salt, in an amount of 0.002 to 0.60 moles
per liter;
a complexing agent for copper ion which is selected from the group
consisting of ammonia and compounds containing at least one of an
amine group, carboxy group and hydroxy group, in an amount of 0.7
to 2.5 times the moles of copper;
a reducing agent for copper ion which is selected from the group
consisting of formaldehyde, paraformaldehyde, trioxane, dimethyl
hydantoin, glyoxal, alkali metal borohydrides, amine boranes, and
alkali metal hypophosphites, in an amount of 0.03 to 1.3 moles per
liter; and
an acid or base capable of adjusting pH; the improvement which
comprises maintaining in the solution a compound soluble in the
solution and providing a small effective amount of at least 0.1
microgram atoms per liter of a metal value selected from the group
consisting of molybdenum, niobium, tungsten, rhenium, rare earths
of the actinide series, rare earths of the lanthanide series, and
mixtures of the foregoing.
2. The solution of claim 1 which includes a water soluble cyanide
compound in an amount of 0.00002 to 0.06 moles per liter.
3. The solution of claim 1 wherein said metal value is present in
amount of between about 0.1 and 3,000 microgram atoms per liter,
said amount being insufficient to prevent autocatalytic deposition
of copper from the solution at the conditions of use, but
sufficient to enhance the stability of the solution at said
conditions.
4. The solution of claim 3 wherein said metal value is present in
an amount of between 1 and 300 microgram atoms per liter.
5. The autocatalytic copper deposition solution of claim 1 wherein
the pH adjuster maintains the pH in the alkaline range.
6. The solution of claim 5 wherein the reducing agent for copper
ion is formaldehyde.
7. In a process for depositing copper on a surface catalytic to the
reception of electroless copper by contacting said surface with an
electroless copper solution consisting essentially of:
water;
a water soluble copper salt, in an amount of 0.002 to 0.60 moles
per liter;
a complexing agent for copper ion which is selected from the group
consisting of ammonia and compounds containing at least one of an
amine group, carboxy group and hydroxy group, in an amount of 0.7
to 2.5 times the moles of copper;
a reducing agent for copper ion which is selected from the group
consisting of formaldehyde, paraformaldehyde, trioxane, dimethyl
hydantoin, glyoxal, alkali metal borohydrides, amine boranes, and
alkali metal hypophosphites, in an amount of 0.03 to 1.3 moles per
liter; and
an acid or base adjuster for pH; the improvement which comprises
maintaining in the solution a compound soluble in the solution and
providing a small effective amount of at least about 0.1 microgram
atoms per liter of a metal value selected from the group consisting
of molybdenum, niobium, tungsten, rhenium, rare earths of the
actinide series, rare earths of the lanthanide series, and mixtures
of the foregoing.
8. The process of claim 7 wherein said solution includes a water
soluble cyanide compound in an amount of 0.00002 to 0.06 moles per
liter.
9. The process of claim 7, wherein the said metal value is present
in an amount of between about 0.1 and 3,000 microgram atoms per
liter, said amount being insufficient to prevent autocatalytic
deposition of copper from the solution at the conditions of use,
but sufficient to enhance the stability of the solution at said
conditions.
10. A process for electrolessly plating copper which comprises
contacting a surface catalytic to the reception of electroless
copper with an alkaline solution consisting essentially of:
water;
a water soluble copper salt, in an amount of 0.002 to 0.60 moles
per liter;
a complexing agent for copper ion which is selected from the group
consisting of tartrates, salicylates, ethylene-aminoacetic acids,
triethanolamine, ammonium hydroxide, Rochelle salts,
nitrilotriacetic acid, gluconic acid and glucono-.DELTA.-lactone,
in an amount of 0.7 to 2.5 times the moles of copper;
formaldehyde; and a compound soluble in the solution and providing
a small effective amount of at least about 0.1 microgram atoms per
liter of a metal value selected from the group consisting of
molybdenum, niobium, tungsten, rhenium, rare earths of the actinide
series, rare earths of the lanthanide series, and mixtures of the
foregoing.
11. A solution for the electroless plating of copper which consists
essentially of:
water;
a water soluble copper salt, from 0.002 to 0.60 moles per
liter;
a complexing agent for copper ion, which is selected from the group
consisting of tartrates, salicylates, ehtylene-aminoacetic acids,
triethanolamine, ammonium hydroxide, Rochelle salts,
nitrilotriacetic acid, gluconic acid and glucono-.DELTA.-lactone,
from 0.7 to 2.5 times the moles of the copper salt;
an alkali metal hydroxide, enough to give a pH of from 10.0 to
14.0;
formaldehyde, from 0.03 to 1.3 moles per liter; and a compound
soluble in the solution and providing a small effective amount of
at least about 0.1 microgram atoms per liter of a stabilizing metal
value selected from the group consisting of molybdenum, niobium,
tungsten, rhenium, rare earths of the actinide series, rare earths
of the lanthanide series, and mixtures of the foregoing.
12. A solution for the electroless plating of copper which consists
essentially of:
water;
a water soluble copper salt, from 0.002 to 0.2 moles per liter;
alkali metal hydroxide, enough to provide a pH of about 10 to
13;
a complexing agent for copper ion, which is selected from the group
consisting of tartrates, salicylates, ethylene-aminoacetic acids,
triethanolamine, ammonium hydroxide, Rochelle salts,
nitrilotriacetic acid, gluconic acid and glucono-.DELTA.-lactone,
from 0.001 to 0.60 moles per liter;
formaldehyde, 0.06 to 0.50 moles per liter; and a compound soluble
in the solution and providing a small effective amount of at least
about 0.1 microgram atoms per liter of a stabilizing metal value
selected from the group consisting of molybdenum, niobium,
tungsten, rhenium, rare earths of the actinide series, rare earths
of the lanthanide series, and mixtures of the foregoing.
13. The solution of claim 12 which includes an alkali metal cyanide
in an amount of 0.00005 to 0.01 moles per liter.
Description
The present invention relates to electroless or autocatalytic
plating of copper, and more particularly to controlling the
stability of autocatalytic copper plating baths and enhancing the
physical properties of the electroless copper deposits produced
therefrom.
One object of the present invention is to improve the stability of
autocatalytic copper baths without adversely affecting the
deposition rate or the physical properties of the electroless
copper produced therefrom.
Another object of this invention is to provide means for monitoring
autocatalytic copper solutions so as to maintain them in a state of
dynamic equilibrium.
A further object of the invention is to provide autocatalytic
copper deposition solutions which are capable of producing
electroless copper having enhanced physical properties including
improved ductility, brightness, and the like.
Still a further object of this invention is to provide new and
useful addition agents for controlling the stability of electroless
copper solutions.
Other objects of this invention will in part be obvious and will in
part be made clear herefrom.
Electroless copper solutions are capable of depositing copper
without the assistance of an external supply of electrons.
Typically, such solutions comprise water, a small amount of copper
ions, e.g., a water soluble copper salt, a reducing agent for
copper ions, a complexing agent for copper ions, and a pH
regulator. The selection of the water soluble copper salt for such
baths is chiefly a matter of economics. Copper sulfate is preferred
for economic reasons, but the halides, nitrates, acetates and other
organic and inorganic acid salts of copper may also be used.
The selection of complexing agents is well within the ability of
those skilled in the art. Illustrative copper ion complexing agents
include ammonia and organic complex-forming agents containing one
or more of the following functional groups: primary amino group
(--NH.sub.2), secondary amino group (>NH), tertiary amino group
(>N--), amino group (.dbd.NH), carboxy group (--COOH), and
hydroxy group (--OH). Cahill, U.S. Pat. No. 2,874,072, for example,
describes complexing agents which are tartrates and salicylates
used in the presence of stabilizing amounts of carbonates. In U.S.
Pat. No. 3,075,856 there are described complexing agents which are
ethyleneaminoacetic acids which are selected from the class
consisting of ethylene diaminetetracetic acid,
diethylenetriaminepentacetic acid and
1,2-cyclohexylenediaminetetraacetic acid. In U.S. Pat. No.
2,938,805 there are described a family of complexing agents
including triethanolamine, ethylenediaminetetraacetic acid, sodium
potassium tartrate, ammonium hydroxide, and others. Complete
details concerning the use of such complexing agents are shown in
the examples of these patents. Still more details concerning copper
ion complexing agents and their use may readily be found by those
skilled in the art by reference to standard works, for example,
William Goldie, METALLIC COATING OF PLASTICS, Volume 1,
Electrochemical Publications, Limited, Middlesex, England, 1968,
the disclosure of which is incorporated herein by reference.
In this invention, Rochelle salts, the sodium salts (mono-, di-,
tri- and tetrasodium), salts of ethylenediaminetetraacetic acid,
nitrilotriacetic acid and its alkali salts, gluconic acid,
gluconates, and triethanolamine are preferred as copper ion
complexing agents, but commercially available
glucono-.DELTA.-lactone and modified ethylenediamineacetates are
also useful, and in certain instances give even better results than
the pure sodium ethylenediaminetetraacetates. One such material is
N-hydroxyethylethylenediaminetriacetate. Other materials suitable
for use as cupric complexing agents are disclosed in U.S. Pat. Nos.
2,996,408 and 3,075,855.
Copper reducing agents which have been used in alkaline electroless
metal baths include formaldehyde, and formaldehyde precursors or
derivatives, such as paraformaldehyde, trioxane, dimethyl
hydantoin, glyoxal, and the like. Also suitable as reducing agents
in alkaline baths are borohydrides, such as alkali metal
borohydrides, e.g., sodium and potassium borohydrides, as well as
substituted borohydrides, e.g., sodium trimethoxyborohydride. As
reducing agents in such baths may also be used boranes, such as
amine borane, e.g., isopropylamine borane, morpholine borane, and
the like.
Typical of the copper reducing agents for use in acid electroless
copper solutions are hypophosphites, such as sodium and potassium
hypophosphite, and the like.
The pH adjuster or regulator may consist of any acid or base, and
here again the selection will depend primarily on economics. For
this reason, the pH adjuster on the alkaline side will ordinarily
be sodium hydroxide. On the acid side, pH will usually be adjusted
with an acid having a common anion with the copper salt. Since the
preferred copper salt is the sulfate, the preferred pH adjuster on
the acid side in sulfuric acid.
In operation of the bath, the copper salt serves as a source of
copper ions, and the reducing agent reduces the copper ions to
metallic form. The reducing agent is itself oxidized to provide
electrons for the reduction of the copper ions. The complexing
agent serves to complex the copper ion so that it will not be
precipitated, e.g., by hydroxyl ions and the like, and at the same
time makes the copper available as needed to the reducing action of
the reducing agent. The pH adjuster serves chiefly to regulate the
internal plating potential of the bath.
It should be understood, however, that every constituent in the
electroless copper bath has an effect on plating potential, and
therefore must be regulated in concentration to maintain the most
desirable plating potential for the particular ingredients and
conditions of operation. Other factors which affect internal
plating voltage, deposition quality and rate include temperature
and degree of agitation, in addition to type and concentration of
the basic ingredients mentioned.
In electroless plating baths, the bath constituents are
continuously being consumed, so that the bath is in a constant
state of change. Control of such baths, so as to maintain a
relatively high plating rate over relatively long periods of time
is exceedingly difficult. As a result, such baths, and particularly
those having a high plating potential, i.e., highly active baths,
tend to become unstable and to spontaneously decompose with use.
Heretofore, spontaneous decomposition of high plating potential
baths has been an important factor in limiting the commercial
acceptance of electroless copper solutions as a substitute for or a
competitor of electroplating baths.
According to the present invention, it has been discovered that
certain agents, when added to electroless copper plating solutions,
serve to maintain the baths in a dynamic state of equilibrium for
long periods of time and to prevent or substantially retard
spontaneous decomposition.
The addition agents of this invention render electroless copper
solutions less sensitive to changes of temperature and
concentration, and therefore permit greater variation in operating
conditions, ingredient concentration, temperature, and types of
ingredients then have heretofore been considered possible.
The present invention and the agents described herein although
applicable to electroless copper solutions generally, are
particularly useful with electroless copper solutions which have
high plating potential under the conditions of use.
The stabilizing agents of this invention are simple or complex
compounds, hereinafter called "metal values," comprising one or
more of the elements, molybdenum, niobium, tungsten, rhenium, rare
earths of the actinide series, e.g., actinium, uranium, and the
like, rare earths of the lanthanide series, e.g., lanthanum,
neodymium, ytterbium, and the like, as well as mixtures of
compounds containing one or more of such metal values.
Preferred for use are those compounds which comprise elements of
the type described which have at least two oxidation states. In
this preferred group are compounds comprising molybdenum, tungsten
and uranium, including mixtures of the foregoing. Such compounds
are preferably added to the electroless copper plating baths in a
form such that the stabilizing element is at its most stable
valence state.
Any compound containing the stabilizing element which is soluble in
the electroless copper solution may be used.
For example, molybdenum may be supplied as molybdic trioxide,
molybdenum pentachloride, MoCl.sub.5, as well as water soluble
organic and inorganic acid salts of molybdenum, as for example,
alkali and alkaline earth metal, or ammonium molybdate: Suitable
sources of tungsten and rhenium are the oxides of such elements, as
well as organic and inorganic acid-water soluble salts of such
elements, e.g., the tungstates, and rhenates of the metal Groups IA
and IIA of the Periodic Table of Elements, and ammonia. Preferred
for use are the sodium, potassium and ammonium salts. Sources of
lanthanum, actinium and other rare earths, e.g., uranium,
neodymium, ytterbium, and the like, are the oxides of such elements
and water soluble organic and inorganic acid salts of such
elements, including the sulfates, nitrates, halides, acetates, and
the like.
The foregoing compounds are merely typical of those which are
capable of providing stabilizing elements of the type and form
described.
The amount of the stabilizing element maintained in the baths will
be a small effective amount. Ordinarily, its concentration will
average between about 0.1 and 3,000 microgram atoms of the element
per liter of solution, preferably between about 1 and 300 microgram
atoms per liter. As used herein, a microgram atom is
1.times.10.sup.-.sup.6 gram atom.
It should be emphasized however that the small effective amount of
stabilizing element will vary with the nature and activity of the
element, and with makeup of the solution and the conditions, e.g.,
temperature, under which it is used. The upper limit of the
stabilizing element is an amount which will stop the bath, i.e.,
prevent autocatalytic deposition of copper under conditions of use.
The lower limit is the least amount of stabilizing element which
will be effective in manifesting the result described herein, again
under the particular conditions of use.
Here it should be noted that excess amounts of compounds comprising
the elements described may stop the bath completely under certain
conditions of use. So sensitive is the concentration on some of the
elements that amounts measured in parts per million may stop the
bath completely and practically instantaneously at a given activity
level, as controlled by a given temperature and given reactant
concentrations and types.
Preferred solutions according to this invention will include a
soluble cyanide compound. Due to some type of cooperative effect,
the reason for which is not clearly understood at this time,
cyanide ion and the specified metal values provide unusually high
stability. Typical of such water soluble cyanide compounds are
alkali metal cyanides, such as sodium and potassium cyanide, and
nitriles, such as alpha-hydroxynitriles, e.g., glycolonitrile and
lactonitrile, and dinitriles, e.g., iminodiacetonitrile and
3,3'-iminodipropionitrile. Such water soluble cyanide compounds may
be present in amounts of between about 0.00002 and 0.06 moles per
liter.
In addition to stabilizing the bath, certain of the metal values
described and particularly the tungstates, molybdates and uranates,
enhance the physical properties of the electroless copper deposits,
particularly brightness and ductility. This is a completely
surprising result and contributes materially to the value of the
baths utilizing the instant invention.
Typical electroless copper deposition bath made according to the
present invention will comprise:
Copper salt 0.002 to 0.60 moles Reducing agent 0.03 to 1.3 moles
Copper ion complexing 0.7 to 2.5 times the moles agent of copper
Stabilizing element 0.1 to 3,000 microgram atoms pH adjustor
sufficient to give desired pH Water sufficient to make 1 liter.
A water soluble cyanide, 0.00002 to 0.06 moles per liter, is
preferably included.
Specific embodiments of a high plating potential solution
comprises:
Copper salt 0.002 to 0.60 moles Formaldehyde 0.03 to 1.3 moles
Copper ion complexing 0.7 to 2.5 times the moles agent of copper
Stabilizing element 0.1 to 3,000 microgram atoms Alkali metal
hydroxide sufficient to give a pH of 10-14 Water sufficient to make
1 liter.
Preferred embodiments of highly active solutions comprise:
A soluble cupric salt, preferably cupric sulfate 0.002 to 0.2 moles
Alkali metal hydroxide preferably sodium hydroxide to give pH of
10-13 Formaldehyde 0.06 to 0.50 Cupric ion complexing agent 0.001
to 0.60 moles (and usually at least about 10% molar excess based on
the amount of cupric salt employed) Stabilizing agent 1 to 300
microgram atoms Water sufficient to make 1 liter.
An alkali metal cyanide, 0.00005 to 0.01 moles per liter, is
preferably included.
In considering the general and specific working formulae set forth
herein, it should be understood that as the baths are used up in
plating, the ingredients will be replenished from time to time.
Also, it is advisable to monitor the pH, and the concentration of
the additive element described, and to adjust them to their optimum
value as the bath is used.
For best results, surfactants in an amount of less than about 5
grams per liter may be added to the baths. Typical of suitable
surfactants are organic phosphate esters, and oxyethylated sodium
salts.
The baths may be used at widely varying temperatures, e.g., between
15.degree.C. and 100.degree.C., although they will usually be used
between about 20.degree.C. and 80.degree.C. As the temperature is
increased, it is usual to find that the rate of plating is
increased, but the temperature is not highly critical and, within
the usual operating range, excellent bright, ductile deposits of
copper are obtained.
Performance data for baths made in accordance with the teachings
contained herein are given in the following examples:
EXAMPLE 1
A solution is prepared which contains:
CuSO.sub.4 .sup.. 5H.sub.2 O 15 g./l. Tetrasodium ethylene-
diaminetetracetic acid 40 g./l. Formaldehyde (37% in water) 6
ml./l. MoCl.sub.5 2.0 g./l. Potassium hydroxide to pH 12 Water (to
make) 1,000 ml.
It is heated to 60.degree. C. and a clean sensitized nonmetallic
surface is placed in the solution. After 18 hours of plating,
bright, ductile (two to two and one-half bends) copper has been
electrolessly deposited to a thickness of 0.00046 inches. The
solution is stable--no copper has precipitated from it.
In contrast, a control bath identical to that described, except
that no molybdenum compound had been added is not stable and at the
end of 18 hours, there is a heavy copper deposit on the bottom of
the container. The plating of electroless copper on the article has
lower ductility (one to one and one-half bends).
The addition of 0.03 grams per liter of sodium cyanide to the first
bath provides a stable bath and enhances the ductility of the
copper deposit three and one-half bends). This level of cyanide
permits the MoCl.sub.5 in such a bath to be reduced stepwise from
2.0 g./l. to 1.0, 0.2, 0.01, 0.005 and 0.001 g./l., with no loss in
stability and with retention of ductility (2 to 4 bends).
EXAMPLE 2
The procedure of Example 1 is repeated, substituting for the
MoCl.sub.5, the tungsten compound K.sub.2 WO.sub.4. In the absence
of added cyanide, ductility is improved (two bends) in comparison
with the control; some copper precipitates from the bath on long
standing.
The addition of 0.030 g./l. of sodium cyanide provides a completely
stable solution and the copper deposited is significantly more
ductile (three to five bends) than that seen in the combination
with the molybdenum values (Example 1).
EXAMPLE 3
The procedure of Example 1 is repeated, substituting for the
MoCl.sub.5, the uranium compound UO.sub.2 (NO.sub.3).sub.2.sup. .
6H.sub.2 O. Instead of 2 g./l., 0.002 g./l. is sufficient to
provide a stable bath and enhanced ductility (two bends).
The addition of 0.030 g./l. of sodium cyanide to this bath enhances
ductility (four to four and one-half bends) and permits the uranium
compound to be reduced stepwise from 0.002 to 0.001 to 0.0005 to
0.0002 g./l. with no loss in stability.
EXAMPLE 4
The procedure of Example 1 is repeated, substituting for the
MoCl.sub.5, the lanthanum compound LaCl.sub.3.sup. . 6H.sub.2 O.
This bath also contains 0.030 g./l. of sodium cyanide. The bath is
stable with 0.020 and 0.200 g./l. of the lanthanum compound and the
copper deposit is highly ductile (four to five bends).
EXAMPLE 5
The procedure of Example 1 is repeated, substituting for the
MoCl.sub.5, the neodymium compound, NdCl.sub.3. This bath also
contains 0.030 g./l. of sodium cyanide. The bath is stable with
0.002, 0.01, 0.02, 1.0 and 3.0 g./l. of the neodymium compound. The
copper deposit is highly ductile (four to four and one-half
bends).
EXAMPLE 6
The procedure of Example 1 is repeated, substituting for the
MoCl.sub.5, the ytterbium compound, YbCl.sub.3.sup. . 6H.sub.2 O.
This bath also contains 0.030 g./l. of sodium cyanide. The bath is
stable with 0.002, 0.20 and 1.0 g./l. of the ytterbium compound.
The copper deposit is highly ductile (four to four and one-half
bends).
In the examples, the solutions were maintained at a pH of about 12
and at elevated temperature of about 60.degree. C. throughout use.
In all instances about 1 ml./l. of an organic phosphate ester was
used as a surfactant.
In the examples, ductility is reported after measurement by bending
the copper deposit through 180.degree., in one direction, creasing,
then returning it to its original position, with pressing along the
crease to flatten it, this cycle constituting one bend.
Use of the metal values described herein in autocatalytic copper
solutions improves stability to a marked degree, as is brought out
in the examples. Similar results are also obtained if, instead of
MoCl.sub.5, there is used niobium (columbium) pentachloride,
CbCl.sub.5 ; and rhenium hexafluoride, ReF.sub.6.
Also shown by the examples, the presence of these metal values also
enhances the ductility of the copper deposits.
In using the autocatalytic or electroless copper solutions to plate
metal, the surface to be plated must be free of grease and other
contaminating material.
Where a nonmetallic surface is to be plated, the surface area to
receive the deposit must first be sensitized to render it catalytic
to the reception of electroless copper, as by the well known
treatment with an acidic aqueous solution of stannous chloride
(SnCl.sub.2), followed by treatment with a dilute aqueous acidic
solution of palladium chloride (PdCl.sub.2).
Alternatively, extremely good sensitization of nonmetallic surfaces
is achieved by contact with an acidic solution containing a mixture
of stannous chloride and precious metal chloride, such as palladium
chloride, the stannous chloride being present in stoichiometric
excess, based on the amount of precious metal chloride.
Other ways of sensitizing nonmetallic surfaces for reception of an
electroless copper deposit from the baths described herein are
disclosed in copending application Ser. No. 785,703, filed Jan. 8,
1959, now abandoned.
Where metal surface is to be plated, it should be degreased, and
then treated with an acid, such as hydrochloric or phosphoric acid,
to free the surface of oxides.
Following pretreatment and/or sensitization, the surface to be
plated is immersed in the autocatalytic copper baths, and permitted
to remain in the bath until a copper deposit of the desired
thickness has been built up.
The invention in its broader aspects is not limited to the specific
steps, processes and compositions shown and described, but
departures may be made therefrom within the scope of the
accompanying claims without departing from the principles of the
invention and without sacrificing its chief advantages.
* * * * *