U.S. patent number 3,716,464 [Application Number 04/889,106] was granted by the patent office on 1973-02-13 for method for electrodepositing of alloy film of a given composition from a given solution.
This patent grant is currently assigned to International Business Machines Corporation. Invention is credited to Zlata Kovac, Judith D. Olsen.
United States Patent |
3,716,464 |
Kovac , et al. |
February 13, 1973 |
METHOD FOR ELECTRODEPOSITING OF ALLOY FILM OF A GIVEN COMPOSITION
FROM A GIVEN SOLUTION
Abstract
The effect of superimposing a sinusoidal alternating current on
a direct current during electrodeposition of Ni--Fe alloys is
disclosed in terms of the following factors: (a) maintaining the pH
at the electrode equal to that of the bulk electrolyte; (b) ionic
diffusion processes; and (c) chemical processes in solution prior
to electrochemical reduction. The effect of frequency, amplitude
and the rate of a-c current to d-c current on the composition of
electrodeposited alloy are given for acid solutions of different pH
and for alkaline solutions of metallic complexes with a variable
concentration of complexing agent. It is shown that by proper
choice of conditions, electrodeposited Fe--Ni alloys can be
prepared with a desired uniform composition throughout their
thickness. In the practice of this disclosure, alternating current
is superimposed on direct current to prevent the pH in the layer of
solution adjacent to the electrode from increasing and thus
influence the electrodeposition of iron group metals or alloys of
any metals which readily form hydroxide. Formation of hydroxides is
thus prevented and their inclusion into deposited film is
precluded. Additionally, the a-c current beneficially affects the
rate of deposition of a metal which is controlled by diffusion.
There is no concentration gradient of composition across the
thickness of a film of Ni-Fe deposited by practice of this
disclosure. Illustratively, Ni and Fe plate out at the same rate
for thickness of film approximately in the range of 300A. to
4,000A. By control of the density of the d-c current, and the
amplitude and frequency of the a-c current, Ni-Fe film of any given
composition approximately in the range of 6 to 60 percent Fe is
electroplated from the same solution.
Inventors: |
Kovac; Zlata (Pittsburgh,
PA), Olsen; Judith D. (Mount Kisco, NY) |
Assignee: |
International Business Machines
Corporation (Armonk, NY)
|
Family
ID: |
25394514 |
Appl.
No.: |
04/889,106 |
Filed: |
December 30, 1969 |
Current U.S.
Class: |
205/259; 205/255;
204/DIG.9 |
Current CPC
Class: |
C25D
5/18 (20130101); C25D 15/02 (20130101); C25D
21/12 (20130101); C25D 3/562 (20130101); Y10S
204/09 (20130101) |
Current International
Class: |
C25D
15/00 (20060101); C25D 5/00 (20060101); C25D
5/18 (20060101); C25D 15/02 (20060101); C25D
3/56 (20060101); C25D 21/12 (20060101); C23b
005/32 () |
Field of
Search: |
;204/DIG.9,43,44,231,228
;340/174TF |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
The Electrochemical Soc., Extended Abstracts of Battery Div., Vol.
13, Abstract No. 487, (1968)..
|
Primary Examiner: Kaplan; G. L.
Claims
What is claimed is:
1. Method of electrodepositing a Fe-Ni alloy film with a given
composition from an electroplating solution having a given pH, a
first concentration of a given metal Fe and a second concentration
of a given alloying agent Ni comprising the steps of:
establishing an electroplating solution wherein the concentration
of a given metal Fe therein is a first given molar and the
concentration of a given alloying agent Ni therein is a second
given molar and the concentration of said metal and said alloying
agent is a third given molar, and the pH of said solution is a
given value, said first, second and third given molars and said pH
being in a given relationship to said concentrations of said metal
and said alloying agent in said solution; said solution is acid,
said solution includes a tartrate as a complexing agent for said
metal, said first given molar concentration of said Fe is
approximately in the range of 10.sup..sup.-3 to 10.sup..sup.-2 ,
said second given molar concentration of said Ni is approximately
in the range of 10.sup..sup.-2 to 10.sup..sup.-1 and said third
molar concentration of said Fe and said Ni is approximately in the
range of 10.sup..sup.-1 to 10.sup..sup.-2 ;
applying a direct current to said electroplating solution having a
given cathodic value;
applying an alternating current to said electroplating
solution;
establishing the peak value of said alternating current in a given
relationship to said given cathodic value of said direct current
such that the oxidation of cathodically adsorbed hydrogen is the
main anodic reaction of said electroplating solution;
said electroplating solution having an electrodeposition
characteristic of percentage of said alloying agent deposited
cathodically from said solution versus frequency of said applied
alternating current exhibiting
a given slope in a first portion over a given low range of
frequencies,
a slope greater than said given slope in a second portion over a
middle range of higher frequencies, and
a slope less than said greater slope in a third portion over a
still higher range of frequencies; an
depositing a given composition of said electrodeposited film by
establishing the frequency of said applied alternating current at a
value in said middle range of higher frequencies of said
characteristic.
2. Method as set forth in claim 1 wherein Fe-Ni film is 20-80
weight percent composition.
3. Method as set forth in claim 2 wherein said frequency is
approximately in the range of 20 Hz to 100 Hz.
4. Method as set forth in claim 2 wherein said frequency is
established in the range of approximately 60 Hz to 100 Hz and said
temperature is established in the range of approximately
25.degree.C to 40.degree.C.
5. Method as set forth in claim 1 wherein said Fe-Ni alloy film has
weight percent composition of Fe/Ni of 20/80 and said solution has
molar concentration of said Fe to molar concentration of said Ni
approximately in the range of 20/80 to 5/95.
6. Method as set forth in claim 1 wherein said solution
includes
NiSO.sub.4 .sup.. 6H.sub.2 O = 6.3 g/l,
FeSO.sub.4 .sup.. 7H.sub.2 O = 1.7 g/l,
NaK-tartrate = 10.0 g/l;
said pH = 3.0 at approximately 25.degree.C;
said direct current = I.sub.d-c = 2 ma/cm.sup.2 ;
said peak value of said alternating current = I.sub.p = 13.7
ma/cm.sup.2 ;
and said frequency of said alternating current = f = 25 Hz;
whereby the rate of deposition of said alloy film=Rate=22A/min.
7. Method as set forth in claim 1 wherein said solution
includes
NiSO.sub.4 .sup.. 6H.sub.2 O = 30.0 g/l,
FeSO.sub.4 .sup.. 7H.sub.2 O = 1.7 g/l,
NaK tartrate = 10.0 g/l;
said pH = 3.0 at approximately 25.degree.C;
said direct current = I.sub.d-c = 2 ma/cm.sup.2 ;
said peak value of said alternating current = I.sub.p = 13.7
ma/cm.sup.2 ;
and said frequency of said alternating current = f = 100 Hz;
whereby the rate of deposition of said alloy
film=Rate=125A/min.
8. Method as set forth in claim 1 wherein said deposited film has a
varying composition profile with thickness and there is included
the step of varying the frequency of said alternating current in
relationship to said profile.
Description
BACKGROUND OF THE INVENTION
Magnetic thin film structures fabricated for computer memory
applications are usually formed of Ni-Fe alloys which are prepared
by vacuum evaporation techniques. Because of the inherent
simplicity of electroplating as a manufacturing technique,
attention has been directed to the application thereof to the
fabrication of magnetic thin films. A severe problem in plating
Ni-Fe magnetic films results when a plating current is initially
applied to a Ni-Fe bath. The initial deposit is very rich in iron
content and thereafter decreases in iron content until an
equilibrium condition is reached and the alloy having the desired
proportion of nickel and iron is plated. Since it is only in the
initial layers plated that this variance in the proportions of
nickel and iron is produced, usually the principal variance is
produced within the first 500A. of film deposited. Therefore, this
problem has not been too severe when the plated film is very thick.
When the final film is to have a thickness of about 1,000A. or
less, and the films are to be used in computer memories, which
demand constant magnetic characteristics across the entire film,
this initial iron rich deposit becomes a severe problem. This is
especially so in terms of the magnetostriction of the deposited
alloy, since zero magnetostriction is achieved with alloys
including approximately 80 percent Ni and 20 percent Fe. When the
alloy varies by any considerable degree from these proportions, it
does not exhibit zero magnetostriction.
Electrodeposition of Ni-Fe alloys is accompanied by considerable
hydrogen evolution which gives rise to alkalization in the vicinity
of an electrode with subsequent formation of metallic hydroxides.
Consequently, there is preferential deposition of Fe with the
characteristics: (a) gradient in composition across film thickness
up to approximately 1,000A.; (b) nonuniformity in composition in
the plane of the film; and (c) inclusions in the films. In
addition, the ratio of the metals in the deposit is not the same as
the ratio of metal ions in the solution.
Ni-Fe films for memory application with thickness in the range of
approximately 1,000A. to 1,200A. must satisfy stringent
requirements in uniformity of both composition and physical
properties. In the prior art, copending patent application Ser. No.
601,951 by J. M. Brownlow et al. filed Dec. 15, 1966, now
abandoned, and commonly assigned, discloses use of specially shaped
current pulses for satisfying these stringent requirements. In
greater detail, the noted copending application by J. M. Brownlow
et al. discloses that a shaped continuous current or a series of
shaped current pulses are applied to effect the plating. The
magnitude of the plating current, or of each of the plating current
pulses, is initially significantly higher than that required to
plate the desired alloy under equilibrium conditions in the bath.
The current, or each current pulse, is thereafter decreased with
time, preferably in inverse proportion to the square root of time,
to provide films with uniform proportions of Ni and Fe throughout
the film thickness.
Alternating current is known to have a significant influence on
many electrode processes and it has been used in such
electrochemical investigations as: (a) the study of electrical
double layers as reported in the articles by Wien, Ann. Phys. Lpz.,
Vol. 58, page 815 (1896); D. C. Graham, J.Amer.Chem.Soc., Vol. 63,
page 1207 (1941) and Vol. 68, page 301 (1946); and M. A. Proskurin
et al., Trans. Faraday Soc., Vol. 31, page 110 (1935); (b) the
kinetics of the formation and dissolution of oxide films as
reported in the article by B. V. Ershler, Trans. 2nd Meeting on
Metal Corrosion, Acad. Sci., U.R.S.S., Vol. 2, Page 52 (1943); (c)
fast electrode reactions as reported in the articles by P. I. Dolin
et al., Acta Physicochim., Vol. 13, page 747 (1940); and J. E. B.
Randles, Disc. Faraday Soc., Vol. 1, page 11 (1947); and (d) in the
electrodeposition and dissolution of metals as reported in the
articles by A. T. Vagramyan et al., "Technology of
Electrodeposition", Robert Draper Ltd. Teddington Page 95, (1961);
and K. M. Gorbunova et al., J. Phys. Chem., 3, 542 (1955).
Further, A. T. Vagramyan et al. reported in Izv. A. N. SSSR, Otd.
Khim Nauk, Vol. 3, Page 410 (1952) that alternating current can
effect the grain size, brightness and porosity of electrodeposited
metals; V. J. Marchese reported in the article J. Electrochem.
Soc., Vol. 99, page (195239 (1952) that the superposition of a-c
current on d-c current reduces internal stresses in
electrodeposited nickel; and V. S. Pat. No. 2,619,454 issued Nov.
25, 1952 by P. P. Zapponi disclosed that the magnetic and
mechanical properties of electroplated Ni-Co films could be
improved by superimposing a-c current on d-c current during their
codeposition. However, it did not disclose any relationship or
critical dependence of any film properties on frequency of the
alternating current.
OBJECTS OF THE INVENTION
It is an object of this invention to provide a method for the
electrodeposition of alloy films which have uniform composition and
uniform physical properties as a function of thickness.
It is another object of this invention to provide a method for
obtaining alloy films of different composition from a plating bath
of constant composition in a controlled manner.
It is another object of this invention to provide a method for
matching the ratio of the metals in an electrodeposited alloy film
to the corresponding ratio of the metal ions in the plating
solution so that the ratio of the metal ions of the plating bath
does not change with time.
It is another object of this invention to provide a method for the
electrodeposition of alloy films by superimposing a-c current on
d-c current with the peak amplitude and frequency of the a-c
current being related to the pH of the electrodeposition
solution.
It is another object of this invention to provide a method for
plating alloy films from elements in a plating bath where the rate
of disposition of a first one of the elements to be plated is
limited by the diffusion rate of that element, and the rate of
deposition of the second element is limited by the rate of the
discharge of that element.
It is another object of this invention to provide a method for
plating alloy films from elements in a complexing plating bath
where the rate of disposition of a first one of the elements to be
plated is limited by a chemical reaction of that element in the
plating bath, and the rate of deposition of the second element is
limited by the discharge rate of that element.
It is another object of the present invention to provide a method
of electroplating Ni-Fe films which are uniform in their
proportions of nickel and iron throughout the thickness of the
films..
It is another object of this invention to provide a method of
electroplating magnetic films using alternating current which may
be successfully practiced with conventional plating baths to
produce uniform binary alloys of nickel and iron.
It is another object of this invention to provide a method of
plating Ni-Fe films for use in magnetic thin film memory
applications in which the plating current is controlled to overcome
the iron rich deposit which is usually produced when a direct
current is first applied to a conventional Ni-Fe bath.
SUMMARY OF THE INVENTION
If the rate of deposition of one of the components of an
electroplating solution having a given pH is under diffusion
control or if it is controlled by a chemical reaction between the
metal ion and its complexing agent in the electroplating solution,
this invention provides a method of electrodepositing an alloy
layer therefrom. There are in the solution a first concentration of
a given metal and a second concentration of a given alloying agent
and the layer is obtained by utilizing an applied alternating
current superimposed on an applied direct current. The steps of the
method of this invention for electrodeposition of Ni-Fe alloys
comprise:
a. establishing said electroplating solution such that the
concentration of the Fe metal is approximately in the range of
10.sup..sup.-3 to 10.sup..sup.-2 molar, the concentration of the Ni
alloying agent is approximately in the range of 10.sup..sup.-2 to
10.sup..sup.-1 molar and that the concentration of both the metal
and the alloying agent is approximately in the range of
10.sup..sup.-1 to 10.sup..sup.-2 molar, and that the pH thereof is
given in relationship to the given concentrations of the metal and
the alloying agent;
b. controlling the peak value excursions of the applied alternating
current in relationship to the value of the applied direct current
such that oxidation of the adsorbed hydrogen is the main anodic
reaction of the electroplating solution; and
c. fixing the frequency of the applied alternating current in
accordance with a plot of percentage of a component of the metallic
alloy deposited from the electroplating solution versus frequency
of the applied alternating current.
The plot of percentage of a component of the metallic alloy
deposited from the electroplating solution versus frequency of the
applied alternating current exhibits the following
characteristics:
a. substantially a constant value over a low range of
frequencies;
b. starting at a given point, an increasing percentage of deposit
of the component over a range of higher frequencies; and
c. after a second point is reached, a substantially constant value
over a high range of frequencies.
Generally, by superimposing a-c current on d-c current during the
electrodeposition of the alloys, the following results are obtained
by the practice of this invention:
1. The difference between the pH of solution at the surface of the
cathode and pH in the bulk of the solution can be maintained
approximately the same to limit hydroxide formation for iron group
metals, and also in all cases where metal ions are used which
readily form hydroxides, e.g., Zn, In, Cd.
2. The composition of an alloy electrodeposited from the same
solution can be varied in the approximate range of 6 to 60 percent
Fe by varying only the frequency.
3. The composition of an electrodeposited alloy film can be
maintained constant over a thickness range of approximately 400A to
4,000A.
4. the ratio of the concentration of the metal to the concentration
of the alloying constituent or agent in an electrodeposited alloy
film can be made to reflect exactly the ratio of the concentrations
of the respective ions in the solution.
Though the inventive method, as summarized above, is disclosed in
this application as being applied principally to the fabrication of
binary alloy films which include only nickel and iron, the
inventive method can be employed to prepare ternary Ni-Fe alloys.
Further, the Ni-Fe alloys, to which this method is principally
directed, are only one example of a rather broad class of alloys
which present similar problems when it is desired to plate a film
which is uniform in composition throughout its thickness.
The following and other objects, features and advantages of the
invention will be apparent from the following more particular
description of preferred embodiments of the invention, as
illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A presents a schematic diagram illustrating an electrical
arrangement for electrodeposition of an alloy film with combined
d-c and a-c currents.
FIG. 1B illustrates the net current curve for the electrical
arrangement of FIG. 1A.
FIG. 1C illustrates the net voltage curve for the electrical
arrangement of FIG. 1A.
FIG. 2 illustrates the Fe content and the rate of alloy deposition
as a function of log f in low Ni concentration solutions of pH =
3.0 and pH = 4.6 for (Fe/Ni).sub.sol = 20/80, with I.sub. 2
mA/cm.sup..sup.+2 and I.sub. p = .iota.13.7 mA/cm.sup..sup.+2.
FIG. 3 illustrates the Fe content and the rate of alloy deposition
as a function of log f in high Ni concentration solution of pH =
3.0 and 4.6 for (Fe/Ni).sub.sol = 5/95, I.sub.d-c = 2
mA/cm.sup..sup.+2 , I.sub. p = 13.75 mA/cm.sup..sup.+2.
FIG. 4 illustrates the Fe content and the rate of alloy deposition
in high Ni concentration solution of pH = 3.8 with I.sub.d-c of 2
mA/cm.sup..sup.+2 and 5 mA/cm.sup..sup.+2 and I.sub.a-c peak =
13.75 mA/cm.sup..sup.+2.
FIG. 5 illustrates the log of the direct current density versus
potential in high citrate solution of pH = 9.25.
FIG. 6 illustrates the Fe content and the rate of alloy deposition
as a function of log f with I.sub.d-c of 2 and 4 mA/cm.sup..sup.+2,
I.sub.a-c peak = 15 maA/cm.sup..sup.+2 and (Fe/Ni).sub.sol =
20/80.
FIG. 7 illustrates the Fe content and the rate of alloy deposition
in low citrate solution of pH = 9.25 (Fe/Ni).sub.sol = 20/80 with
I.sub.d-c of 2 and 4 mA/cm.sup..sup.+2, and I.sub.peak = 15
mA/cm.sup..sup.+2.
FIG. 8 illustrates the Fe content as a function of direct current
density for f = 0, 30 and 400 Hz with I.sub.peak = 13.75
mA/cm.sup..sup.+2, (Fe/Ni).sub.sol = 5/95, and pH = 3.8.
FIG. 9 illustrates the Fe content as a function of direct current
density for f = 0, 30 and 400 Hz in high citrate solution of pH =
9.25, and (Fe/Ni).sub.sol = 20/80 and I.sub.peak = 16.7
mA/cm.sup..sup.+2.
FIG. 10 illustrates the Fe content as a function of the amplitude
of a-c current in low Ni concentration, (Fe/Ni).sub.sol = 20/80 and
high Ni solution, (Fe/Ni).sub.sol = 5/95 for f = 20 and 100 Hz, and
pH = 4.6.
FIG. 11 illustrates the Fe content and the rate of alloy deposition
as a function of log f in high citrate solution, with I.sub.d-c = 2
mA/cm.sup..sup.+2, I.sub.peak = 15 mA/cm.sup..sup.+2 for T =
25.degree. C and 40.degree.C.
FIG. 12 illustrates the rate of alloy Ni-Fe deposition as a
function of .omega..sup..sup.-1/2 in low nickel solution,
(Fe/Ni).sub.sol = 20/80 and pH = 3,00, I.sub.d-c = 2
(mA/cm.sup..sup.+2, I.sub.peak = 13.75 mA/cm.sup..sup.+2.
FIG. 13 illustrates the rate of Fe deposition as a function of
.omega..sup..sup.-1/2 in high Ni solution, (fe/Ni).sub.sol = 5/95
at pH = 3, 38 and 4.6, I.sub.d-c = 2 mA/cm.sup..sup.+2, I.sub.peak
= 13.75 mA/cm.sup..sup.+2.
FIG. 14 illustrates the rate of Fe deposition as a function of
.omega..sup..sup.-1/2 at I.sub.d-c of 2 and 4 mA/cm.sup..sup.+2 in
low and high citrate solution.
FIG. 15 illustrates the rate of Ni deposition as a function of
.omega..sup..sup.-1/2 at 2 and 4 mA/cm.sup..sup.+2 in low and high
citrate solutions.
FIG. 16 illustrates the Fe content as a function of film thickness
in acid and alkaline solutions.
APPARATUS FOR THE INVENTION
Apparatus for electrodepositing an alloy film for the practice of
this invention is presented schematically in FIG. 1A and the net
current and voltage curves therefor are shown in FIGS. 1B and 1C,
respectively.
In FIG. 1A the electrolytic cell 10 consists of two compartments 12
and 14. The working compartment 12 includes a vessel 16 electrolyte
18, horizontal working electrode 20 masked on one surface with
insulating material 22, and a platinum mesh auxiliary electrode 24.
The working electrode 20 and auxiliary electrode 24 are connected
to the external electrical circuit 23 by means of conductors 21 and
25, respectively. The working compartment 12 is connected to the
reference compartment 14 by means of a Luggin capillary 26. The
reference compartment 14 includes an electrolyte 30 contained in a
vessel 28. The reference electrode 32 is saturated Calomel
Electrode suspended in electrolyte 30. Reference electrode 32 is
connected to the external electrical circuit 23 by conductor 33.
The electrical circuit 23 includes a d-c power supply 36 having
positive and negative terminals 38 and 40. A signal generator 42 is
provided to produce an a-c current which is superimposed on the d-c
current. A by-pass capacitor 43 connected between terminals 38 and
14 provides a path for the a-c current.
The negative terminal 40 of the d-c power supply 36 is connected to
the working electrode 20 through conductor 41, variable resistor
44, conductor 49 ampere meter 66, and conductor 21. The current
through the circuit as a function of time is monitored by dual-beam
oscilloscope 50 via terminals 54 and 55 which is connected across
the variable resistor 44 at connections 46 and 48. The potential on
the working electrode 20 with respect to the saturated Calomel
Electrode 32 is measured by volt-meter 62 which is monitored as a
function of time by oscilloscope 50 at connections 56 and 57.
Oscilloscope 50 presents trace 51 as function of time on tube face
52 of either the current measured by ampere-meter 66 or the voltage
measured by volt-meter 62 as selected.
THEORY OF THE INVENTION
The effect of a-c current of variable frequency and amplitude on
the composition and uniformity of electrodeposited Ni-Fe alloys
will now be considered. Cases 1, 2 and 3 will be examined for the
ways in which superimposed alternating current can affect the
electrodeposition process.
CASE 1
In Case 1 for some portion of each cycle, the a-c component
converts the electrode from cathode to anode as reported in the
article by A. Brenner, "Electrodeposition of Alloys", Vol. 1,
Academic Press, New York, Page 84 (1963 ).
During electrodeposition of most metals, discharge of H.sub.3
O.sup.+.sup.+ or H.sub.2 O occurs concurrently with pH changes in
the vicinity of the electrode surface. For metals with small
hydrolysis constants, this alkalization will be reflected in the
formation of metallic hydroxides, which subsequently can be
incorporated into the deposit, thus causing non-uniformity. In the
codeposition of two or more metals this phenomenon can cause
preferential deposition of one metal. Further, a concentration
gradient across the deposit thickness, which will be the most
pronounced in the first 500A, is reported in the article by H.
Dahms et al., J. Electrochem. Soc., Vol. 112, No. 8, 1965.
If a-c current is superimposed on d-c current during
electrodeposition of such metals, during the time for which the
electrode is the anode, oxidation of adsorbed hydrogen formed in
the cathodic cycle will take place according to the reaction:
H.sup.+ + e.sup.- .sub.anod. H .sub.ads
In the ideal case of balancing the rate of cathodic discharge of
H.sup.+ ions with its rates of oxidation and diffusion from
solution, control of pH can be achieved on the surface such that pH
(surface) .fwdarw. pH(bulk). Hence, the above-mentioned
difficulties should be minimized if not completely eliminated.
Mathematically, this presents a complex problem. However,
experimentally the condition can easily be found where there is no
preferential deposition of one of the metals and where there is no
composition gradient in the deposit; i.e., the condition of
constant pH.
Case 2
In Case 2 the current is controlled by ionic diffusion in the
electrolyte.
Passage of either direct or alternating current through an
electrolytic cell will produce concentration changes, which are
susceptible to mathematical treatment. Sand, as reported in the
article, Phil. Mag., Vol. 1, Page 45 (1901), solved the diffusion
equation for the case of electrolysis with a constant direct
current. Further, E. Warburg and F. Kruger solved the diffusion
equation for the case of sinusoidal alternating current as reported
in the respective articles Wied. Ann., Vol. 67, Page 493 (1899);
and J. Phys. Chem., Vol. 45, Page 1 (1903 ). Both treatments start
from Fick's second law:
.delta.c/.delta.t = D (.delta..sup.2 c)/(.delta.X.sup.2)
where c is the concentration of one ionic species, D is its
diffusion coefficient and x is the distance from the electrode into
the solution.
Both d-c and a-c currents have the same boundary conditions;
namely,
c.sub.x.sub.=0 = c.sub.x.sub.=.sub..infin. for t = 0
and
.delta.c/.delta.x = 0 for x .fwdarw. .infin. and t > 0
Here, C.sub.x.sub.=0 is the concentration at the electrode surface
and c.sub.x.sub.=.sub..infin. is the bulk concentration.
The solution of Equation 1 for constant d-c current is:
c.sub.(o,t) = c.sub..infin. -2i/nF .sqroot. t/.pi.D (2)
where i is the current density, t is time, n is the number of
electrons involved in the electrode reaction and F is Faraday's
constant. For steady state conditions
c.sub.0 - c.sub..infin. = - i.delta./nfD (3)
or
.DELTA.C = Ki.delta.
where .delta. is the thickness of the diffuse layer and K includes
all constant terms.
For sinusoidal a-c current the solution of Equation 1 is:
where I is the amplitude of the current density, and .omega. =
2.pi.f where f is the a-c current frequency.
At the electrode surface where x = 0, Equation 4 becomes
or
where A/.sqroot..omega. is the amplitude of concentration wave.
If both currents act simultaneously on the system, the net
concentration changes can be obtained by adding together the
concentration change that would be produced by each current taken
separately (since the sum of a number of solutions of a linear
differential equation is likewise a solution) as reported in the
article by T. R. Roseburg et al., J. Phys. Chem., Vol. 14, Page 816
(1910). Thus:
.delta.C = -[i.delta. + I .sqroot.D/.omega. sin (.omega.t - .pi./4]
/nFD 6
Consider electrodeposition of a binary alloy with one of the
depositable metal ions under diffusion control and the other under
charge transfer control. In such a case Equation 6 is applicable to
only one constituent of the alloy and the other constituent will be
deposited
as if the a-c current were not present, since a-c current does not
effect charge transfer reactions.
The conditions will now be examined under which a-c current and d-c
current have comparable affects on concentration change of Fe,
which is deposited under diffusion control. For a 10.sup..sup.-3 M
Fe solution and a total direct current density of 2
mA/cm.sup..sup.+2, the partial current for discharge of Fe is found
to be 0.32 mA/cm.sup..sup.+2, which from Equation 3 gives .delta.c
= 8.5 .times. 10.sup..sup.-6 m cm.sup.+.sup.3. . Consider I is
taken to be 15 mA/cm.sup..sup.+2, the amplitude of the
concentration wave from Equation 5 is 2.6 .times. 10.sup..sup.-6
and 0.37 .times. 10.sup..sup.-6 M cm.sup..sup.-3 for a frequency of
20 and 1,000 Hz, respectively; i.e., a-c current of low frequency
produces 30 percent and of high frequency produces 4 percent of the
total concentration change. If the d-c current is increased, the
affect of a-c current becomes even smaller (2 percent for 1,000 Hz
and I.sub.d.sub.-c of 4 mA/cm.sup..sup.+2). Clearly, the effect of
diffusion becomes progressively smaller with increasing frequency.
Theoretically, in accordance with Equation 5, the effect of a-c
current can be increased by increasing its amplitude. Practically,
it is not desirable to go too high into the anodic region, where
dissolution of the alloy and oxide formation can take place.
CASE 3
In Case 3 deposition at the electrode is preceded by a chemical
reaction in the solution.
If electrodeposition is carried out from a solution of complex
ions, a reduction to the metallic state can take place either
directly from the complex ion or this electrochemical step can be
preceded by a chemical step or several steps in series.
If electrochemical reduction is preceded by a homogeneous chemical
reaction of a type
(z.sub.1 +z.sub.2) k.sub.f z.sub.1 z.sub.2
M.sub.m C.sub.n mM + nC
then the rate of formation of the metallic ions is
v = k.sub.f C.sub.MC - k.sub.b (c.sub.M).sup.m (c.sub.C).sup.n
(7)
where k.sub.f is the rate constant for dissociation of the complex
and k.sub.b the rate constant for the recombination, and c.sub.MC,
c.sub.M, c.sub.C are the concentrations of metallic complex, metal
ion and complexing agent, respectively. Equation (7) can be written
as
v = v.sub.o - kc.sub.M.sup.p (8)
where v.sub.o is the reaction exchange rate, k = k.sub.b c.sub.C is
the reaction rate constant, and p is the reaction order.
As a result of diffusion and chemical reaction the change of
concentration with time and distance at the surface of electrode
can be represented by Fick's second law in extended form:
(.delta.c)/(.delta.t) = D(.delta..sup.2 c)/(.delta.x.sup.2) + v
Equation 9 applies to both direct and alternating currents. The
direct current due to the deposition of metal with a slow chemical
step and p = 1 is:
where c.sub.M is equilibrium concentration of metal ions determined
by c.sub.M = Kc.sub.MC /c.sub.C, K being the stability constant for
a given complex, as reported by H. Gerescher et al., Z Physik
Chem., Vol. 197, Page 92 (1951). When the concentration of metal
ions at the surface, c.sub.s, becomes zero, a limiting reaction
current i.sub.r is reached, given by
i.sub.r = - nF .sqroot.v.sub.o c.sub.M D (11)
and from its value v.sub.o and k can be calculated (since at
equilibrium v = 0 and v.sub.o becomes equal to k.sup.. c.sub.M).
The reaction exchange rate is also related to the thickness of the
reaction layer, .delta..sub.i, by the following equation:
.delta..sub.i = .sqroot.Dc.sub.M /v.sub.o (12)
Passage of a-c through a system where chemical reaction occurs
prior to charge transfer will produce concentration changes which
depend not only on .omega..sup.-.sup.1/2 but also on k.
K. J. Vetter, as reported in the book "Electrochemical Kinetics",
Academic Press, New York, Page 253 (1967), gives the concentration
change as a difference of ohmic and capacitive components of the
electrolyte, both of which are function of .omega..sup.-.sup.1/2
and k/.omega.. The concentration wavelength as well as penetration
depth are also dependent upon the same parameters. This derivation
is valid only for very small differences between c.sub.M and
c.sub.s. Further, the a-c and d-c solutions of the differential
equation cannot be added in this case, since the differential
equation is non-linear. Therefore, quantitative treatment has not
been attempted. Qualitatively, it is expected that at a low
frequency the concentration wave will be able to follow the slowly
varying current, and that the penetration depth would be of the
same length as d-c reaction layer thickness. At higher frequencies,
the formation and decomposition of metal complexes will be
increasingly less important, since they cannot follow fast changes
of current. In addition the penetration depth of the concentration
wave will become smaller. For both these reasons, it is to be
expected that at high frequencies the d-c current behavior will
dominate.
When two or more metallic complexes are present in the system, a-c
current will affect them differently depending upon the value of
k/.omega.for each complex. Hence, in accordance with the principles
of this invention, by superimposing a-c current on d-c current, the
deposition kinetics of alloys can be affected in a practical
way.
PRACTICE OF THE INVENTION
Measurements were performed with two compartment cells as shown in
FIG. 1A. The cathode 20 was Cu-sheet or evaporated Ag on glass (2
.times. 2 cm), placed horizontally in one compartment 12 of the
cell. The back of the electrode was masked by mask 22 so that
electrodeposition was carried out on one side only. A Pt-mesh
auxiliary electrode 24 was placed approximately 2 cm above the
working electrode 20. The reference containing electrode 9
compartment 14 saturated Calomel electrode was connected with the
main compartment 12 through a Luggin capillary 26 carefully bent to
avoid any shielding effect.
The conventional electrical circuit is shown in FIG. 1A. Current
time and potential time curves, FIGS. 1B and 1C, respectively, were
simultaneously recorded on a dual-beam oscilloscope 50. It is
important that the potential is recorded, since this provides a way
of determining the conditions under which the oxidation of hydrogen
takes place by an electrochemical mechanism which minimizes
dissolution of alloy and avoids its oxidation.
Measurements were carried out in acid and alkaline solutions. The
acid solutions had the following compositions: "Low Ni": 0.024 M
NiSO.sub.4, 0.006 M FeSO.sub.4, 0.035 M NaKC.sub.4 H.sub.4 O.sub.6,
pH = 3 or 4.6. The molar ratio of (Fe/Ni) in solution was 20/80.
"High Ni": had composition as above for "Low Ni", but with 0.114 M
NiSO.sub.4 and pH = 3, 3.8 or 4.6. The (Fe/Ni) ratio in solution
was 5/95. The alkaline solutions were ammoniacal-citrate solutions,
the compositions of which were: "High citrate": 0.125 M NiCO.sub.3,
0.032 M Fe dust, 0.301 M C.sub.6 H.sub.8 O.sub.7, 0.332 M
(NH.sub.4).sub.2 M C.sub.6 H.sub.5 O.sub.7 and NH.sub.4 OH for pH =
9.25. The "low citrate" solution had the same pH and concentration
of Ni and Fe but it contained 0.127 M C.sub.6 H.sub.8 O.sub.7 and
0.137 M (NH.sub.4).sub.3 H C.sub.6 H.sub.5 O.sub.7. The molar ratio
of (Fe/Ni) in solution was 20/80.
The solutions were made of reagent grade chemicals and deionized
water. The citrate solutions were prepared according to British
Pat. No. 925,144.
After electroplating, the samples were cut into 1.5 .times. 1.5 cm
squares and analyzed by the x-ray fluorescence technique for wt. %
Fe (accuracy .+-. 1 wt. %) and thickness (accuracy .+-. 150A.).
The effect of frequency on the rate of deposition and on the
composition of the deposited alloy were examined. In the FIGS. 2
and 3 the rate and percent Fe are shown as a function of log
frequency in low and high nickel solutions, respectively, for
conditions of constant pH, I.sub.d.sub.-C and I.sub.peak. On the
left hand sides are given values for direct current plating
only.
In accordance with the theory of this invention, a diminishing
effect of a-c current with increasing d-c current in the system is
expected. This prediction is clearly validated by FIG. 4. With
I.sub.d.sub.-c of 2 mA/cm.sup.+.sup.2, the Fe content varies from
9.5 to 30 percent, but changes only from 15.2 to 18 percent with
I.sub.d.sub.-c of 5 mA/cm.sup.+.sup.2 at constant I.sub.peak and pH
= 3.8.
FIG. 5 shows a log current vs. voltage plot for the high citrate
solution. It can be seen that for high values of total current,
I.sub.Fe reaches a limiting value, which is taken as the limiting
reaction current according to Vetter's criteria as set forth
hereinbefore in the Theory of the Invention section. In FIGS. 6 and
7 the deposition rates and percent Fe are given as a function of
log frequency for two values of direct current density.
The variation in composition with the density of direct current at
constant frequency and amplitude of alternating current is given in
FIGS. 8 and 9 for acid and alkaline solutions, respectively. For
the purpose of comparison, data for d-c current plating alone are
also given and designated as f = 0.
From Equation 5 the amplitude of the diffusion concentration wave
is expected to increase with increasing I.sub.peak, and that the
iron content of both the surface electrolyte and the deposit should
decrease. This is validated in FIG. 10.
Since temperature affects the equilibrium constant for the
dissociation of metallic complexes, it can be expected to exert an
influence on the deposition rate. In FIG. 11 deposition rates and
percent Fe are given for the high citrate solution as a function of
frequency for temperatures of 25.degree. and 40.degree.C. At higher
temperatures the corrosion rate of the alloy becomes too large for
meaningful study.
It is validated in FIGS. 2, 3, 4, 6, 7 and 11 that to a large
extent the composition of the deposit is influenced by frequency.
Since the percentage of one metal is a function both of its
deposition rate and of the total rate of metal deposition, it is
more meaningful to examine how the iron rate alone varies with
frequency. The diffusion law predicts a linear dependence upon
.omega..sup.-.sup.1/2, e.g., Equation 6. From the plots given in
FIGS. 12 to 15 it can be seen that the rate of Fe deposition is
linearly dependent upon .omega..sup.-.sup.1/2, approaching its d-c
current value at high frequencies, where the contribution from the
a-c component becomes negligible. However, there are two regions,
one being that of low frequency, i.e., 20 to 100 Hz, and the other
from 100 to 1,000 HZ for which the slope of the line has different
values, being smaller at lower frequencies. The explanation of this
behavior is discussed separately below for the two different types
of solutions employed.
DEPOSITION FROM ACID SOLUTIONS
In the solution of pH = 3, the rate of alloy deposition is lower
under a-c current plus d-c current, than under d-c current alone.
This indicates that some dissolution of alloy is taking place. It
might be argued that Fe dissolves faster than Ni, and that there is
less Fe present in a deposit. However, there is no trend in the
variation of alloy deposition rate with frequency. Further, in the
solutions of pH = 4.6, the total rate is not affected by a-c
current, but the Fe rate is lower and shows the same clearly
defined two regions of different dependence on frequency. In the
region of low frequency the contribution of a-c current is
two-fold. Firstly, its affect on diffusion is the largest, and
secondly there is an effect on the surface pH. When the potential
is varied slowly, the electrode remains in the anodic region
sufficiently long to allow oxidation of adsorbed hydrogen on its
surface. Hence, pH.sub.surface is brought back to its original
value for the next cathodic cycle. If pH.sub.surface does not
increase, the formation of hydroxides does not occur, and there is
no anomalous deposition of iron and the Ni deposition is not
suppressed. This can be clearly seen from FIG. 12. With increasing
frequency, the electrode spends less and less time in the anodic
region, and the kinetic processes apparently cannot follow such
rapid changes. As a result, pH.sub.surface increases sufficiently
to cause the formation of iron hydroxide, which prevents the
discharge of Ni. At 100 Hz, Ni and Fe deposit with the same rate as
shown in FIG. 12, even though the bulk concentration of Ni is four
times higher than that of Fe. Above 100 Hz, Fe deposits with a
higher rate than Ni. In FIG. 13 the rates of Fe deposition are
shown for three values of bulk pH. Within the experimental error,
Fe deposits from the solutions of pH = 3.8 and pH = 4.6 with the
same rate, indicating that a-c current produced the same surface
pH.
With increasing bulk pH, or by increasing the d-c current level,
the a-c current component becomes less effective in controlling the
pH of the surface as shown in FIGS. 2, 3, and 4. According to
Bockris et al., as reported in the article in Electrochemistry
Acta, vol. 4, page 325 (1961), the Fe rate is closely connected
with pH through the relationship (.delta.ln i.sub.Fe /.delta. log
c.sub.OH -) = 1.
By examining FIG. 2, it can be seen that in the low Ni solution of
pH = 4.6, the rate of alloy deposition is higher under a-c current
plus d-c current than under d-c current alone. If adsorbed
hydroxides block the surface, a hydrogen evolution reaction from
the rather dilute bath might be kinetically the most favorable
reaction. With a-c current present, adsorption of hydroxides doe
not occur, and the rate is higher.
DEPOSITION FROM COMPLEX SOLUTIONS
Deposition of the alloys from complex solutions with superimposed
a-c current on d-c current is interesting on account of the
dependence on the k/.omega. ratio. Further, in such systems the two
currents are more comparable since the reaction layer thickness for
d-c current is approximately the same as the penetration depth for
a-c current (approximately 7.5 .sup.. 10.sup.-.sup.5 cm). It can be
seen from FIGS. 6 and 7 that by varying frequency alone the Fe
content can be varied from 14 to 59 percent, or, by decreasing the
concentration of complexing agent for Fe, from 8 to 63 percent.
In FIG. 14 rates of Fe deposition are given as a function of
.omega..sup.-.sup.1/2 for two values of d-c current and two
concentrations of complexes of citrate ions. At I.sub.d.sub.-c = mA
cm.sup.-.sup.2 a quite surprising effect is found, namely, Fe
deposits with a higher rate from the solution containing more of
its complexing agent. When I.sub.d.sub.-c is increased to 4 mA
cm.sup.-.sup.2, Fe deposits with the same rate from both citrate
solutions in low frequency region. However, at higher frequencies
the situation becomes "normal", i.e., with more complexing agent
less Fe ions are available for deposition. This "abnormality" can
be explained if tee values of the rate constant are compared for
low and high citrate solution.
The reaction exchange rate, v.sub.o, can be calculated from
Equation 11 if the limiting reaction current, i.sub.r, is
determined experimentally. For the high citrate solution i.sub.r =
1.54 mA cm.sup.-.sup.2, giving v.sub.o = 2.06 .sup.. 10.sup.-.sup.4
. For the low citrate solution, i.sub.r = 2.02 mA cm.sup.-.sup.2
and v.sub.o = 1.37 .sup.. 10.sup.-.sup.4 mole cm.sup.-.sup.3
sec.sup.-.sup.1. From these v.sub.o values, k is calculated to be
4.63 .sup.. 10.sup.3 and 1.19 .sup.. 10.sup.3 sec.sup.-.sup.1 for
high and low citrate, respectively. The rate depends not only on
.omega..sup.-.sup.1/2 but also on the ratio of k to .omega.. This
ratio varies from 37 to 0.74 in the high citrate solution, but only
from 9.5 to 0.19 in the low citrate, when f is varied from 20 to
1,000 Hz. The rate constant is equal to .omega. at 740 Hz and 190
Hz for high and low citrate, respectively. Since k is an order of
magnitude larger than .omega. at low frequencies in the high
citrate solution, Fe deposits with a higher rate than from low
citrate solution where k and .omega. are of the same order of
magnitude. At 1,000 Hz the ratio of k/.omega. in both solutions are
of same magnitude, i.e., 0.74 and 0.19, and there is very little
difference in Fe rates as shown on the left side of FIG. 15.
By increasing I.sub.d-c, more material is required according to
Faraday's law, and the effect of d-c current becomes more
pronounced. When the frequency is increased, the effect of a-c
current is still further diminished, and the transition to "normal"
behavior is observed.
If the concentration of citrate ions is changed, changes are not
expected in Ni rate, since Ni is present in solution as the [Ni
(NH.sub.3).sub.n ].sup.+.sup.+ complex. The data given in FIG. 15
supports the expectation.
By superimposing a-c current on d-c current it is expected, in
accordance with the principles of this invention, that variation in
Fe composition on the surface and consequently in the deposit will
take place within the time of one cycle, i.e., approximately
10.sup.-.sup.2 sec. On a microscopic scale this means uniform
composition, which is observed in practice of this invention, as
shown in FIG. 16. The line at the bottom of the graph represents %
Fe obtained from the solution with molar ratio of Fe/Ni = 5/95. The
composition of the solution is reflected exactly in the deposit
throughout its thickness.
EXAMPLES OF THE INVENTION
Alloys of 80-20 Ni-Fe are obtained by the practice of this
invention from solutions having the parameters identified
below:
(a)
NiCO.sub.3 = 16.2 g/l (45%Ni)
Fe dust = 1.78 g/l
Citric acid = 63.3 g/l
Nh.sub.4 -citrate = 75.5 g/l
pH = 9.25 at approximately 25.degree.C
i.sub.d-c = 2 ma/cm.sup.2
I.sub.p = 15 ma/cm.sup.2
f = 60 Hz
Rate = 380A/min.
(b)
NiCO.sub.3 = 16.2 g/l (45%Ni)
Fe dust = 1.78 g/l
Citric acid = 63.3 g/l
Nh.sub.4 -citrate = 75.5 g/l
pH = 9.25 at approximately 25.degree.C
i.sub.d-c = 4 ma/cm.sup.2
I.sub.p = 15 ma/cm.sup.2
f = 20 Hz
Rate = 380A/min.
(c)
NiCO.sub.3 = 16.2 g/l
Fe dust = 1.78 g/l
Citric acid = 26.6 g/l
Nh.sub.4 -citrate = 31.0 g/l
pH = 9.25 at approximately 25.degree. C
i.sub.d-c = 2 ma/cm.sup.2
I.sub.p = 15 ma/cm.sup.2
f = 100 Hz
Rate = 100A/min.
(d)
NiSO.sub.4 .sup.. 6H.sub.2 O = 6.3 g/l
FeSO.sub.4 .sup.. 7H.sub.2 O = 1.7 g/l
NaK-tartrate = 10.0 g/l
pH = 3.0 at approximately 25.degree.C
I.sub.d-c = 2 ma/cm.sup.2
I.sub.p = 13.7 ma/cm.sup.s
f ' 25 Hz
Rate = 22A/min.
(e)
NiSO.sub.4 .sup.. 6H.sub.2 O = 30.0 g/l
FeSO.sub.4 .sup.. 7H.sub.2 O = 1.7 g/l
NaK-tartrate = 10.0 g/l
pH = 3.0 at approximately 25.degree.C
i.sub.d-c = 2 ma/cm.sup.2
I.sub.p = 13.7 ma/cm.sup.2
f = 100 Hz
Rate = 125A/min.
* * * * *