U.S. patent number 3,725,220 [Application Number 05/248,160] was granted by the patent office on 1973-04-03 for electrodeposition of copper from acidic baths.
This patent grant is currently assigned to Lea-Ronal, Inc.. Invention is credited to Richard B. Kessler, Fred I. Nobel.
United States Patent |
3,725,220 |
Kessler , et al. |
April 3, 1973 |
ELECTRODEPOSITION OF COPPER FROM ACIDIC BATHS
Abstract
An acid copper plating bath which contains a copper metal salt
and a minor amount of a sulfoniumalkanesulfonate or
sulfoniumalkanecarboxylate as a brightening agent. Illustrative
sulfonium compounds are N-cyclohexyl-2-benzothiazol
sulfonium-1-propanesulfonate, bis (dimethylthiocarbamyl)
sulfonium-1-propanesulfonate, and bis (dimethylthiocarbamyl)
sulfonium-1-propanecarboxylate. Preferred amounts of the sulfonium
compounds range from about 0.001 to 1.0 grams per liter. The use of
such acid copper plating baths in the electrodeposition of copper
metal is also disclosed.
Inventors: |
Kessler; Richard B. (Jericho,
NY), Nobel; Fred I. (Roslyn, NY) |
Assignee: |
Lea-Ronal, Inc. (Freeport,
NY)
|
Family
ID: |
22937944 |
Appl.
No.: |
05/248,160 |
Filed: |
April 27, 1972 |
Current U.S.
Class: |
205/296;
205/298 |
Current CPC
Class: |
C25D
3/38 (20130101) |
Current International
Class: |
C25D
3/38 (20060101); C23b 005/20 (); C23b 005/46 () |
Field of
Search: |
;204/52R,52Y,44,106
;106/1 ;117/13E |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; G. L.
Claims
What is claimed is:
1. In an acid copper electroplating bath containing a salt of
copper and a free acid as the essential constituents, the
improvement which comprises the addition to said bath of an amount,
sufficient to provide a bright electrodeposit, of a sulfonium
compound having the structure
wherein R is a radical selected from the group consisting of
hydrogen; alkyl having from one to eight carbon atoms; aryl having
from six to 12 carbon atoms; ##SPC2##
wherein R' is a lower alkyl radical having from one to six carbon
atoms, and r is 1 or zero; n is an integer from 1 to 6; R" is
selected from the group consisting of hydrogen and methyl; and Z is
an anion selected from the group consisting of SO.sub.3.sup.- and
COO.sup.-.
2. In the acid copper plating bath of claim 1 wherein the sulfonium
compound is added to said bath in an amount ranging from about
0.001 to 1.0 gram per liter.
3. In the acid copper plating bath of claim 1 wherein the sulfonium
compound is N-cyclohexyl-2-benzothiazol
sulfonium-1-propanesulfonate.
4. In the acid copper plating bath of claim 1 wherein the sulfonium
compound is bis(dimethylthiocarbamyl)
sulfonium-1-propanesulfonate.
5. In the acid copper plating bath of claim 1 wherein the sulfonium
compound is bis(dimethylthiocarbamyl)
sulfonium-1-propanecarboxylate.
6. In the acid copper plating bath of claim 1 wherein the sulfonium
compound is bis(benzothiazole)sulfonium-1-propanesulfonate.
7. In the acid copper plating bath of claim 1 wherein the bath also
contains a glycol selected from the group consisting of
polyethylene glycol and methoxypolyethylene glycol in an amount
sufficient to enhance the brightness of the electrodeposit.
8. In the acid copper plating bath of claim 7 wherein the bath also
contains a triphenyl methane dye in an amount sufficient to enhance
the brightness of the electrodeposit.
9. In the acid copper plating bath of claim 8 wherein the dye is
Methyl Violet.
10. In the acid copper plating bath of claim 7 wherein the bath
also contains 2-thiazolidienethione.
11. In a process of electrodepositing copper, the step which
comprises electrolyzing an aqueous acid copper solution containing
a copper metal salt and an amount, sufficient to provide a bright
electrodeposit, of a sulfonium compound having the structure.
wherein R is a radical selected from the group consisting of
hydrogen; alkyl having from one to eight carbon atoms; aryl having
from six to 12 carbon atoms; ##SPC3##
wherein R' is a lower alkyl radical having from one to six carbon
atoms, and r is 1 or zero; n is an integer from 1 to 6; R" is
selected from the group consisting of hydrogen and methyl; and Z is
an anion selected from the group consisting of SO.sub.3.sup.- and
COO.sup.-.
12. In the process of claim 11 wherein the amount of the sulfonium
compound ranges from about 0.001 to 1.0 gram per liter.
13. In the process of claim 11 wherein the sulfonium compound is
bis(dimethylthiocarbamyl)sulfonium-1-propanesulfonate.
Description
The present invention relates to the electroplating of copper from
an aqueous acidic bath. More particularly the invention pertains to
an acid copper plating bath containing a minor proportion of a
novel brightening agent.
In the art of copper plating it has been customary to add various
brightening agents to the acidic baths. Illustrative brightening
agents are disclosed in U.S. Pat. Nos. 3,276,979; 3,288,690;
2,707,166; 2,707,167; 2,733,198; 2,830,014; and 2,910,413.
Brightening agents such as the organic sulfonic acids and
carboxylic acids or their salts offered considerable promise but
suffer from certain serious disadvantages. For example, these
brighteners have a limited low current density brightness range. On
standing or after a period of electrolysis the decomposition
products or sludge resulting from the use of these brighteners
further reduced the low current density brightness range and
furthermore required the use of auxiliary brighteners or
purification procedures. Moreover, it was found that the degree of
stability of the alkane mercapto sulfonates or carboxylates was
markedly reduced or rendered ineffective in baths having high acid
concentrations.
In accordance with the present invention it has now been found that
the above described disadvantages can be avoided by utilizing
organic sulfonium sulfonates or carboxylates as brightening agent
additives in acidic aqueous baths for the electroplating of copper.
The novel brightening agents of this invention are very stable in
both standard and high acid concentration plating baths even after
prolonged electrolysis or storage. In addition the low current
density brightness range is not adversely affected as is the case
with the previously described alkane mercapto sulfonates or
carboxylates.
The novel sulfonium sulfonate or carboxylate brightening agents of
this invention have the following formula:
wherein each R radical, which may be the same or different, is
selected from the group consisting of hydrogen; alkyl having from
one to eight carbon atoms, for example; methyl or ethyl; aryl
having from six to 12 carbon atoms, for example; phenyl or
naphthyl; ##SPC1##
Wherein each R' radical may be the same or different and is a lower
alkyl having from one to six carbon atoms; and r is 1 or zero; n is
an integer from 1 to 6; R" is selected from the group consisting of
hydrogen and the methyl radical; and Z is an anion selected from
the group consisting of SO.sub.3.sup.- and COO.sup.-.
In the practice of this invention, the preferred brightening agents
are those of the general formula
with each R being
wherein r is zero and each R' is lower alkyl having from one to six
carbon atoms; Z is SO.sub.3.sup.- and n is an integer from 1 to 6.
Especially preferred is the brightening agent wherein each R' is
methyl; n is 3; Z is SO.sub.3.sup.- ; and r is zero. However, it
should be understood that other brightening agents of this
invention also provide satisfactory results.
The sulfoniumalkanesulfonates encompassed by the above formulas are
disclosed in U.S. Pat. No. 2,813,898 along with various methods for
their preparation. Broadly the classes of sulfoniumalkanesulfonates
include:
a. dialkylsulfoniumalkanesulfonates having from one to 18 carbon
atoms in the alkyl radical,
b. diarlsulfoniumalkanesulfonates;
c. bis(alkaryl)sulfoniumalkanesulfonates;
d. bis(aralkyl)sulfoniumalkanesulfonates;
e. bis(alkarylalkyl)sulfoniumalkanesulfonates;
f. di(cycloalkyl)sulfoniumalkanesulfonates; and derivatives
thereof, including nitrogen-containing derivatives.
Typical sulfoniumalkanesulfonates include for example:
N-cyclophenxyl-2-benzothiazol sulfonium-1-propanesulfonate;
Bis benzothiazole-thio-2-sulfonium-1-propanesulfonate;
2-dimethylsulfonium-1-propanesulfonate;
Bis(dimethylthiocarbamyl)sulfonium-1-propanesulfonate;
2-(diphenyl)sulfonium-1-butanesulfonate;
Furfurylmethylsulfoniumpropanesulfonate; etc.
It should be understood that the use of other mono- and disulfonium
sulfonates and carboxylates are also contemplated in the broad
aspects of the present invention. For example, it would be possible
to convert the sulfur-containing acyclic organic compounds
disclosed in the Strauss et al. U.S. Pat. No. 2,910,413 to the
corresponding sulfonates and carboxylates and to employ the
resulting compounds as brighteners in the present invention. The
general structural formula of the Strauss et al. acyclic organic
compounds, which can be used as the raw material, is as
follows:
wherein R is a lower aliphatic radical; Q and Q' are selected from
the group consisting of hydrogen, lower alkyl and lower
hydroxy-alkyl; X, Y and Z are selected from the group consisting of
oxygen, sulfur, nitrogen, and the imino radical, at least one of
them being sulfur; and X', Y', and Z' are selected from the group
consisting of oxygen, sulfur, nitrogen and the imino radical, at
least one of them being sulfur. The conversion to the sulfonium
derivative can be accomplished by use of the general procedures
known to the art.
The sulfoniumalkanecarboxylates which can be effectively employed
as brightening agents in the practice of the present invention are
similar to the above described classes of sulfoniumalkanesulfonates
except that a carboxyl radical is substituted for the sulfonate
radical. Typical sulfoniumalkanecarboxylates include:
Bis(dimethylthiocarbamyl)sulfonium-1-propanecarboxylate;
Dibenzylsulfoniumpropanecarboxylate;
Methylbutylsulfoniumethanecarboxylate; etc.
Bis(dimethylthiocarbamyl)sulfonium-1-propanesulfonate can be
prepared by the reaction of tetramethyl thiuram monosulfide and
propane sultone in accordance with the procedure described by
Gaertner in U.S. Pat. No. 2,813,898. Other sulfonium sulfonates can
be prepared by the same general procedure utilizing the appropriate
sulfides and sultones.
The corresponding
bis(dimethylthiocarbamyl)sulfonium-1-propanecarboxylate can be
prepared by the Gaertner procedure, except that propriolactone is
substituted for the propane sultone.
Although the novel stable brightening agents of this invention may
be employed by themselves to obtain very satisfactory brightening
effects in the electroplating of copper, they may also be utilized
in conjunction with known brightening agents or other additives to
improve further the brightening and leveling. For example, the use
of the brightening agents of this invention in conjunction with
such prior art substances as the carbon-oxygen compounds disclosed
in U.S. Pat. No. 3,288,690; polyethylene glycols and methoxy
polyethyleneglycols, imparts excellent brightness and leveling
qualities to the electroplated product. Furthermore, the qualities
of the electroplated end product can be enhanced by the inclusion
in the electroplating bath of such materials as amine dyes such as
described in U.S. Pat. Nos. 2,707,166; and 2,882,209; or a
triphenyl methane dye or such other leveling agents as disclosed in
U.S. Pat. No. 2,733,198. Preferred other additives include
polyethylene glycols and methoxy polyethylene glycols such as
Carbowax 5000 having a molecular weight range of 2,000 to 6,000;
aminothiazoles and aminothiazolines such as 2-thiazolidinethione;
and dyes such as Methyl Violet, Crystal Violet, and Fuchsin.
Mixtures of these other additives may also be employed. In general,
these other additives are utilized in minor, conventional
amounts.
To obtain the satisfactory results of this invention a minor but
effective amount of the novel brightening agents of this invention
are incorporated into the aqueous plating bath prior to the
inception of the electrolytic plating operation. The amount of the
novel brightening agent to be incorporated into the plating bath
should be sufficient to obtain the brightening effect desired in
each particular case as may be determined by the worker skilled in
the art. It has been found in practice that satisfactory results
are obtained when the novel brightening agents are present in the
electrolyte plating bath in a concentration of from about 0.0001 to
1.5 grams per liter, and most preferably from 0.001 to 1.0 gram per
liter.
Conventional acidic copper baths having the usual components and
proportions can be employed in the practice of this invention.
The usual bath will have the following composition:
CuSO.sub.4 (5H.sub.2 O) -- 150-250 g./l.
Conc. sulfuric acid -- 45-110 g./l.
The sulfuric acid may be substituted with sulfamic or fluoboric
acids, while the copper may be salts of other acids such as
sulfamic or fluoboric .
The invention will be further understood by reference to the
following illustrative examples:
EXAMPLE 1
An aqueous acid copper plating bath was prepared having
incorporated therein the following materials:
Material Concentration CuSO.sub.4 (5H.sub.2 O) 250 gm./liter
H.sub.2 SO.sub.4 60 gm./liter Cl.sup.- 75 ppm
Bis(dimethylthiocarbamyl) sulfonium-1-propanesulfonate 0.01
gm./liter
The plating bath was operated at 70.degree. F. in a Hull cell with
vigorous air agitation at a current of 2.0 amps for 5 minutes. The
copper deposit on the plated material was smooth and semi-lustrous
over a current density range of from 2 to 75 amps/sq.ft. (ASF).
EXAMPLE 2
The procedure of Example 1 was followed except that the following
material was also incorporated into the plating bath:
Material Concentration Carbowax 5000 0.4 gm./liter
The copper deposit on the plated material was bright and leveled
over a current density range of from 1 to 100 ASF.
EXAMPLE 3
The procedure of Example 1 was followed except that the following
materials were also incorporated into the plating bath:
Material Concentration Carbowax 5000 0.4 gm./liter Methyl violet
0.015 gm./liter
The copper deposit on the plated material was very bright and
leveled in the range of from 1 to 100 ASF, and showed increased
brightness and leveling in the low current density range of from 1
to 10 ASF.
EXAMPLE 4
The procedure of Example 1 was followed except that the following
materials were also incorporated into the plating bath:
Material Concentration Carbowax 5000 0.4 gm./liter Methyl violet
0.015 gm./liter 2-Thiazolidienethione 0.001 gm./liter
A Hull cell panel which was preroughened with a 220 grit abrasive
was electroplated in accordance with the procedure of Example 1 and
provided a final plated product possessing optimum brightness and
leveling properties.
EXAMPLE 5
The electroplating bath of Example 3 was set aside and allowed to
remain standing for a period of 30 days. Thereafter, Hull cells
were rerun in accordance with the procedure set forth in Example 1
yielding a plated final product which showed no substantial
deterioration of the brightness or low current density dullness. In
addition no brightener decomposition products formed in the plating
tank.
EXAMPLE 6
An aqueous acid copper plating bath was prepared having
incorporated therein the following materials:
Material Concentration CuSO.sub.4 (5H.sub.2 O) 250 gm./liter H.sub.
2 SO.sub.4 60 gm./liter Cl.sup.- 35 ppm Bis(dimethylthiocarbamyl)
sulfonium-1-propanecarboxylate 3.2 gm./liter
The above bath was operated at room temperature in a Hull cell at
2.0 amperes for 5 minutes with mechanical agitation. The final
plated product possessed a semi-bright to bright deposit over a
current density range of from 20 to 100 ASF.
EXAMPLE 7
An aqueous copper plating bath was prepared having incorporated
therein the following materials:
Material Concentration CuCO.sub.3 105 gm./liter HBF.sub.4
sufficient to neutralize bath to pH 1.0 Cl.sup.- 36 ppm
Bis(dimethylthiocarbamyl) sulfonium-1-propanesulfonate 0.60
gm./liter
A Hull cell panel was run at 2.0 amperes for 5 minutes with
mechanical agitation at 70.degree. F. yielding a bright lustrous
deposit over a current density range of from 3 to 100 ASF.
It is well recognized that high acid-low copper plating bath
formulations are particularly effective where better throwing power
is required for proper copper plating. Heretofore, the high acid
concentrations of the baths caused deterioration of the known
organo-sulfur brightening agents which resulted in the baths being
relatively short lived. This caused an increase in the stress of
the copper deposit and led to dullness of the resultant
copperplating, requiring frequent purification of the plating bath.
By the practice of the instant invention, the prior art
disadvantages experienced with these high acid-low copper plating
baths have been obviated, in that these baths are stable over
extended periods of time, breakdown of the brighteners into harmful
by-products has been eliminated, and the copper deposits are bright
with low stress properties. These advantages of the present
invention are illustrated below:
EXAMPLE 8
A high acid-low copper aqueous electroplating bath was prepared
having the following materials incorporated therein:
Materials Concentration CuSO.sub.4 (5H.sub.2 O) 75 gm./liter
H.sub.2 SO.sub.4 (1.84 sp. gr.) 184 gm./liter
Bis(dimethylthiocarbamyl) sulfonium-1-propanesulfonate 0.005
gm./liter Carbowax 5000 0.16 gm./liter Methyl Violet 0.006
gm./liter
A printed circuit board with hole dimensions of 0.06 inch in length
and 0.06 inch in diameter was plated in the above bath at an
average current density of 20 ASF, at 70.degree. F., with 1 mil of
copper which was very bright in appearance, and had a thickness
ratio, surface to hole, of 1.1-1.0. The bath was then permitted to
stand idle for a period of 30 days, whereupon the procedure set
forth above was repeated. The same results were obtained without
substantial loss of brightness, current density range or metal
distribution ratio in the plated product.
While particular embodiments of this invention are shown above, it
will be understood that the invention is obviously subject to
variations and modifications without departing from its broader
aspects.
* * * * *