U.S. patent application number 11/682987 was filed with the patent office on 2007-09-27 for electroplating method.
This patent application is currently assigned to C. Uyemura & Co., Ltd.. Invention is credited to Toru Murakami.
Application Number | 20070221506 11/682987 |
Document ID | / |
Family ID | 38460475 |
Filed Date | 2007-09-27 |
United States Patent
Application |
20070221506 |
Kind Code |
A1 |
Murakami; Toru |
September 27, 2007 |
ELECTROPLATING METHOD
Abstract
A cycle of electroplating is repeated in an electroplating bath
containing at least one metal ion selected from cobalt, nickel and
iron, a buffering agent and a conducting agent by use of a soluble
anode. The concentration of the conducting agent in an initially
prepared electroplating bath is set at 70 to 95% of a saturated
concentration. The electroplating is repeated in such a way that a
first replenishment solution containing a buffering agent and a
conducting agent at concentrations of 0.5 to 1.2 times the
concentrations in the initially prepared electroplating bath and
free of the metal ion is added so as to replenish the agents that
have been reduced in amount during the course of the electroplating
and a concentration of the conducting agent in the electroplating
bath after the replenishment of the first replenishment solution is
adjusted to 70 to 95% of a saturated concentration thereof.
According to the invention, the electroplating can be repeated
while keeping the electroplating bath over a long time in a good
condition sufficient to provide a plated film having high throwing
power and a good appearance, so that there can be stably obtained
plated films over a long time without frequent regeneration such as
by electrolysis for lowering the concentration of a metal ion in
the plating bath, thus being good at economy.
Inventors: |
Murakami; Toru;
(Hirakata-shi, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
C. Uyemura & Co., Ltd.
Osaka-shi
JP
|
Family ID: |
38460475 |
Appl. No.: |
11/682987 |
Filed: |
March 7, 2007 |
Current U.S.
Class: |
205/261 |
Current CPC
Class: |
C25D 21/14 20130101;
C25D 21/18 20130101 |
Class at
Publication: |
205/261 |
International
Class: |
C25D 3/00 20060101
C25D003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 27, 2006 |
JP |
2006-085043 |
Claims
1. An electroplating method wherein a cycle of electroplating a
substrate for plating is repeated by use of a soluble anode in an
electroplating bath containing at least one metal ion selected from
those of cobalt, nickel and iron, a buffering agent, and a
conducting agent, the method comprising: setting a concentration of
said conducting agent in an initially prepared electroplating bath
at a level within a range of 70 to 95% of a saturated
concentration; replenishing said buffering agent and said
conducting agent, each reduced in amount during the repetition of
the electroplating, by adding, to said electroplating bath, a first
replenishment solution that contains a buffering agent and a
conducting agent each at a concentration of 0.5 to 1.2 times the
concentration contained in the initially prepared electroplating
bath and is free of said at least one metal ion; and adjusting the
concentration of said conducting agent in said electroplating bath
after the replenishment of said first replenishment solution to 70
to 95% of a saturated concentration under which the electroplating
is repeated.
2. The method according to claim 1, wherein said buffering agent
and said conducting agent used in said first replenishment solution
are, respectively, the same as those used in said initially
prepared electroplating bath.
3. The method according to claim 1, wherein said electroplating
bath further comprises a halide ion, and the electroplating is
carried out in such a way that a halide ion in the electroplating
bath reduced in amount during the course of the repetition of the
plating is replenished by adding, to said electroplating bath, said
first replenishment solution that further comprises a halide ion at
a concentration of 0.5 to 1.2 times the concentration in the
initially prepared electroplating bath.
4. The method according to claim 3, wherein said halide ion used in
said first replenishment solution is the same as said halide ion
used in said initially prepared electroplating bath.
5. The method according to claim 1, wherein said electroplating
bath further comprises an organic brightener, and the
electroplating is carried in such a way that said organic
brightener reduced in amount during the course of the repetition of
the electroplating in said electroplating bath is replenished by
adding, to said electroplating bath, said first replenishment
solution further comprising an organic brightener at a
concentration of 0.5 to 1.2 times that in the initially prepared
electroplating bath.
6. The method according to claim 5, wherein said organic brightener
used in said first replenishment solution is the same as said
organic brightener used in said initially prepared electroplating
bath.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This non-provisional application claims priority under 35
U.S.C. .sctn.119(a) on Patent Application No. 2006-085043 filed in
Japan on Mar. 27, 2006, the entire contents of which are hereby
incorporated by reference.
TECHNICAL FIELD
[0002] This invention relates to an electroplating method wherein
in case where a cycle of electroplating a substrate for plating is
repeated by use of a soluble anode in an electroplating bath
capable of yielding a film of nickel, cobalt, iron or an alloy
thereof having high throwing power, plated films having high
throwing power and an good outer appearance can be stably formed
over a long time.
BACKGROUND ART
[0003] For an electroplating solution capable of forming plated
films having high throwing power, there are known, for example,
electroplating solutions containing water soluble salts of nickel,
cobalt or iron (hereinafter referred generically to merely as a
nickel series metal), conducting agents, buffering agents, halide
ions, organic brightening agents and the like (see Japanese Patent
Laid-open Nos. Sho 62-103387 and Sho 62-109991).
[0004] Where electroplating is carried out by use of such an
electroplating solution and a soluble anode, an anode current
efficiency becomes close to 100%, whereas a cathode current
efficiency is usually at 95%, thereby causing an efficiency
difference to develop. If the plating is continued, a nickel series
metal (nickel series metal ion) increases in the electroplating
solution. It is known that if the concentration of the
nickel-series metal increases in excess, throwing power lowers. In
order to keep high throwing power, there has been proposed a method
wherein a nickel series metal increased to an extent exceeding an
allowable range in the electroplating solution is removed (Japanese
Patent Laid-open No. Hei 8-53799).
[0005] In the method, an anodic solution and an electroplating
solution are separated from each other by means of a cationic
exchange resin membrane, under which electrolysis is carried out by
immersing an insoluble anode in the anodic solution and a cathode
in the electroplating solution, respectively, thereby causing metal
ions in the electroplating solution to be removed by deposition on
the cathode as a metal. However, this method needs to stop a
plating equipment for 1 to 2 days and treat at a current density of
1 A/dm.sup.2, and it is not good at economy to carry out such a
treatment frequently. If the electroplating solution is treated
according to the above method, repeated use of the electroplating
solution over a long time may lead to a lowering of throwing power
of the resulting plated films.
[0006] With the electroplating, there is a so-called "drag-out"
phenomenon wherein an electroplating solution is entrained outside
a tank along with substrates for plating. By this, concentrations
of components other than metal ions vary. In order to carry out the
plating repeatedly, individual components reduced in amount by the
drag-out are replenished, whereupon precipitates or crystals may
occur.
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0007] Under these circumstances in the art, an object of the
invention is to provide an electroplating method wherein in case
where a cycle of electroplating a substrate for plating is repeated
by use of a soluble anode in an electroplating bath capable of
yielding a film of nickel, cobalt, iron or an alloy thereof having
high throwing power, the throwing power of the plated films is kept
high over a long time without causing disfigurement of the plated
films.
MEANS FOR SOLVING THE PROBLEMS
[0008] We made intensive studies in order to solve the above
problems and, as a result, found that in order to keep high
throwing power in the course of repeated use of a plating bath, it
is important not only to suppress a nickel series metal ion from
increasing in an electroplating bath, but also to permit a
concentration of a conducting agent to be continuedly kept at a
high level while suppressing a variation thereof. In this
connection, however, where the concentration of the conducting
agent in the electroplating bath is kept at a high level, it is
liable to cause the conducting agent to be precipitated or
crystallized in the electroplating bath and, if precipitation or
crystallization of the conducting agent takes place, the resulting
plated film becomes poor in appearance.
[0009] It has been found that in order to keep good throwing power
and appearance of the plated film over a long time, it is necessary
(1) to suppress an increase in concentration of a nickel series
metal ion in an electroplating bath, (2) not to make the
concentration of a conducting agent in a replenishment solution at
a level beyond necessity in order that while keeping the
concentration of the conducting agent in the electroplating bath at
a high level, a saturated concentration is not exceeded, and (3) to
set the concentration of the conducting agent to a level lower that
a saturated concentration upon initial preparation of an
electroplating bath or after replenishment of a replenishment
solution so as not to cause the conducting agent to be precipitated
or crystallized owing to the evaporation of water in the
electroplating bath.
[0010] In this way, it has been found effective that where a cycle
of electroplating a substrate for plating is repeated by use of a
soluble anode in an electroplating bath containing at least one
metal ion selected from those of cobalt, nickel and iron, a
buffering agent, and a conducting agent, the concentration of the
conducting agent in an initially prepared electroplating bath is
set at a level within a range of 70 to 95% of a saturated
concentration, the buffering agent and the conducting agent, each
reduced in amount during the repetition of the electroplating, are
replenished by adding, to the electroplating bath, a first
replenishment solution that contains a buffering agent and a
conducting agent each at a concentration of 0.5 to 1.2 times the
concentration contained in the initially prepared electroplating
bath and is free of the at least one metal ion, and the
concentration of the conducting agent in the electroplating bath
after the replenishment of the first replenishment solution is
adjusted to 70 to 95% of a saturated concentration.
[0011] If the electroplating bath further includes a halide ion,
the electroplating is carried out in such a way that the halide ion
reduced in amount during the course of the repetition of the
plating in the electroplating bath is replenished by adding, to the
electroplating bath, the first replenishment solution that further
includes a halide ion at a concentration of 0.5 to 1.2 times the
concentration in the initially prepared electroplating bath.
[0012] Further, if the electroplating bath further includes an
organic brightener, the electroplating is carried in such a way
that the organic brightener in the electroplating bath reduced in
amount during the course of the repetition of the plating is
replenished by adding, to the electroplating bath, the first
replenishment solution which further includes an organic brightener
at a concentration of 0.5 to 1.2 times that in the initially
prepared electroplating bath. The invention has been accomplished
based on these findings.
[0013] More particularly, the invention provides:
[1] an electroplating method wherein a cycle of electroplating a
substrate for plating is repeated by use of a soluble anode in an
electroplating bath containing at least one metal ion selected from
those of cobalt, nickel and iron, a buffering agent, and a
conducting agent, the method including setting a concentration of
the conducting agent in an initially prepared electroplating bath
at a level within a range of 70 to 95% of a saturated
concentration, replenishing the buffering agent and the conducting
agent, each reduced in amount during the repetition of the
electroplating, by adding, to the electroplating bath, a first
replenishment solution that contains a buffering agent and a
conducting agent each at a concentration of 0.5 to 1.2 times the
concentration contained in the initially prepared electroplating
bath and is free of the at least one metal ion, and adjusting the
concentration of the conducting agent in the electroplating bath
after the replenishment of the first replenishment solution to 70
to 95% of a saturated concentration, under which the electroplating
is repeated; [2] the method of [1] above, wherein the
electroplating bath further includes a halide ion, and the halide
ion in the electroplating bath reduced in amount during the course
of the repetition of the plating is replenished by adding, to the
electroplating bath, the first replenishment solution that further
includes a halide ion at a concentration of 0.5 to 1.2 times the
concentration in the initially prepared electroplating bath; and
[3] The method of [1] or [2] above, wherein the electroplating bath
further includes an organic brightener, and the organic brightener
in the electroplating bath reduced in amount during the course of
the repetition of the plating is replenished by adding, to the
electroplating bath, the first replenishment solution which further
includes the organic brightener at a concentration of 0.5 to 1.2
times that in the initially prepared electroplating bath.
BENEFITS OF THE INVENTION
[0014] According to the invention, the electroplating can be
repeated while keeping the electroplating bath over a long time in
a good condition sufficient to provide a plated film having high
throwing power and a good appearance, so that there can be stably
obtained plated films over a long time without frequent
regeneration such as by electrolysis for lowering the concentration
of a metal ion in the plating bath, thus being good at economy.
BEST MODE FOR CARRYING OUT THE INVENTION
[0015] The invention is now described in more detail.
[0016] The invention relates to a method for repeating a cycle of
electroplating a substrate for plating by use of a soluble anode in
an electroplating bath containing at least one metal ion selected
from those of cobalt, nickel and iron, a buffering agent and a
conducting agent. In the method, the electroplating is repeatedly
carried out by setting a concentration of the conducting agent in
an initially prepared electroplating bath at a level of 70 to 95%
of a saturated concentration, replenishing the buffering agent and
the conducting agent in the electroplating bath reduced during the
repetition of the plating by adding, to the electroplating bath, a
first replenishment solution, which is free of the metal ion and
contains a buffering agent and a conducting agent at concentrations
of 0.5 to 1.2 times those in the initially prepared electroplating
bath, respectively, and adjusting the concentration of the
conducting agent in the electroplating bath after the replenishment
of the first replenishment solution to a level of 70 to 95% of a
saturated concentration thereof.
[0017] The electroplating bath, to which the invention is directed,
should be one which exhibits high throwing power and includes at
least one metal (nickel series metal) ion selected from those of
nickel, cobalt and iron, a buffering agent and a conducting agent.
Preferably, the bath further includes, aside from the components
mentioned above, a halide ion and/or an organic brightener.
[0018] The metal (nickel series metal) ion can be contained in the
electroplating bath by use of a water-soluble salt of a nickel
series metal such as nickel, cobalt or iron. Examples of the
water-soluble salts include sulfates, sulfamates, and halides such
as chlorides, bromides and the like. Specific examples include
sulfates such as nickel sulfate, ferrous sulfate, cobalt sulfate
and the like, sulfamates such as nickel sulfamate, ferrous
sulfamate, cobalt sulfamate and the like, and halides such as
nickel bromide, nickel chloride, ferrous chloride, cobalt chloride
and the like. Of these, sulfates such as nickel sulfate, ferrous
sulfate, cobalt sulfate and the like and sulfamates such as nickel
sulfamate, ferrous sulfamate, cobalt sulfamate and the like are
preferred. These water-soluble nickel series metal salts should
preferably be used at a concentration of 5 to 400 g/liter, more
preferably from 5 to 200 g/liter. It will be noted that when a
halide is used as a water-soluble nickel series metal salt, part of
all of such a halide ion as described hereinafter may be
simultaneously contained in the electroplating solution.
[0019] The electroplating bath containing such a water-soluble
nickel series metal salt contains an ion of the nickel series
metal. For the nickel series metal ion, a nickel ion, cobalt ion or
iron ion may be contained singly or in combination of two or more.
It is preferred that the concentration of the nickel series metal
ion in the electroplating bath is within a range of 1 to 20
g/liter.
[0020] For a buffering agent, examples include organic acids such
as malic acid, succinic acid, acetic acid, tartaric acid, ascorbic
acid, citric acid, lactic acid, pyruvic acid, propionic acid,
formic acid and the like, salts of these organic acids, amine
compounds such as ethylenediamine, triethanolamine, ethanolamine
and the like, boric acid, and the like. These may be used singly or
in combination. Preferably, boric acid, citric acid or salts
thereof are used. The concentration of the buffering agent in the
electroplating bath is within a range of from 10 to 100 g/liter,
preferably from 20 to 80 g/liter.
[0021] The conducting agent is added separately from the
above-mentioned water-soluble metal salt and the buffering agent.
For the conducting agent, a water-soluble salt of a metal selected
from alkali metals, alkaline earth metals and aluminum is
preferred. Examples include halides of alkali metals, alkaline
earth metals or aluminum, e.g. chlorides such as lithium chloride,
sodium chloride, potassium chloride, magnesium chloride, aluminum
chloride and the like, and bromides such as sodium bromide,
potassium bromide, magnesium bromide, aluminum bromide and the
like. In addition, there are favorably used sulfates such as
lithium sulfate, sodium sulfate, potassium sulfate, magnesium
sulfate, aluminum sulfate and the like, methanesulfonates such as
sodium methanesulfonate, potassium methanesulfonate and the like.
These may be used singly or in combination of two or more. Where it
is desired to obtain a plated film whose color tone is excellent,
it is preferred to use sulfates such as lithium sulfate, sodium
sulfate, potassium sulfate, magnesium sulfate, aluminum sulfate and
the like, sulfamates such as sodium sulfamate, potassium sulfamate
and the like, and methanesulfonates such as sodium
methanesulfonate, potassium methanesulfonate and the like.
[0022] The concentration of the conducting agent contained in an
initially prepared electroplating bath is within a range of from 70
to 95%, preferably from 80 to 90%, of a saturated concentration at
a plating temperature. If the concentration is smaller than 70%,
high throwing power cannot be kept. Over 95%, when the
concentration of the conducting agent in a first replenishment
solution described hereinafter is high, a precipitate or crystals
are liable to occur in the electroplating bath upon replenishment
of the conducting agent. It will be noted that where a halide is
used as a conducting agent, part or all of a halide described
hereinafter may be simultaneously contained in the electroplating
bath.
[0023] With respect to a halide ion, where a halide of a nickel
series metal is used as a water-soluble nickel series metal salt or
a halide is used as a conducting agent, such a halide yields a
halide ion in the electroplating bath, so that the electroplating
bath eventually contains the halide ion. On the other hand, where
no halide ion is yielded in the electroplating bath from a
water-soluble nickel series metal salt or conducting agent, an
anode-dissolving agent that is made of a halide salt may be added
to so as to contain a halide ion in the bath. It is to be noted
that even when a nickel series metal halide is used as a
water-soluble nickel series metal salt or a halide is used as a
conducting agent, an anode-dissolving agent may be added.
[0024] For the anode-dissolving agent, there can be used halides of
alkali metals, alkaline earth metals or aluminum including
chlorides such as lithium chloride, sodium chloride, potassium
chloride, magnesium chloride, aluminum chloride and the like, and
bromides such as sodium bromide, potassium bromide, magnesium
bromide, aluminum bromide and the like.
[0025] It should be noted that the concentration of a halide in the
electroplating bath is within a range of from 5 to 150 g/liters,
preferably from 10 to 100 g/liter, as including those ions derived
from a water-soluble nickel series salt or a conducting agent.
[0026] Moreover, if necessary, surface active agents such as an
anionic surface active agent may added. Further, organic
brighteners such as saccharin, sodium naphthalenedisulfonate,
sodium naphthalenesulfonate, sodium allyl sulfonate, butynediol,
propargyl alcohol, coumarin, formalin and the like may be added to
the electroplating bath. Each may be contained in an amount of 0.01
to 0.5 g/liter.
[0027] In the practice of the invention, the electroplating bath
should preferably be acidic in nature, with the pH being within a
range of from 2 to 6, preferably from 3 to 5.
[0028] The electroplating bath containing such a nickel series
metal, a buffering agent, a conducting agent and a halide ion as
set out hereinabove permits high throwing power. For instance, it
is preferred that when measurement is carried out using a Haring
cell at a distance ratio between two cathode plates and an anode
plate, the throwing power (T) represented by the following equation
is 35% or over
T(%)=[(P-M)/(P+M-2)].times.100
wherein T is throwing power, P is at 5 (distance ratio between the
anode and the cathode) and M is a ratio by weight of a plated film
deposited on two cathodes.
[0029] In the present invention, using a soluble anode, e.g. an
anode made of nickel, cobalt, iron or an alloy thereof, a cycle of
electroplating a substrate for plating is repeated, for example, at
a cathode current density of 0.01 to 5 A/dm.sup.2 at a plating
temperature of 10 to 70.degree. C., if necessary, while agitating
appropriately by a known method. During the electroplating, a
buffering agent and a conducting agent reduced in amount by the
repetition of the plating in the electroplating bath are,
respectively, replenished by adding, to the electroplating bath, a
first replenishment solution that contains a buffering agent and a
conducting agent at concentrations of 0.5 to 1.2 times those in an
initially prepared electroplating solution, respectively, and is
free of a nickel series metal ion.
[0030] As mentioned above, the first replenishment solution
contains the buffering agent and the conducting agent at 0.5 to 1.2
times, preferably 0.8 to 1.05 times, the concentrations of the
agents in the initially prepared electroplating bath and is free of
a nickel series metal ion. Since this first replenishment solution
is free of a nickel series metal ion, a nickel series metal in the
electroplating bath is not increased at all by the supply of the
replenishment solution. This makes it possible to suppress a
lowering of the throwing power to an extent as small as possible as
would otherwise occur by an increase in concentration of the nickel
series metal ion in the electroplating solution. If the
concentration is smaller than 0.5 times the concentration of the
initially prepared electroplating bath, the feed of the
replenishment solution increases, resulting in much labor for
concentration of water such as by evaporation. In contrast, when
the concentration exceeds 1.2 times the concentration of the
initially prepared electroplating bath, a precipitate or crystals
are liable to occur when a replenishment solution is supplied to
the electroplating solution. It will be noted that the times for
the concentration of a buffering agent should preferably be the
same as the times for the concentration of a conducting agent.
[0031] Specific examples of these buffering and conducting agents
are those as exemplified with respect to the initially prepared
electroplating bath. Especially, it is preferred to use the same
agents as those used in the initially prepared electroplating bath,
respectively.
[0032] If a halide ion is contained in an initially prepared
electroplating bath, a halide ion is preferably added to the first
replenishment solution. In this connection, the concentration of
the halide ion is within a range of from 0.5 to 1.2 times,
preferably from 0.8 to 1.05 times, the concentration in the
initially prepared electroplating bath. Especially, the times for
this concentration are preferably the same as the times for the
concentration of a conducting agent.
[0033] It will be noted that the halide ion can be added to the
first replenishment solution by adding a halide as such a
conducting agent as set out above and/or a halide as a conducting
agent, and where a water-soluble nickel series metal halide is used
as a supply source of a nickel series metal ion at the initial time
of preparation of an electroplating bath, a halide serving as a
conducting agent and/or a halide serving as an anode dissolving
agent is added in a given amount in place of a water-soluble nickel
series metal halide, thereby permitting the halide ion to be set at
a concentration thereof, to which an amount of the halide ion
derived from the water-soluble nickel series metal salt in the
initially prepared electroplating bath is added, without addition
of a nickel series metal ion. Specific examples of the halide
serving as a conducting agent and the halide serving as a
conducting agent are those indicated as contained in the initially
prepared electroplating bath, and it is preferred to use the same
halide as used in the initial electroplating bath.
[0034] Where an organic brightener is contained in the initially
prepared electroplating bath, it is preferred to add an organic
brightener to the first replenishment solution. In this case, the
concentration of the organic brightener can be at a level of from
0.5 to 1.2 times, preferably, from 0.8 to 1.05 times, the
concentration in the initial electroplating bath. More preferably,
the times for the concentration are the same as those of the
conducting agent. For the organic brightener, mention is made of
those exemplified as contained in the initial electroplating bath.
It is preferred to use the same material as contained in the
initial electroplating bath.
[0035] Without replenishing an organic brightener by addition to
the first replenishment solution for supply to an electroplating
bath, separate replenishment of an organic brightener is possible
by use of a second replenishment solution containing an organic
brightener alone at a concentration of 20 to 2,000 times,
preferably 50 to 1,000 times, the concentration in the initial
electroplating bath.
[0036] This is for the reason that although the buffering agent,
conducting agent and halide ion are reduced in amount mainly by
"drag-out" the organic brightener is reduced not only by
"drag-out", but also by entrainment in a plated film and partial
removal with a filter, so that there is some case where it is
preferred to supply the brightener separately from the buffering
agent, conducting agent and halide ion.
[0037] If an amount of a nickel series metal ion reduced by
"drag-out" is large with a shortage of the nickel series metal ion,
a third replenishment solution containing a nickel series metal ion
can be added. For the third replenishment solution, there can be
used, for example, a solution that contains such a water-soluble
nickel series metal salt as set out hereinabove and, if necessary,
an acid or alkali added for adjustment of pH. Examples of the
water-soluble nickel series metal salts are those exemplified as
contained in an initially prepared electroplating bath. Preferably,
those other than halides such as, for example, sulfates, sulfamates
and the like are preferred. It will be noted that the concentration
of a nickel series metal ion in the third replenishment solution
should preferably be within a range of 40 to 100 g/liter.
[0038] The pH values of the first, second and third replenishment
solutions are each from 2 to 6, preferably from 3 to 5.
[0039] The replenishment solutions may be replenished to an
electroplating bath in a plating tank where reduced such as by
"drag-out". The replenishment solutions can be properly selected
depending on the following standards. More particularly, when an
increase in amount (I.sub.M) at a given unit (time) and a reduction
in amount (D.sub.M) of a metal caused such as by "drag-out" at the
given unit (time), both of which are caused by a difference between
a cathode current efficiency and an anode current efficiency, is
such that I.sub.M.ltoreq.D.sub.M, the first replenishment solution
alone or the first and second replenishment solutions are used, and
if I.sub.M<D.sub.M, the first and third replenishment solutions
or the first, second and third solutions are used.
[0040] The amounts of the replenishment solutions may be determined
according to any of methods including (1) a method wherein the
concentrations of a nickel series metal ion, a buffering agent, a
conducting agent, a halide ion, and, if necessary, an organic
brightener in the electroplating bath after repetition of the
plating are periodically analyzed at every given unit (time or the
like) prior to supply, thereby determining the amounts depending on
the results of the analysis, and (2) a method wherein an increase
or decrease in concentration of individual components in the
electroplating bath is measured, for example, according to a line
test (real machine test) and variations of the components are used
to determine the amounts at every given unit (time or the like).
The given unit (time) is preferably within a range of 1 to 200
hours.
[0041] The concentration of a conducting agent in the
electroplating bath after replenishment of the replenishment
solution or solutions is adjusted to a level of 70 to 95% of a
saturated concentration thereof. In case where the concentration of
a conducting agent in the electroplating bath after replenishment
of the replenishment solution is within such a range as indicated
above only by replenishment of the replenishment solution,
electroplating can be carried out in a condition of the bath where
the replenishment solution is replenished. If, however, such a
range as indicated above is not met in a condition of replenishing
a replenishment solution, the concentration is adjusted to be
within such a range as indicated above by addition of water or by
removal of water through evaporation.
EXAMPLES
[0042] Examples and Comparative Examples are shown to particularly
illustrate the invention, which should not be construed as limiting
to the following examples.
Example 1
[0043] 1000 liters of electroplating bath A indicated in Table 1
was placed in a plating tank, and a substrate for plating having a
plating surface of 100 dm.sup.2 was placed in the electroplating
bath, under which plating operations were repeated under conditions
of 55.degree. C. and 1 A/dm.sup.2 for 20 minutes while sucking air
in the vicinity of the bath solution surface.
[0044] In every 12 hours (upon 36 repetition cycles of plating),
water was added to the electroplating bath to adjust the volume of
the electroplating bath to 1000 liters and concentrations of a
nickel ion and sodium sulfate were, respectively, measured
according to a hydrometric method. Because the concentration of the
nickel ion increased over the case where the bath was initially
prepared, replenishment solution A indicated in Table was not used
but replenishment solution B was replenished in such a way that a
total amount of sodium sulfate was same as at the time of initial
preparation of the bath and water was evaporated to return the
volume of the electroplating bath to 1000 liters, followed by
re-starting the plating. The results of evaluation of throwing
power and outer appearance of plated films obtained after
repetition cycles of 500, 1,000, 1,500, 2,000, 2,500 and 3,000 are
shown in Table 3. The evaluation methods are set out below.
[0045] Throwing Power
[0046] The plating bath was transferred to a Haring cell and
measurement was carried out at a distance ratio between two cathode
plates and an anode plate, under which the case where throwing
power (T) represented by the following equation is not lower than
35% or over is evaluated as "good" and the case where the
uniformity is smaller than 35% is evaluated as "bad".
T(%)=[(P-M)/(P+M-2)].times.100
wherein T is throwing power, P is at 5 (distance ratio between the
anode and the cathode) and M is a ratio by weight of a plated film
deposited on two cathodes.
[0047] Film Appearance
[0048] The resulting plated film was visually observed whereupon
the case where a plated appearance in the Hull cell test (capable
of observing from a high current density portion to a low current
density portion) is uniform without involving a considerable degree
of appearance irregularity is evaluated as "good" and the case
where the appearance is non-uniform and irregular with respect to
the plated appearance is as "bad".
Comparative Example 1
[0049] The electroplating was repeated in the same manner as in
Example 1 except that replenishment solution C indicated in Table 2
was used in place of replenishment solution B and the throwing
power of the resulting plated films in all the cycles was evaluated
along with the plated film appearance. The results are shown in
Table 3.
Comparative Example 2
[0050] The electroplating was repeated in the same manner as in
Example 1 except that replenishment solution D indicated in Table 2
was used in place of replenishment solution B and the throwing
power of the resulting plated films in all the cycles was evaluated
along with the plated film appearance. The results are shown in
Table 3.
Example 2
[0051] The electroplating was repeated in the same manner as in
Example 1 except that replenishment solution E indicated in Table 2
was used in place of replenishment solution B and the throwing
power of the resulting plated films in all the cycles was evaluated
along with the plated film appearance. The results are shown in
Table 3.
Comparative Example 3
[0052] Replenishment solution F indicated in Table 2 was
replenished in place of replenishment solution B, but the
replenishment solution could not be replenished at one time in such
a way that a total amount of sodium sulfate was the same as that at
the time of initial preparation of the bath.
Test Example 1
[0053] 1,000 liters of electroplating bath B indicated in Table 1
was placed in a plating tank, into which a substrate for plating
having a plating surface of 100 dm.sup.2 was placed and plating
operations were repeated under conditions of 55.degree. C. and 1
AS/dm.sup.2 for 20 minutes while sucking air in the vicinity of a
plating bath surface.
[0054] Water was added to the electroplating bath, with which
plating was repeated 50 cycles, in order to adjust the volume of
the electroplating bath to 1,000 liters. Thereafter, the
concentration of sodium sulfate was measured according to a
hydrometric method. Replenishment solution B was replenished such
that a total amount of sodium sulfate was the same as at the time
of initial preparation of the bath, and no crystal were found in
the electroplating bath.
Test Example 2
[0055] The replenishment solution was replenished in the same
manner as in Test Example 1 except that replenishment solution E
indicated in Table 2 was used in place of replenishment solution B,
revealing that no crystals were found in the electroplating
bath.
Test Example 3
[0056] The replenishment solution was replenished in the same
manner as in Test Example 1 except that replenishment solution G
indicated in Table 2 was used in place of replenishment solution B,
revealing that crystals were found in the electroplating bath.
TABLE-US-00001 TABLE 1 Electroplating bath A Electroplating bath B
Nickel sulfate hexahydrate 54 g/liter 54 g/liter (as Ni) (12
g/liter) (12 g/liter) Sodium sulfate anhydride 285 g/liter 335
g/liter (ratio to a saturation at 55.degree. C.) (80%) (95%) Boric
acid 45 g/liter 45 g/liter Sodium chloride (as Cl ion) (11 g/liter)
(11 g/liter) Anionic surface active agent 0.05 g/liter 0.05 g/liter
pH 4.2 4.2
TABLE-US-00002 TABLE 2 Replenishment solution A B C D E F G
Concentration ratio -- 1 1 1.5 0.7 0.3 -- Nickel sulfate
hexahydrate 360 -- 54 -- -- 16 65 (g/liter) Sodium sulfate
anhydride -- 285 285 428 200 86 342 (g/liter) Boric acid -- 45 45
67.5 31.5 13.5 54 (g/liter) Sodium chloride (as Cl ion) -- 11 11
16.5 7.7 3.3 13.2 (g/liter) Anionic surface active agent -- 0.05
0.05 0.075 0.035 0.015 0.06 (g/liter) pH 3.8 3.8 3.8 3.8 3.8 3.8
3.8
TABLE-US-00003 TABLE 3 Plating cycles 500 1,000 1,500 2,000 2,500
3,000 Example 1 Throwing good good good good good good power
Appearance of good good good good good good plated film Comparative
Throwing good bad bad bad bad bad Example 1 power Appearance of
good good good good good good plated film Comparative Throwing good
good bad bad bad bad Example 2 power Appearance of bad bad bad bad
bad bad plated film Example 2 Throwing good good good good good
good power Appearance of good good good good good good plated
film
[0057] Japanese Patent Application No. 2006-085043 is incorporated
herein by reference.
[0058] Although some preferred embodiments have been described,
many modifications and variations may be made thereto in light of
the above teachings. It is therefore to be understood that the
invention may be practiced otherwise than as specifically described
without departing from the scope of the appended claims.
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