U.S. patent number 3,645,749 [Application Number 05/043,553] was granted by the patent office on 1972-02-29 for electroless plating baths with improved deposition rates.
This patent grant is currently assigned to Photocircuits Division of Kollmorgen Corporation. Invention is credited to Milan Paunovic.
United States Patent |
3,645,749 |
Paunovic |
February 29, 1972 |
ELECTROLESS PLATING BATHS WITH IMPROVED DEPOSITION RATES
Abstract
There are provided compositions comprising imino compounds,
specifically, ethoxylated cyclohexylamines and benzyliminodiacetic
acid, complexed with copper ions. These compositions in aqueous
alkaline media, in the presence of a reducing agent, provide baths
for the autocatalytic electroless deposition of the copper metal.
The new baths have improved stability and plating rates.
Inventors: |
Paunovic; Milan (Port
Washington, NY) |
Assignee: |
Photocircuits Division of
Kollmorgen Corporation (Hartford, CT)
|
Family
ID: |
21927745 |
Appl.
No.: |
05/043,553 |
Filed: |
June 4, 1970 |
Current U.S.
Class: |
427/443.1;
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
;117/130,13E,160,355,47A |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3403035 |
September 1968 |
Schneble et al. |
|
Primary Examiner: Hayes; Lorenzo B.
Claims
What is claimed is:
1. In an aqueous alkaline chemical plating solution capable of
autocatalytically depositing copper metal on a substrate in contact
therewith comprising
a. water;
b. a water-soluble complexing agent
c. copper ion, and
d. a reducing agent; wherein the pH is between about 10 and 14; the
improvement which comprises the use as a complexing agent an
effective amount of a compound selected from the group consisting
of:
wherein x and y are each at least 1 and x and y together are from 2
to 25, or a mixture of said compounds.
2. A solution as defined in claim 1 wherein said imino compound is
of the formula
wherein x and y are each at least 1 and x and y together are from 2
to 25.
3. A solution as defined in claim 2 wherein said imino compound is
cyclohexylaminediethanol.
4. A solution as defined in claim 1 wherein said imino compound is
N-benzyliminodiacetic acid.
5. A solution as defined in claim 1 wherein ammonia or an organic
compound other than an imino compound of the formula defined is
present, which organic compound contains at least one amine group,
hydroxy group or carboxy group.
6. A solution as defined in claim 5 wherein said organic compound
is cyclohexanediaminetatraacetic acid, ethylene diamine, diethylene
triamine, triethylene tetramine, ethylenediaminetetraacetic acid,
N,N,N',N'-tetrakis-2-(2-hydroxypropyl)ethylenediamine, citric acid,
tartaric acid, 1,3-propane diamine, diethylenetriamine pentaacetic
acid, Rochelle salts, sodium salts (mono-, di- and tri-sodium) of
N-hydroxyethylenediaminetriacetic acid, nitrilotriacetic acid and
alkali metal salts thereof, gluconic acid and alkali metal salts
thereof or triethanolamine.
7. In a process for electrolessly depositing a copper metal on a
catalytic surface which comprises contacting said catalytic surface
with an aqueous alkaline chemical plating bath comprising
a. water;
b. a water soluble complexing agent,
c. copper ion, and
d. a reducing agent, wherein the pH is between about 10 and 14, the
improvement which comprises the use as a complexing agent an
effective amount of a compound selected from the group consisting
of:
wherein x and y are each at least 1 and x and y together are from 2
to 25 or a mixture of said compounds.
8. A process as defined in claim 7 wherein said imino compound is
of the formula
wherein x and y are each at least 1 and x and y together are from 2
to 25.
9. A process as defined in claim 8 wherein said imino compound is
cyclohexylaminediethanol.
10. A process as defined in claim 9 wherein said imino compound is
N-benzyliminodiacetic acid.
11. A process as defined in claim 7 wherein ammonia or an organic
compound other than an imino compound of the formula defined is
present, which organic compound contains at least one amine group,
hydroxy group or carboxy group.
12. A process as defined in claim 11 wherein said organic compound
is cyclohexanediaminetetraacetic acid, ethylene diamine, diethylene
triamine, triethylene tetramine, ethylenediamine tetraacetic acid,
N,N,N',N'-tetrakis-2-(2-hydroxypropyl)ethylene diamine, citric
acid, tartaric acid, 1,3-propane diamine,
diethylenetriaminepentaacetic acid, Rochelle salts, sodium salts
(mono-, di- and tri-sodium) of N-hydroxyethylenediamine triacetic
acid, mitrilotriacetic acid and alkali metal salts thereof,
gluconic acid and alkali metal salts thereof or triethanolamine.
Description
The present invention relates to improved solutions for
autocatalytic deposition of copper metal and to processes for their
use. More particularly, it is concerned with solutions containing
certain imino compounds complexed with the copper ion. These
solutions for the electroless deposition of the metals have
improved stability and increased plating rate.
BACKGROUND OF THE INVENTION
Chemical plating solutions for continuously depositing copper metal
by autocatalytic chemical reduction of ions of copper dissolved in
the solutions and in contact with a catalytic surface of an article
to be plated are well known. Broadly, the solutions comprise an
aqueous alkaline solution of a water-soluble salt of copper metal,
a reducing agent and a complexing agent for copper ion. Such
solutions, which do not utilize electricity, are sometimes referred
to in the art as electroless metal plating solutions, to
distinguish them from electroplating solutions, which do require
the use of electricity. Electroless metal deposition is also to be
distinguished from displacement metal plating of the type described
in Metals Finishing Guide Book, 27th Edition, 1959, page 469 et
seq., and metal mirroring procedures, wherein the metal plating
desired and achieved is only a few millionths of an inch in
thickness.
This invention is primarily concerned with the complexing agents
used in electroless copper baths.
Any complexing agent in general has to form a sufficiently strong
complex with the copper ions to prevent the precipitation of the
copper metal or salts thereof. Further, the complexing agent must
be capable of forming a complex with the copper ions which is
soluble in the plating solution, and also which is sufficiently
stable so that it will not react with the reducing agent in the
main body of the plating solution, but only at or in the vicinity
of the catalytic surface to be plated.
Somewhat surprisingly, many complexing and sequestering agents have
been found to be suitable for use. However, only a very few by
themselves give both good stability and rapid plating rates. One of
these, cyclohexanediaminetetraacetic acid, gives an excellent
combination of stability and plating rate when complexed with
copper.
Unfortunately, the few known, highly efficient complexers, e.g.,
cyclohexanediaminetetraacetic acid, are too expensive to be used by
themselves, in spite of the advantages noted.
It has now been found possible to use a family of imino compounds
as complexing agents and to obtain stabilities and plating rates
surprisingly approaching, and sometimes even surpassing those
obtained with cyclohexanediaminetetraacetic acid. The imino
compounds can also be used in mixtures with one another and with
cyclohexanediaminetetraacetic acid to obtain stable baths with
rapid plating rates. These advantages are obtained at unexpectedly
low cost.
In addition to their influence on the rate of dissociation of the
complex with copper ion, the new family of imino compounds also
influence the oxidation of the reducing agent, e.g., formaldehyde.
Therefore, mixtures of imino compounds with themselves or with
other complexers can provide enhanced stability and deposition rate
by controlling the oxidation rate of the reducing agent, which is
an essential component in all electroless copper baths.
This invention is concerned therefore with providing electroless
metal plating solutions containing complexes of copper ions with a
complexing agent which is an imino compound of a specified
type.
DESCRIPTION OF THE INVENTION
According to this invention, there are provided aqueous alkaline
chemical plating solutions capable of autocatalytically depositing
copper metal on a substrate in contact therewith comprising
a. water;
b. a water soluble complex of an imino compound of the formula
wherein x and y are each at least 1 and x and y together are from 2
to 25, or a mixture of said compounds, with copper ion; and
c. a reducing agent; and wherein the pH is between about 10 and
14.
One preferred family of imino compounds is depicted by FORMULA
IaP:
wherein x and y are each at least 1 and x and y together are from 2
to 25. An especially preferred member of this family is
cyclohexylaminediethanol, i.e., a compound of FORMULA Ia wherein x
and y are each 1. These compounds can be made by techniques
familiar to those skilled in the art. For example cyclohexylamine
can be reacted with ethylene oxide in an amount sufficient to give
polyoxyethylene chains of predetermined length.
Compounds of FORMULA Ia are commercially available under the name
ABBOMEENS E-2 to E-25 from Abbott Laboratories, North Chicago,
Illinois. The compound ABBOMEEN E-2 is
cyclohexylaminediethanol.
Another preferred complexing agent is of FORMULA Ib:
This compound is known as N-benzyliminodiacetic acid (BiDA). It can
be prepared by techniques familiar to those skilled in the art. For
example, sodium cyanide and formaldehyde can be added to an
alkaline solution of benzylamine. This forms the trialkali metal
salt of BiDA and acidification yields BiDA.
Benzyl iminodiacetic acid is commercially available from Aldrich
Chemical Company, Inc., Milwaukee, Wisconsin.
Also contemplated by the present invention are embodiments wherein
in addition to a compound of FORMULA Ia or Ib, another complexing
agent is present. The other sequestering or complexing agents can
comprise ammonia or an organic compound containing at least one
amine group, hydroxy group or carboxy group. Especially suitable
for use are ammonia and organic complex-forming agents containing
one or more of the following functional groups: primary amine group
(--NH.sub.2), a secondary amine group (>NH), tertiary amino
group (>N--), imino group (.dbd.NH), carboxy group (--COOH), and
hydroxy group (--OH). Among such agents may be mentioned
specifically cyclohexanediaminetetraacetic acid, ethylene diamine,
diethylene triamine, triethylene tetramine,
ethylenediaminetetraacetic acid,
N,N,N',N'-tetrakis-2-(2-hydroxypropyl)ethylenediamine, citric acid,
tartaric acid, 1,3-propane diamine, and ammonia. Related polyamines
and N-carboxymethyl derivatives thereof, such as
diethylenetriaminepentaacetic acid, may also be used.
Rochelle salts, the sodium salts (mono-, di- and tri-sodium) salts
of N-hydroxyethyethylenediaminetriacetic acid, nitrilotriacetic
acid and its alkali salts, gluconic acid, gluconates, and
triethanolamine are preferred as complexing agents, but
commercially available glucono-.gamma.-lactone and modified
ethylenediamineacetates are also useful, and in certain instances
give even better results than the pure sodium
ethylenediaminetetraacetates and
N-hydroxyethylethylenediaminetriacetate.
The water-soluble complex of copper used in this invention can be
prepared by adding the complexing agents to an aqueous solution of
the copper metal salt, e.g., the water soluble sulfates, chlorides,
acetates or nitrates thereof.
According to this invention, there are also provided processes for
electrolessly depositing copper on a catalytic surface which
comprise contacting the surface with an aqueous alkaline solution
of a complexed copper ion according to this invention; a reducing
agent, and wherein the pH is between about 10 and 14.
The reducing agent may consist of formaldehyde or any water-soluble
borohydride or amine borane having a good degree of solubility and
stability in aqueous solutions. Aqueous formaldehyde or
paraformaldehyde are preferred. Sodium and potassium borohydrides
are also suitable for use in the baths. Also may be mentioned
substituted borohydrides, such as sodium trimethoxy borohydride,
NaB(OCH.sub.3).sub.3 H. The amine boranes, such as isopropyl amine
borane and dimethyl amine borane are good reducing agents too and
can be used with the copper baths.
The plating solutions described herein will ordinarily be operated
at high pH, preferably at between pH 10 and 14.
When formaldehyde is used as the reducing agent, the pH will
ordinarily be between 10 and 14. When sodium borohydride is used as
the reducing agent, the pH will ordinarily be in the vicinity of
13-14. With potassium borohydride, the pH will generally be
maintained between about 11 and 12.
In preparing the electroless copper deposition baths, it is
desirable to combine the bath ingredients in such a manner as to
avoid reaction between the soluble metal salt and the reducing
agent.
It is therefore preferred to first add the complexing agent to the
aqueous solution of the metal salt to form the water-soluble
complex of the copper metal cations. The complexing agent can be
added as the free acid, or base, as the case may be, or as a salt
or other water-soluble derivative. The pH will determine the
species present. If the reducing agent is added before the metal
complex is formed, there will be a tendency for it to react
instantaneously with the copper metal salt to copper metal or a
salt of copper. After forming the copper complex, the pH is
adjusted to the proper value, e.g., by adding an acid or a base,
before adding the reducing agent. The reducing agent will
ordinarily be added in the form of an aqueous solution, e.g., 37
percent aqueous formaldehyde, preferably alkaline too.
The catalytic surfaces which may be plated with the baths of this
invention include metals such as nickel, cobalt, iron, steel,
palladium, platinum, copper, brass, manganese, chromium,
molybdenum, tungsten, titanium, tin or silver. All such metals are
catalytic to the reduction of the copper cations dissolved in the
solutions described.
Materials such as glass, ceramic, and various plastics are, in
general, noncatalytic. However, the surfaces of such noncatalytic
materials can be rendered catalytic by producing a film or
particles of one of the catalytic materials thereon. This can be
accomplished by a variety of techniques known to those skilled in
the art. One suitable sensitization procedure involves dipping
noncatalytic materials in an acidic solution of stannous chloride,
washing with water, and then contacting the material with an acidic
solution of a precious metal salt, e.g., palladium chloride. A
monolayer of precious metal is thus produced, which monolayer is
catalytic to reduction of the copper ions in the electroless metal
plating solutions.
Alternatively, such materials as glass, ceramic and plastic may be
sensitized or rendered catalytic by treatment with an acidic
aqueous solution containing, in combination, stannous tin ions and
precious metal ions.
A further sensitization procedure involves adhering to the normally
noncatalytic surface, finely divided particles of metals or metal
oxides which are catalytic to electroless copper solutions.
The term catalytic surface as used herein refers to the surface of
any article composed of the catalytic material described
hereinabove or covered therewith or to the surface of a
noncatalytic material which has been sensitized by producing a film
of particles of said catalytic materials on its surface.
The baths of this invention will deposit copper metal electrolessly
on the catalytic surfaces of metals and nonmetals, such as paper,
glass, ceramic, synthetic resins and plastics, including but not
limited to silicones, phenolics, alkyds, epoxies, styrenes,
acrylics, vinyl chlorides, nylon, mylar,
acrylonitrile-butadiene-styrene, and the like.
The quantities of the various ingredients in the baths of this
invention are subject to wide variation. Typically, however, the
bath constituents will be as follows:
Water soluble copper salt 0.002 to 0.60 moles/liter Reducing Agent
0.0002 to 2.5 moles/liter Complexing Agent 0.7 to 10 times the
moles of the metal salt Alkali metal hydroxide sufficient to
provide a pH of 10 to 14
There is theoretically required from 1 to 2 moles of formaldehyde
for every mole of copper salt. There is theoretically required
one-fourth to one-eighth moles of borohydride for every mole of
copper salt. These then may be considered the minimum amounts of
respective reducing agents required.
The amount of complexing agent to be added to the plating solution
depends upon the nature of the complexing agent and the amount of
copper salt present in the bath. In alkaline solutions, the
preferred ratio of copper salt to the complexing agent lies between
about 1:0.7 and 1:10. A small excess of the complexing agent, based
upon copper salt, generally is advantageous. The ratio of the
complexing agents, when used in admixture, may be varied over
rather broad limits without sacrificing the economic advantages
secured by this invention.
With the baths disclosed, copper metal deposition occurs
autocatalytically at a uniform rate wherever there is contact
between the catalytic surface being plated and the plating
solution. There is no substantial variation in the plate thickness
even for the most complicated shapes. Thus, copper may be uniformly
deposited in recesses, as well as on exposed parts of the object
being plated, and there is no buildup of coating at points or
edges. These conditions are difficult or impossible to achieve by
electroplating. Because of the uniform deposition achieved, the
plating process described is particularly suitable for plating
objects of irregular to complicated shapes which are difficult or
impossible to metallize by conventional techniques.
The process of this invention permits copper to be deposited on
practically any conceivable substratum and to practically any
thickness desired.
It should be understood that as the baths are used up in plating,
the copper salt, and the reducing agent may be replenished from
time to time, and also that it may be advisable to monitor the pH,
and the solution ingredients, 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 are added to the baths disclosed herein. Typical of
suitable surfactants are organic phosphate esters, and oxyethylated
sodium salts. Such surfactants may be obtained under the Tradenames
"Gefac RE 610" and "Triton QS-15," respectively.
In using the autocatalytic or electroless copper solutions, the
surface to be plated must be free of grease and other contaminating
material.
Where a nonmetallic surface is to be plated, the surface areas to
receive the deposit should first be sensitized as described
hereinabove.
Where a metal surface, such as stainless steel, is to be treated,
it should be degreased, and then treated with acid, such as
hydrochloric acid or phosphoric acid, to free the surface of
oxides.
Following pretreatment and/or sensitization, the surface to be
plated is immersed in the autocatalytic bath, and permitted to
remain in the bath until a copper metal deposit of the desired
thickness has been built up.
Description of the Preferred Embodiments. Typical plating baths
made in accordance with the teachings contained herein are given
below:
Example 1
__________________________________________________________________________
Copper sulfate pentahydrate 0.050 moles/liter (CuSO.sub.4.sup..
5H.sub. 2 O) Cyclohexylaminediethanol 0.170 moles/liter (CADE)
Formaldehyde (6 ml. of 37%) 0.074 moles/liter Sodium cyanide (5
mg.) 0.0001 moles/liter Water q.s.a.d. pH 12.80
__________________________________________________________________________
a clean copper strip is immersed in the bath at 50.degree. C.
Copper is deposited at a plating rate of 115 mg./10 cm..sup.2 /hr.
(0.60 mils per hour).
Example 2 Copper sulfate pentahydrate 0.050 moles/liter
(CuSO.sub.4.sup.. 5H.sub.2 O) Cyclohexylaminediethanol 0.20
moles/liter (CADE) Formaldehyde (6 ml. of 37%) 0.074 moles/liter
Sodium cyanide (30 mg.) 0.0006 moles/liter Water q.s.a.d. pH 13.00
__________________________________________________________________________
the plating rate at 60.degree. C. is 100 mg./10 cm..sup.2 /hr.
(0.44 mils per hour).
Example 3
__________________________________________________________________________
Copper sulfate pentahydrate 0.050 moles/liter (CuSO.sub.4.sup. .
5H.sub.2 O) Cyclohexylaminediethanol 0.40 moles/liter (CADE)
Formaldehyde (6 ml. of 37%) 0.074 moles/liter Sodium cyanide (30
mg.) 0.0006 moles/liter Water q.s.a.d. pH 13.00
__________________________________________________________________________
the plating rate at 60.degree. C. is 100 mg./10 cm..sup.2 /hr.
(0.44 mils per hour).
Example 4
__________________________________________________________________________
Copper sulfate pentahydrate 0.025 moles/liter (CuSO.sub.4.sup. .
5H.sub.2 O) Cyclohexylaminediethanol 0.20 moles/liter (CADE)
Formaldehyde (6 ml. of 37%) 0.074 moles/liter Sodium cyanide (30
mg.) 0.0006 moles/liter Water q.s.a.d. pH 13.00
__________________________________________________________________________
the plating rate at 60.degree. C. is 55 mg./10 cm..sup.2 /hr. (0.24
mils per hour).
Example 5
__________________________________________________________________________
Copper sulfate pentahydrate 0.050 moles/liter . . 5H.sub.2 O)
Cyclohexylaminediethanol 0.20 moles/liter (CADE) Formaldehyde (6
ml. of 37%) 0.074 moles/liter Sodium cyanide (30 mg.) 0.0006
moles/liter Ammonium Sulfate (0.5 g.) 0.0038 moles/liter Water
q.s.a.d. pH 13.00
__________________________________________________________________________
the plating rate at 60.degree. C. is 45 mg./10 cm..sup.2 /hr. (0.20
mils per hour).
Example 6
__________________________________________________________________________
Copper sulfate pentahydrate 0.050 moles/liter (CuSO.sub.4.sup..
5H.sub.2 O) Cyclohexylaminediethanol 0.20 moles/liter (CADE)
Abbomeen E-25 0.01 molelliter (Abbott Laboratories, Ill.)
Formaldehyde (6 ml. of 37%) 0.074 moles/liter Sodium cyanide (20
mg.) 0.0004 moles/liter Water q.s.a.d. pH 13.00
__________________________________________________________________________
the plating rate at 60.degree. C. is 24 mg./10 cm..sup.2 /hr. (0.11
mils per hour).
Example 7
__________________________________________________________________________
Copper sulfate pentahydrate 0.050 moles/liter CuSO.sub.4.sup..
5H.sub.2 O) Cyclohexylaminediethanol 0.20 moles/liter (CADE)
o-Cyclohexanediaminetetraacetic 0.05 moles/liter acid (CDTA)
Formaldehyde 0.074 moles/liter Sodium cyanide (10 mg.) 0.0002
moles/liter Water q.s.a.d. pH 12.80
__________________________________________________________________________
the plating rate at 60.degree. C. is 40 mg./10 cm..sup.2 /hr. (0.18
mils per hour).
Example 8
__________________________________________________________________________
Copper sulfate pentahydrate 0.05 moles/liter (CuSO.sub.4.sup..
5H.sub.2 O) N-Benzyliminodiacetic acid 0.20 moles/liter (BIDA)
Formaldehyde 0.074 moles/liter Water q.s.a.d. pH 12.50
__________________________________________________________________________
the plating rate at 25.degree. C. is 40 mg./10 cm..sup.2 /hr. (0.18
mils per hour).
Example 9
__________________________________________________________________________
Copper sulfate pentahydrate 0.05 moles/liter (CuSO.sub.4.sup..
5H.sub.2 O) N-Benzyliminodiacetic acid 0.10 moles/liter (BIDA)
Ethylenediaminetetraacetic 0.10 moles/liter acid (EDTA)
Formaldehyde (6 ml. of 37%) 0.074 moles/liter Sodium cyanide (30
mg.) 0.0006 moles/liter Water q.s.a.d. pH 12.50
__________________________________________________________________________
the plating rate at 60.degree. C. is 35 mg./10 cm..sup.2 /hr. (0.15
mils per hour).
Example 10
__________________________________________________________________________
Copper sulfate pentahydrate 0.05 moles/liter (CuSO.sub.4.sup..
5H.sub.2 O) Cyclohexylaminediethanol 0.10 moles/liter (CADE)
N-Benzyliminodiacetic acid 0.15 moles/liter (BIDA) Formaldehyde (6
ml. of 37%) 0.074 moles/liter Sodium cyanide (30 mg.) 0.0006
moles/liter Water q.s.a.d. pH 13.50
__________________________________________________________________________
the plating rate at 55.degree. C. is 40 mg./10 cm..sup.2 /hr. (0.18
mils per hour).
Metallized surfaces produced by utilizing the autocatalytic metal
deposition solution of this invention are useful as ornamental
designs, markings, and the like. Similarly, using these baths
copper may be deposited in predetermined patterns on insulating
substrata and serve as electrical conductors. Electrically
conductive circuit patterns, e.g., printed circuits, may thus be
selectively plated on the activated areas of an inexpensive sheet
of a wide variety of insulating material.
It has been shown that mixing of complexers in different
proportions in electroless baths provides new and unexpected
results in the variation of plating rates and bath stabilities.
There have been provided novel, alternative and simultaneous
pathways for the reduction of copper metal complexes. Also provided
are novel species in the bath (mixed metal complexes, two or more
different complexers on the same metal ion, and all permutations
thereof). Novel intermediates and new chemical reactions are also
obtained with the teachings herein.
The invention in its broader aspects is not limited to the specific
steps, processes and compositions described and 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.
* * * * *