D e p o s i t i o n f r o m A q u e o u s S o l u t i o n s :

A n O v e r v i e w
M o r t o n S c h w a r t z
1 . 0 I N T R O D U C T I O N
E le ct ro d e p o sit ion , a lso ca lle d e le ct ro p la t in g o r sim p ly p la t in g, is a n
economical technology to protect and enhance the functionality of parts used
in many diverse industries including home appliances, jewelry, automotive,
aircraft/aerospace, and electronics in both decorative and engineering
applications. Although decorative applications have diminished somewhat
primarily due to added expenses and problems associated with plant effluent
(pollution) control and waste treatment, its applications in engineering,
electroforming, and electronics have increased. The emphasis is on the
latter applications, and the structures and properties of deposits.
The purpose of decorative plating is to provide a durable, pleasing finish
to the surfaces of manufactured articles, so the corrosion characteristics of
the deposits and their ability to protect the substrate are important factors.
These and other deposit properties involved in the selection and performance
of decorative coatings including hardness, wear resistance, ductility, and
stress are also important to the engineering applications of plated coatings.
Engineering applications of plated coatings involve imparting special or
improved properties to significant surfaces of a part or assembly and/or
protecting or enhancing their function in their operating environment. Other
applications include salvage of mismachined or worn parts and other types
of reworking as well as material savings, use of less expensive materials,
and substitution of materials more easily fabricated, Special technologies
5 0 6
D e p o s i t i o n f r o m A q u e o u s S o l u t i o n s 5 0 7
such as electroless deposition, electroforming, anodizing, thin films, magnetic
coatings, and printed wiring (circuit) boards have been selected for discussion
as representing specific engineering applications.
Although electroplating and vacuum deposition processes are generally
considered competitive processes, there are increasing applications in
which they are (or can be) highly complementary. These involve utilizing the
a d v a n t a g e s o f b o t h d e p o s i t i o n t e c h n o l o g i e s :
V a c u u m D e p o s i t i o n A q u e o u s D e p o s i t i o n
  C l o s e t o l e r a n c e s   L o w e r c o s t s
Wide choice of substrates Thicker coatings
Wide choice of coatings Coating complex shapes
  C o n t r o l a n d m o d i f i c a t i o n
o f d e p o s i t p r o p e r t i e s
  C o n t r o l o f r e s i d u a l s t r e s s
A combined process permits almost any substrate to be coated with a
much wider ran ge of deposits than either used alone. It extends the
application of aqueous deposition to substrates which are difficult to coat,
p a rt icu la r l y n o n -m e t a ll ics ( ce ra m i cs) o r a ct i ve m e t a ls n o t re a d il y o r
s a t i s f a c t o r i l y p r o c e s s e d .
E xa m p l e s o f c o m b i n e d p r o c e s s i n g i n c l u d e t h e e l e c t r o d e p o s i t i o n o f
such metal substrates as Mo, Ti, and Be by initially sputtering a thin Cu or Au
deposit to provide substantially improved adhesion.[1] The plating of plastics
using chemical preparation is expensive, requires rigorous control, and
presents formidable waste treatment problems. A pre-plate treatment using
vacuum techniques to condition the surface by RF glow discharge followed
by sputtering or electron beam evaporation of 1000 angstrom Ni and 1000
angstrom Cu deposits permits direct electroplating to final thicknesses.[2]
In printed wiring board (PW B) fabrication, plasma processing is being
employed to clean drilled holes and to remove drill smear. However, in some
cases, this leaves undesirable interfering ash and decomposed residues
requiring further chemical clean-up. Sputtering processes for depositing the
initial Cu deposit on PWB’s and through-hole deposition have been developed
to replace the electroless Cu deposition processes.[3] It has been predicted
t h a t su ch p ro ce sse s m a y re p la ce t h e p re se n t ly u se d e le ct ro le ss Cu
s y s t e m s c o m p l e t e l y . [ 4 ]
508 Deposition Technologies for Films and Coatings
E l e c t r o d e p o s i t i o n h a s b e e n u s e d t o f a b r i c a t e m a g n e t r o n s p u t t e r in g
targets of well defined shapes. The advantages include deposition precisely
where needed or desired, eliminating waste. Such electrod eposited targets
are quite pure with a minimum of oxygen or other gases. Sputtering targets
of Ag, Cr, Au, Fe, Ni, Co and alloys have been prepared by electroplating.[5]
2 . 0 G E N E R A L P R I N C I P L E S
Figure 10.1 represents a simplified plating cell. A DC source, usually
a rectifier or motor generator, supplies current flowing in one direction
through the external portion of the circuit when a potential difference is
imposed across the system. The current flow is that of electrons in the
external conductors. The mechanism of electrical transfer in the solution is
by means of electrically charged “particles” called ions. Positive ions
(cations) travel toward the negative electrode (cathode) and negative ions
(anions) travel toward the positive electrode (anode) when the potential is
applied, thus completing the electrical circuit. The electrolyte usually
contains other components which influence the process (see Fig. 10.7 later
i n t h i s c h a p t e r ) .
F i g u r e 1 0 . 1 . P l a t i n g C e l l
D e p o s i t i o n f r o m A q u e o u s S o l u t i o n s 5 0 9
T h e ca t h od e o r de p o sit io n re a ct io n s a re ch a ra ct e ri ze d a s re d u ct io n
reactions since electrons are “consumed,” and the valence states of the ions
involved are reduced. The anodic reactions are oxidation reactions wherein
electrons are liberated, and the valence states are increased. Each set of
reactions represents half-cell reactions and proceeds independently of the
other, limited by a condition of material balance, i.e., electrons liberated in the
anode reactions must equal the number of electrons “consumed” i n the
c a t h o d e r e a c t i o n s .
The above describes systems such as nickel or copper deposition from
acidic solutions* of their simple ions. Since these are divalent ions (Ni2+,
Cu2+), the equations shown in Fig. 10.1 would involve two electrons.
Deposition from solutions in which the metallic ions are combined with
other ions or ligands as complex ions involves more complicated mechanisms.
The cyanide-containing electrolytes represent the largest group of such
systems. Some of these complex ions are so tightly co nstituted, i.e., the
ionization constant of the metal ion is so small, that reduction or deposition
of the metal atoms at the cathode occurs directly from the complex ions. This
appears to be the mechanism involved with copper, silver and gold cyanide
c o m p l e x i o n s :
E q . ( 1 ) [ C u ( C N ) 3 ] = + e -   C u o + 3 ( C N ) -
E q . ( 2 ) [ A g ( C N ) 2 ] - + e -   A g o + 2 ( C N ) -
E q . ( 3 ) [ A u ( C N ) 2 ] - + e -   A u o + 2 ( C N ) -
The stability of the gold cyanide complex ion is such that it exists in mildly
a c i d i c g o l d p l a t i n g s o l u t i o n s .
It should be noted that the complex ions described above and other
types are anionic and would migrate to the anode during electrolysis. Yet,
deposition still takes place at the cathode, indicating that mechanisms other
than simple electron reactions are involved in the cathode film. These
complex anions approach the cathode by convection and/or diffusion where
specific adsorption effects can occur in the double layer as discussed by
Wagner, citing Frumkin and Florianovich.[6] The influence of simple cations
present in the film are also involved in the reduction process.
Faraday’s Laws of electrolysis (1833) are basic to electrodeposition.
* Most acidic plating solutions fall into this category, involving the simple ions.
510 Deposition Technologies for Films and Coatings
* Thickness in m 0.0394 = thickness in mils.
** The Faraday can be derived from the fact that 1 gram-atomic weight of an element
contains 6.023 x 1023 atoms (Avogadro’s Number, N). If the charge on the ion is A,
then Z x N electrons are required to deposit 1 gram-atomic weight, and Z x N/A =
6.023 electrons are required to deposit (or dissolve) 1 equivalent weight of an
element. Since the charge on an electron is 1.602 x 10-19 coulombs, 6.023 x 1023
electrons x 1.602 x 10-19 coulombs = 96,496 coulombs.)
They relate the current flow, time, and the equivalent weight of the metal with
the weight of deposit and may be stated as follows:
1. The amount of chemical change at an electrode is directly
proportional to the quantity of electricity passing through the
s o l u t i o n .
2. The amounts of different substances liberated at an electrode
by a given quantity of electricity are proportional to their
c h e m i c a l e q u i v a l e n t w e i g h t s .
Faraday’s Laws may be expressed quantitatively:
I · t E q
E q . ( 4 ) W = _ _ _ _ _ _ _ _ _ _ _ _
F
w h e r e : W = w e i g h t o f d e p o s i t i n g r a m s
I = c u r r e n t f l o w i n a m p e r e s
t = t i m e i n s e c o n d s
E q = E qu i va le n t we i gh t o f d e po sit ed e le m en t
F = Faraday, a constant, = 96,500 coulombs (approx.)
I · t is the quantity of electricity used (coulombs = ampere-seconds) and Eq,
the equivalent weight of the element, is the atomic weight divided by the
valence change, i.e., the number of electrons involved. If the current is not
c o n s t a n t , t h e n I · t m u s t b e i n t e g r a t e d :
t 2
I d t
t 1
From a practical standpoint, the weight of the deposit is converted to the
more meaningful thickness of the deposit using the relationship, W (gms) =
volume (cm3)/deposit density, with the volume of the deposit equal to the
thickness (in μm)* times the area (in m2). The Faraday**, F, can be
experimentally determined by rearranging Eq. (4):
D e p o s i t i o n f r o m A q u e o u s S o l u t i o n s 5 1 1
I · t E q E q . ( 5 ) F = _ _ _ _ _ _ _ _ _ _ _ _
W
R e a r r a n g i n g E q . ( 4 ) t o
W F
E q . ( 6 ) I t = _ _ _ _ _ _ _ _ _
E q
permits the determination of the charge passing through a circuit by the
known deposition or dissolution of an element, usually silver. Devices which
utilize this applica tion of Faraday’s Laws are known a s coulometers.
Coulometers are used to determine the efficiency of a deposition process.
T h e y a re a ls o e m p l o ye d a s e it h e r t i m e r s o r in t e g r a t o r s p o s s e s s i n g
“electrochemical memory” and producing sharp potential “end -points,” i.e.,
significant changes in electrode potentials which activate electronic circuits.
Figure 10.2 schematically illustrates such a device—an electrochemical cell
called an E-cell as part of an electronic circuit.
Figure 10.2. Microcoulometer E-Cell (Courtesy Plessey Electro-Products)
Fa ra d a y’s L a ws a r e a b so lu t e la ws, a n d n o de via t io n s o r e xce p t io n s
have been found. Apparent exceptions can be shown to be incorrect or
explained by failure to take into account all the chemical or electrochemical
reactions involved at the electrode. Thus, the efficiency of an electrochemical
r e a c t i o n c a n b e d e t e r m i n e d :
512 Deposition Technologies for Films and Coatings
E q . ( 7 )
t h e o r e t i c a l w t . o f d e p o s i t
a c t u a l w e i g h t o f d e p o s i t
% E l e c t r o d e E f f i c i e n c y   1 0 0 ×
Table 10.1 indicates typical cathode current efficiencies for some common
deposits from various electrolytes. With knowledge of the actual efficiency,
predicted (average) thickness of deposit c an be obtained, limited by the
c o n t r o l o f t h e c u r r e n t d i s t r i b u t i o n .
Table 10.1. Cathode Current Efficiencies of Various Plating Solutions
_____________________________________________________
D e p o s i t E l e c t r o l y t e R a n g e , %
_____________________________________________________
A g C N 1 0 0
A u A c i d
N e u t r a l 5 0 - 1 0 0
C N
C d C N 8 5 - 9 5
C r C r O 3 / H 2 S O 4 1 0 - 1 5
C r O 3 / S O 4 - F 1 8 - 2 5
C u A c i d S O 4 9 7 - 1 0 0
C N ( l o w e f f . ) 3 0 - 4 5
C N ( h i g h e f f . ) 9 0 - 9 5
P 2 O 7 ~ 1 0 0
F e A c i d 9 0 - 9 8
I n A c i d o r C N 3 0 - 5 0
N i A c i d 9 3 - 9 8
P b A c i d 9 5 - 1 0 0
R h A c i d 1 0 - 5 0
S n A c i d 9 0 - 9 5
A l k a l i n e 7 0 - 9 5
Z n A c i d ~ 9 5
C N 5 0 - 8 0
___________________________________________________
D e p o s i t i o n f r o m A q u e o u s S o l u t i o n s 5 1 3
The current flowing through a conductor is driven by a potential
difference or voltage, the magnitude of which is determined by the relationship
e x p r e s s e d a s O h m ’ s L a w ( 1 8 2 6 - 2 7 ) :
E q . ( 8 ) E = I R
where E = volts, I = amps, and R = ohms. This law regulates both the current
flow and its paths in an electrodeposition cell. A commercial electroplating
installation and operation involves a multiplicity of series and parallel
electrical circuits with only the total current and applied voltage controlled.
The current distribution on each individual part or portion of a part (and
resulting deposit thickness and properties) depends on the electrode potentials
and resistances involved in the “mini-circuits” as well as the geometry and
spacing of parts. Since the resistances of the solid, metallic conductors in
the circuit are several orders of m agnitude lower than the electrolytic
(solution) resistances, they can usually be neglected. The potentials within
the electrolyte and, more importantly, the electrode -electrolyte interfaces,
are fundamental controlling factors and are not as straight -forward as
s u g g e s t e d b y O h m ’ s L a w .
When a metal is immersed in a solution containing its ions, an equilibrium
condition is set up between the tendency for the metal to go into solution and
the tendency for the metallic ions in solution to deposit on the metal: M0 
Mn+ + ne-. However, before this equilibrium is established (i.e., the exchange
currents or current densities are equal |i+| = |i-|= i0), one of the reactions may
be faster than the other, resulting in a “charge separation.” If the reaction
proceeding to the right is faster than to the left, the metal surface would be
negatively charged. If the deposition reaction (to the left) is faster, then the
surface would be positively charged. This resulting potential between the
metal and the solution (at unit activity) is called the single or standard
electrode potential. Since this is a half-cell reaction, a reference electrode,
the saturated hydrogen electrode (SHE) is used to complete the circuit and
is given the arbitrary value of zero potential. In many ins tances other
reference electrodes such as the calomel electrode are substituted with
appropriate corrections. Potential measurements made in this manner (or
va l u e s d e r i ve d t h e r m o d yn a m i ca l l y) r e s u l t i n a se r i e s k n o wn a s t h e
E l e c t r o m o t i v e F o r c e ( E M F ) S e r i e s .
This origin of the electrode potential was first formulated by W . Nernst
(1889). The magnitude of the potential difference between the metal and its
ionic solution is given by the Nernst equation:

514 Deposition Technologies for Films and Coatings
R T a x ( p r o d u c t s )
E q . ( 9 ) E = E o + _ _ _ _ _ l n _ _ _ _ _ _ _ _ _ _ _ _ _ _
n F a y ( r e a c t a n t s ) *
where E = observed EMF, potential difference (volts)
E o = s t a n d a r d E M F
R = g a s c o n s t a n t , 8 . 3 1 4 ( j · o K - 1 m o l - 1 )
T = a b s o l u t e t e m p e r a t u r e , o K
n = v a l e n c e c h a n g e ( e l e c t r o n t r a n s f e r )
F = Faraday, 96,500 coulombs (A · sec mol -1)
a = activity (apparent degree of dissociation)
If the natural logarithm is converted to logarithm base 10, and T is 298oK
( 2 5 o C ) , t h e n E q . ( 9 ) b e c o m e s :
Eq. (10) E = Eo + (0.059/n)** log a (or log c approx.)
Thus, a tenfold change in ion concentration changes the electrode potential
by 59 mV/n (a negative change makes the electrode potential less positive).
This is significant when complexing agents are present since the ionic
concentration can be reduced drastically with the accompanying change in
electrode potential.*** For example, Eo = -0.76 volts for zinc. But, when zinc
i s c o m p l e x e d w i t h c y a n i d e :
E q . ( 1 3 ) Z n 2 + + 4 ( C N ) -   [ Z n ( C N ) 4 ] =
the electrode potential shif ts to approximately -1.1volt. The standard
electrode potential for the Cu1+/CuM half cell is +0.52 volts which shifts to ~-
1 . 1 v o l t s w h e n c o m p l e x e d w i t h c y a n i d e :
* Since the metal (solid) is the reactant in a plating cell, its activity is considered =
1 for all practical purposes and can be neglected. Also, as a practical approximation,
the concentration in moles/L can be substituted for activities.
* * 0 . 0 5 9 = 2 . 3 0 3 x 8 . 3 1 6 x 2 9 8 . 1 / 9 6 , 4 9 6 .
*** W hen complex ion reactions are involved:
E q . ( 1 1 ) M n + + q X p -   [ M X q ] n - p q
where q is the coordination number, then the Nernst equation is modified:
E q . ( 1 2 ) E = E o -
R T
n F l n K f +
R T
n F l n
a
a
M
n p q
X
q
q
p


Kf is the stability constant of the complex ion. Since Kf will be quite large for very
stable complexes, the potential can shift substantially negati vely.

D e p o s i t i o n f r o m A q u e o u s S o l u t i o n s 5 1 5
E q . ( 1 4 ) C u 1 + + 3 ( C N ) -   [ C u ( C N ) 3 ] =
The practical significance is that a copper cyanide strike provides the best
undercoat on a zinc surface since the potentials are essentially the same.
Attempts to use an acid copper (Cu2+) (Eo = +0.34 volts) solution would
provide a potential difference of 1.1 volts, resulting in an immersion or
displacement deposit with poor adhesion. The closeness of the electrode
potentials for the [Zn(CN)4]= and [Cu(CN)3]= complexes also permits these
metals to be deposited simultaneously as a brass alloy deposit from cyanide
s o l u t i o n s .
For electrodeposition reactions to occur, an additional potential is
required to overcome the equilibrium conditions discussed above, i.e., to
provide a non-equilibrium, irreversible condition. Referring to Fig. 10.1, the
total plating voltage is the sum of three components. E2 represents the
potential required to overcome the resistance of the electrolyte and obeys
Ohm’s Law; it would be the only potential required if only the single electrode
potentials were involved in the electrodeposition process. E1 and E3 are the
potentials at the electrodes required to sustain the electrolysis process when
the current is flowing and exceed the single electrode pote ntials. The
additional voltage is called polarization which usually increases as the
current increases. The electrical energy is converted to heat according to
J o u l e s L a w :
E q . ( 1 5 ) E h e a t = I E t = I 2 R t
resulting in increased temperatures of the electrolyt ic solutions.
Polarization, also called overpotential or overvoltage*, is an important
controlling factor in electrodeposition processes. A minimum energy which
the reactants must possess is a requisite for any chemical reaction to occur.
For an electrochemical reaction to proceed, an overpotential is required to
overcome the potential barrier at the electrode/solution interface; this is
called the activation overpotential. It is the overpotential required for the
charge-transfer reaction itself and is kinetically controlled. Cathodic activation
overpotential shifts the energy level of the ions in the inner electrical
double layer nearer to the potential barrier, so that more ions can cross it in
* In more rigorous treatments, the term overvoltage is restricted to the excess
potential required for a single reaction (usually irreversible) to proceed at a specified
electrode whereas the term polarization is more general and includes all reactions
a t t h e e l e c t r o d e .
516 Deposition Technologies for Films and Coatings
F i g u r e 1 0 . 3 . C o n c e n t r a t i o n p o l a r i z a t i o n
a given time, producing a deposit on the surface. Activation overpotential
also exists at the anode but in the opposite direction.
Changes in the ion concentrations at the electrodes are major contribut ions
to polarization. Figure 10.3 depicts the increased metallic ionic
concentration at the anode and the decreased concentration at the cathode
as a result of the dissolution and deposition processes. This results in
corresponding changes in the equilibrium potentials per the Nernst equation
(Eq. 9) since it changes the value of log CE/CS, CE being the ionic concentration
at the electrode and CS the concentration in the bulk of the solution
(see Eq. 10). This ef fect due to the concentration cha nges is ca ll ed
concentration polarization and is mass transport controlled.
Figure 10.4 illustrates a typical current/potential curve indicating the
regions of activation polarization (a), concentration polarization (C), limiting
current followed by a post limiting region (with gas evolution). The open
circuit (rest) potential is indicated by (EM)R. Where anodic and cathodic
polarization curves intersect, |io| is indicated.
I n cre a se d a n o d e co n ce n t ra t io n p o la ri za t io n u lt im a t e l y re su lt s in t h e
evolution of oxygen which reacts with the electrode to produce oxide
insulating films increasing the ohmic resistance. The oxygen may also
react with various solution constituents such as organic compounds or cyanides,
D e p o s i t i o n f r o m A q u e o u s S o l u t i o n s 5 1 7
F i g u r e 1 0 . 4 . T y p i c a l p o l a r i z a t i o n c u r v e
thereby consuming them and/or converting them into other compounds which
may be detrimental to the electrodeposition process. In some processes,
such as anodizing of aluminum or where insoluble anodes are
involved such as in chromium platin g, anode polarization is desirable.
Cathodic concentration polarization may result in the evolution of
hydrogen as the competing reaction. The pH of the cathode film increases
and hydrates or hydroxides may precipitate and be occluded in the deposit.
The co-deposition of hydrogen may result in brittleness of the deposit and,
by migration and diffusion into the substrate, result in hydrogen embrittlement.
Hydrogen overvoltage which is the polarization for the specific reaction
discharging hydrogen at a specified electrode surface involves at least two
s t e p s :
Eq. (16) 2H+ + 2e 2Hadsorbed H2 (gas molecule)
The latter step is usually the slower, rate -determining step, and a higher
p o t e n t i a l i s r e q u i r e d t o d i s c h a r g e t h e g a s .
The factors influencing hydrogen o r oxygen overvoltage include:
a . E l e c t r o l y t e c o m p o s i t i o n
b . T y p e o f m e t a l e l e c t r o d e
c . N a t u r e o f e l e c t r o d e s u r f a c e
d . C u r r e n t d e n s i t y
e . T e m p e r a t u r e
518 Deposition Technologies for Films and Coatings
A g i t a t io n a n d i n c re a se d o p e r a t in g t e m p e ra t u r e o f t h e s o l u t io n h e lp
minimize concentration polarization, permitting higher current densities and
f a s t e r p l a t i n g r a t e s .
T h e " t h r o wi n g p o we r " ( T P ) o f a p l a t i n g s o l u t i o n o r , m o r e p r o p e r l y,
macrothrowing power since it indicates the degree of plate uniformity
(thickness distribution) over the substrate surface contours, is an important
characteristic because the deposit properties and overall quality are affected.
F a c t o r s i n f l u e n c i n g d e p o s i t ( p l a t e ) d i s t r i b u t i o n a r e s h o wn i n T a b l e
10.2. Generally, electrolytes contai ning free metallic ions exhibit poorer
throwing power than those in which the ions are complexed or contain
supporting, non-depositing, ions, the latter improving solution conductivity.
The overall “geometry” of the plating system influences current distri bution.
Significantly increased cathode polarization at higher current densities
results in decreased current efficiency, improving throwing power. Thus,
cathode current efficiency-current density curves are useful in predicting the
throwing power of a plating solution. If the cathode efficiency decreases with
increased current density, the throwing power improves proportionately.
The shape and slope of the curves are indicative of the throwing power.
However, if the cathode efficiency remains high over a wide range of current
densities, the throwing powe r is usually poor. E xamples of desirable
cathodic polarization are complex ion-containing solutions such as alkaline
s t a n n a t e ( t i n p l a t i n g ) a n d a l k a l i n e - c ya n i d e ( z i n c p l a t i n g ) s o l u t i o n s .
Based on Haring-Blum %TP values, Schaefer and Pochapsky[7]
reported that conventional plating solutions generally fall into four classes:
(i) alkaline stannate and zincate (%TP > 50), (ii) most other cyanide
solutions (%TP = 25 to 50), (iii) most acid solutions (%TP > 0 to 25), (iv)
c h ro m iu m p la t in g ( %T P = - 1 0 0 t o 0 ) . T h e wi d e r a n ge o f “ n e ga t i ve ”
macrothrowing power for chromium (from chromic acid solutions) is due to
the fact that, within limits, the cathode current efficiency increases with
increasing current density, thereby greatly exaggerating the non -uniformity
o f t h e d e p o s i t s .
Rothschild[8] showed substantial improvement in the throwing power of
the so-called high throw acid copper sulfate plating solutions containing low
metal/high acid concentrations employed for through-hole plating of printed
circuits boards, 87% vs. 14% for a conventional high metal/low acid concentration
s o l u t i o n .
Foulke and Johnson[9] investigated the throwing power characteristics
of various precious metal plating solution formulations. Percent throwing
power values for both macro- and microthrowing power characteristics were
r e p o r t e d .
D e p o s i t i o n f r o m A q u e o u s S o l u t i o n s 5 1 9
The term throwing power is sometimes mistakenly applied to another
property of plating soluti ons: namely, covering power. Covering power
relates to the lowest applied current density at which a plating solution
produces a deposit, i.e., it is a measure of a solution’s ability to deposit into
geometric recesses of an article to be plated. At very low current densities
in some plating solutions, the potential required for metal deposition (sometimes
referred to as the decomposition potential) may not be reached, and
some other electrode reactions support the passage of current; these may
include hydrogen evolution or the reduction of addition agents or other
reducible species or ions. Poor covering power or the inability to deposit
metal into areas of low current density can sometimes be overcome or
avoided by using a high current density (“strike”) to initiate plating into the
recess and then reducing the current density to the normal operating range.
Table 10.2: Factors Influencing Current/Plate Distribution
T y p e o f E l e c t r o l y t e
S i m p l e “ F r e e ” I o n s
C o m p l e x I o n s
S u p p o r t i n g I o n s
P o l a r i z a t i o n
C o n d u c t i v i t y
C a t h o d e E f f i c i e n c y -
C u r r e n t D e n s i t y C u r v e s
G e o m e t r y o f P l a t i n g S y s t e m
O t h e r F a c t o r s
S u b s t r a t e C o m p o s i t i o n a n d S t r u c t u r e
S u r f a c e P r e p a r a t i o n a n d P r e - t r e a t m e n t
Current distribution over the electrode surfaces influence plate distribution
and is differentiated as primary, secondary, and tertiary. Primary current
distribution involves the plating system geometry with the potential constant
over the electrode surface and negligible polarization influences. Secondary
current distribution involves activation ove rpotential (a), electrode kinetics,
and solution conductivity. Tertiary current distribution involves concentration
overpotential (C), the diffusion (boundary) layer, and solution agitation,
i . e . , m a s s t r a n s p o r t i s a f a c t o r .
Current and plate distributio ns, and methods and calculations for
determining throwing power, such as the Hull Cell,[10] the Haring -Blum
520 Deposition Technologies for Films and Coatings
Cell,[11] and Wagner number are reviewed and analyzed by Ibl.[12] Shawki et
al[13] devised a method for measuring throwing power into recesses and holes
using cathodes with varying tube diameters and determining plate thickness
a l o n g t h e d e p t h o f t h e t u b e s .
The concept of microthrowing power is discussed later.