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Ekrtrochlmica Ana Vol 39, No ifS, pp .

1091-1103,1994
Copynaht ® 1994 Ebsuer Semnee Ltd
Pergamon Pnnizd m Gwet B.W. AS Mhta mmnsd
0013-4656,94 $700 + OM
0013 .46S6(94)E0023-5

ELECTRODEPOSITION OF METALS AND ALLOYS-NEW


RESULTS AND PERSPECTIVES
ReNI: WINAND •

Universite Libre de Bruxelles, Department Metallurgy-Electrochemistry, CP 165,50 avenue Roosevelt,


B 1050 Brussels, Belgium

(Received 10 November 1993)

Abstract-After a summary of the theory, Wmand's diagram is introduced This diagram gives the fields
of stability of Fischer's mom types of eleetrodeposits as a function of two main parameters the ratio of
the current density to the diffusion limiting current density (mass transfer) and the inhibition
The diagram has been used at Umversitc Libre de Bruxelles as the basis for the chloride electrodepo-
sition of metals, for high current density plating and electrorefining, and for initiating research concerning
organic additives Important industrial applications have been denved, especially in continuous steel
sheet electroplating The diagram has also been useful for alloys electrodeposition
New research areas include nucleation and imtial growth, substrate influenced transition zone, thin
film electroplating and electrofonmng accurate hydrodynamic characterization of electrolytic cells,
organic additives and secondary inhibition studies under plant simulation conditions, metallographic
image analysis, micro- and nanoalloys studies, time dependent structures investigation, and deposit to
substrate adhesion

Key words electrocrystalhzatton, metals, alloys

1 . INTRODUCTION of the liquid metal or by condensation of the metal


vapor, thus without the presence of foreign atoms
Most of the content of this paper was published and without charge transfer
recently Accordingly, only a summary of the theory In the absence of any crystal of the metal, three-
and of the resulting applications will be given New dimensional nucleation is first needed It is well
trends will be emphasized known that increasing the supersaturation increases
Electrocrystallization will be considered in this the rate of three-dimensional nucleation and
paper as the science and technique of obtaining a decreases the diameter of the nuclei a metal solidi-
solid metal at the cathode of an electrolytic cell fied very quickly has a smaller grain sin than a
Moreover, the field will be restricted to aqueous metal solidified close to the equilibrium temperature
solutions Many factors have an influence on the between the liquid and solid phases
type of deposit obtained at the cathode current An important factor is the interfacial tension it
density J, concentration of the ion containing the appears with exponent three in the equation giving
metal CNez + , agitation, temperature, pH, other the work to generate the three-dimensional nucleus,
cations and anions, complexation, inhibitors, sub- while the supersaturation has only an exponent two
strate, etc In order to solve practical problems, a In an important experiment, Volmer and Ester-
guide is needed to set forth experimental programs roman showed that atoms from the fluid phase that
allowing a reasonable time to fulfil the research collide with the solid are not immediately entrapped
objectives into the lattice surface diffusion must be taken into
Fundamental research is mainly done on single account[4] At the same time, the concept of two-
crystals, while practical problems deal with poly- dimensional nucleation (generation of a new plane at
crystalline deposits A bridge must be established the crystal surface), and one-dimensional nucleation
between these two approaches (generating a new row at the crystal surface) was
introduced
Until it was realized that crystal growth can occur
2. ELECTROCRYSTALLIZATION- by means of the rotational movement of a growing
THEORETICAL CONSIDERATIONS [1-4] spiral originating at a screw dislocation, the ideas of
Kossel and Stranski in[4] were largely accepted, re
There is no true "theory" of electrocrystallization that crystal growth occurs in repeated monoatomic
The field is still largely experimental, and is investi- layers after two-dimensional nucleation The most
gated by comparison with physical crystallization In probable incorporation site is the so-called kink site,
this case, metal crystals are formed by solidification which is at the same time a repeatable step , it is
positioned at the front of a row growing along a
• Keynote lecture presented at the 44th ISE Meeting in growing plane When the row is completed, the next
Berlin best position creates a new one-dimensional nucleus

1091

1092 R WINAND

along the developing plane When this has been More generally, if 6 is likely to vary widely, the
completed, a new two-dimensional nucleus is formed coordinates should be J/J d and the inhibition inten-
Thus, the growth of a single crystal occurs, sity (J, is the diffusion tinting current density)
according to Kossel and Stranski, through com- However, if the meaning and the influence of the first
petition between vertical growth, depending on two- coordinate (J/CM,,- or J/J d) are rather easy to
dimensional nucleation rate, and horizontal growth, understand because it vanes in the same direction
depending on the rate of the repeatable step A not only as the total overvoltage but also of the dif-
perfect crystal grown almost at equilibrium will have ferent parts of the total overvoltage, the second coor-
faces where the energy of incorporation of an dinate (inhibition intensity) deserves more
adatom at the surface of the face is the lowest, explanation
because those planes will have sufficient time to According to Fischer[4, 9], inhibition is due to the
develop laterally presence at the surface of the electrode, in the double
When supersaturation increases, the following layer, or in the diffusion layer, of substances
phenomena occur more than one step are growing (molecules, atoms or ions) different from Me' or the
at a time, so that vertical and lateral growth occur at corresponding adatom These substances hinder the
the same time, other planes may appear, the external cathodic process and are called inhibitors They
shape of the crystal becomes round, a dendrite may usually do not completely cover the cathode surface
appear, and three-dimensional nucleation is finally and favor active sites They are physically or chemi-
observed It should also be remembered that in cally adsorbed They have an effect on the cathodic
physical crystallization, defects in crystal lattice play process and hence on the four types of overvoltages,
a large role (twins and screw dislocations) on the metallographic structure and on the texture
In electrocrystallization, the problem is much of the deposits The sensitivity of metals to inhibitors
more complicated than for physical crystallization is higher when the surface affinity of the metal for
because of charge transfer to a more or less solvated the inhibitor increases, and when the adatoms
ion, the very high electric field at the electrode- surface diffusion coefficient decreases
solution interface (10'Vcm - i) and the presence of Metals can be classed in three groups normal,
adsorbed molecules and ions at the surface of the intermediate and inert Normal metals (Cd, Zn, Sn,
electrode Accordingly, a pragmatic approach is Ag) have low melting points and high exchange
used to apply the knowledge of physical crys- current densities (J0 > 1 Adm -2 ) Intermediate
tallization, one seeks a correlation between the metals (Au, Cu, Ag) have moderate melting points
observed crystalline shapes and the deposits and a and medium exchange current densities (J 0 between
measurable physical parameter characteristic of the 10 -2 and 1 Adm -i) Inert metals (Fe, Ni, Co, Pt, Cr,
supersaturation, ie the cathodic overvoltage Mn) have high melting points and low exchange
The overvoltage is in fact a complex parameter current densities (J0 between 10 -2 and
According to Vetter[5], it can be separated in four 10 -12 Adm -2 ) So-called "secondary inhibition" due
additive terms charge transfer overvoltage q„ diffu- to an adsorbed layer of McOH is usually observed,
sion overvoltage rid, reaction overvoltage q, and even in the absence of any added inhibitor to the
crystallization overvoltage q,, electrolyte Different types of inhibitors may be con-
At first sight, only the crystallization overvoltage sidered, having different effects Inorganic canons,
2+ ,
should be taken into consideration However, it is not dischargeable at the cathode (Na', K', Mg
difficult to measure and a more detailed analysis Cat Al 3 (H+)) have only a small effect, if any,
shows that it is also necessary to take into account pH may, however, play a role especially in "second-
the charge transfer, the diffusion and the eventual ary inhibition" Inorganic amons can change the
reaction overvoltages because they may influence the structure of the double layer, and thus influence the
local distribution of the current density and also the charge transfer overvoltage The activating anions
equilibrium concentration in adatoms (ie metal are Cl - , Br, I - , the intermediate anions are
atoms diffusing at the surface of the crystal before S02- and the inhibiting anions are BF4,
NO-,3
being incorporated in the lattice) at the surface of the NH S022-, CIO- The organics in solution have
metal various effects, they give strong inhibition if they are
Due to experimental difficulties, a detailed analysis adsorbed at the metal and have no affinity for water
of the total overvoltage is usually lacking As making Organics in colloidal suspension are often strongly
use of the total overvoltage as a single parameter adsorbed at the metal, and it is difficult to avoid
does not allow us to explain the observed crystal some secondary inhibition
shapes, the author has suggested[6, 7] that use Inhibition intensity is obviously a complicated
should be made of two main parameters the ratio parameter Many problems are still to be solved
J/C M,,- , the apparent cathodic current density to before satisfactory theoretical considerations can be
the bulk concentration in metallic ions to be dis- derived In this paper however, inhibition intensity
charged, and the inhibition intensity will be assumed to be linked through a biunivoqual
Although the approach was initially mainly intu- relationship to the concentration of a given species
itive, it can be shown[2, 8] that if the hydrodynamics in solution or adsorbed at the surface of the metal
of the electrolyte flow is constant, at any spot in a the inhibitor
diagram having J/C M „t and the inhibition intensity Experimental work largely shows that the same
as coordinates, it should be possible to calculate (or observations are made in electrocrystallization and
assign) a value for q, and P1, the exchange current in physical crystallization[10-14] It was observed
density J o being, at a given inhibition intensity, func- however that screw dislocations are easily blocked
tion only of J/CM„ • and 6 by adsorbates, so that the growth mechanism based

Electrodeposition of metals and alloys 1093

J IC Me

Very Very
Low Medium High
low high

No deposit FI dendrites Fl powder


or Fl or screw _
Very
dislo- ~ ~~
low cation G p~ O
Nonur
leation increases 9 y .. N c, 2 cre s,n
.,n___
_ ._ .____s_ _9 _N c,3
BR BR BR Fl Fl powder
N or
°
z % y i bad
Low hydrogen
Y a
crystal-
F lization evolution
_ mcreasin N mere sin N c .3 or
-_gig fl_
C BR BR ZorFT FT UD discharge
' of M/ _M== of
+
Medium ZwErn another
ion
Y
a
t z FT UD UD
G ~.
..
High ;~

z, zZ in powder
w' o"
UD E' LID EE,
h dro en evolution
Very or
high _ discha ge of anott er ion
in powder y

Fig I Detailed diagram showing different possible types of polycrystalline electrodeposits as a function
of J/C,,,, • and inhibition intensity

on one- and two-dimensional nucleation and the ation in the thickness of the deposit AN these con-
repeatable kink site plays the important role[15-293 siderations are summarized in Fig 1 .
Growth steps are generally thicker than one atomic Fischer[4] proposed five main growth types of
layer (bunching effect)[30-32] The crystalline shapes polycrystalline electrodeposits
result accordingly from a competition between (1) field orientated isolated crystals type (FI),
growth parallel and perpendicular to the substrate (2) basis-orientated reproduction type (BR),
The latter depends on the two-dimensional nucle- (3) twinning intermediate type (Z),
ation frequency. It was observed experimentally that (4) field orientated texture type (FT),
the thickness of the growth layers increases with (5) unorientated dispersion type (UD)
current density, but decreases when inhibition The first type (FI) is usually observed at low inhi-
increases Thus, the lateral growth speed decreases at bition With increasing current density whiskers,
constant inhibition when the current density prismatic crystals, dendrites and, finally, powder
increases, favoring isolated crystals, or even den- deposits are successively obtained The second type
dntes On the contrary, when inhibition increases at (BR) is observed at moderate inhibition and/or
constant current density, the lateral growth speed current density Sufficient time is available for good
increases, giving dense and coherent deposits At lateral growth, though the crystals may become large
very low inhibition and at very low values of the enough to entrap electrolyte in the deposit If the
ratio J/Css,, • , it is possible that not enough energy electrolysis proceeds for a long time, surface rough-
is available to generate two-dimensional nucleation ness increases, and BR type can be degraded to FT
The growth of the deposit is only possible in that type Type three (Z) is considered by Fischer as being
case if screw dislocations are available and active intermediate between types two (BR) and four (FT)
Finally, when the inhibition intensity and/or the The fourth type (FT) is observed at fairly strong
value of the ratio J/Ci,• . • are high enough, new inhibition and/or current density and is character-
crystals are generated by three-dimensional nucle- ized by a large number of elongated crystals perpen-

1094 R WINAND

dicular to the substrate, forming a coherent deposit crystallization problems, some experimental results
Type five (UD) is obtained at still higher inhibition obtained in the author's laboratory will be discussed,
and/or current density It is formed by a large and their eventual industrial use emphasized For the
number of small crystals, forming a coherent deposit electrodeposition of metals, the first idea was to vali-
Except for the first type (FI) which can be identi- date the diagram Industrial applications were
fied by direct external observation of the deposit, derived during that process As it was soon realized
cross section metallographic examination is neces- that organic additives have a complex behavior, pure
sary to do so for the other types It should also be solutions were studied first The vertical coordinate
emphasized that the different types of deposits are was in that case checked by making use of different
thus defined on a metallographic structure basis, and metals, eventually with different anions The hori-
not on a crystallographic texture one it is well pos- zontal coordinate was checked by changing the
sible to observe FT and UD deposits of a given current density and the agitation Organic additives
metal, having the same crystallographic texture were considered separately The influence of the sub-
However, the four first types of deposits are obtained strate on initial crystallization and growth resulted
through two-dimensional nucleation only (or even- in new applications in thin films For the electro-
tually without nucleation for FI crystals if a screw deposition of alloys, hydrogen evolution was identi-
dislocation is active), whereas the last type requires fied as an important side factor in mass transfer, and
three-dimensional nucleation These main growth slow room temperature changes of crystallographic
types are included in Fig 1, showing their fields of structures after electrolysis were observed New
stability Figure 2 is only a simplified version of Fig research areas are also emphasized
I It should be kept in mind that boundaries between
the fields of stability are not abrupt, except between
two- and three-dimensional nucleation Moreover,
Electrodeposition of metals
the diagram does not take into account the influence
of the substrate it is based only on electrolysis Validation of the diagram without organic additives
The vertical coordinate inhibition intensity
parameters Fischer introduced two more types of
deposits[33, 34] nodular (N) and rhythmic lamellar
• Silver from nitrate solutions[35]
(RL) They correspond to special cases, difficult to The silver lattice is face-centered cubic Although
very different results are obtained depending on the
include in the general diagrams of Figs I and 2
measurement method, its exchange current density in
pure nitrate solutions is high, in the order of 10-
3. APPLICATIONS 100A dm -2 The anion NO3 was found to be slight-
ly activating
To illustrate the way the diagrams of Figs 1 and 2
Accordingly, the metal should show low inhibition
can be used or interpreted in connection to electro-
intensity, and the deposits should be of the type
described in Figs I and 2 on the horizontal line near
the abscissa coordinate Experimental results show
in fact that after a thin layer of BR type crystals
grown by epitaxy on the silver substrate, large den-
dntic crystals of FI type are observed (Fig 3)
This is well known in silver electrorefining, where
these crystals are continuously removed from the
cathode by moving arms in order to avoid shorts
with the anode The thickness of the dense BR layer
was found to increase if the silver concentration in
solution increases and/or if the current density
decreases These observations did not find any prac-
tical interest
• Copper from pure sulfate solutions[26, 36, 37]
The copper lattice is face-centered cubic Exchange
current density values are found between 10 -3 and
Fl Field oriented isolated crystals,
lOAdm - ' in pure solutions The most probable
BA Basis reproduction, values are between 0 2 and 2 A d in -z
Fr Field oriented texture type, H 2 SO, acts as a very weak inhibitor Accordingly,
UD Unmerited duipersion type
the deposits should be on a horizontal line at low or
medium inhibition intensity in the diagrams of Figs
ii abuisu masstrans rercharactenzedby31c„z .orJ/J,
em density 1 and 2 In fact, experimental results show BR (Z),
i1M i, bulk concentrationofmetal on to be discharged FT and UD deposits at increasing values of the ratio
J,' diffusion limiting current density
J/C on , . Crystallographic texture is found to be (110)
tocedione inhibmon,nteneny
at 50°C
20 bid, .ene.onal nudeamn • Copper from pure chloride solutionsi[38, 39]
3o mdtmen„onainudeaion
In concentrated chloride solutions, Cu can be sta-
bilized in complex chloride species This makes it
Fig 2 Simplified diagram showing different possible types possible to operate an electrolytic cell with the
of polycrystalline electrodeposits as a function of J/CM. z cathodic production of copper by the use of one elec-
and inhibition intensity tron instead of two in sulphate solutions, and with

Electrodeposition of metals and alloys 1095

Fig 3 Typical silver deposit obtained from a pure nitrate solution Thin BR layer on the substrate
followed by large FI dendntea The distance between two lines on the scale is 1 mm (from [35])

the anodic oxidation of Cu' to Can instead of oxygen


evolution in sulfate solutions Owing to a better
reversibility of the reactions and to the high electri-
cal conductivity of the solutions, copper electro-
winning could be operated in chloride solutions at
about a quarter of the specific energy consumption
needed for sulfate solutions However, exchange
current densities for the reduction of Cu' to Cu°
were found in the range of 20-30Adm -2 Accord-
ingly, copper should show in chloride solutions a
behavior very similar to that observed for silver in
nitrate solutions This is effectively the case as shown
in Fig 4 without added inhibitor, a horizontal line
is followed in Figs 1 and 2 at very low inhibition,
and BR-F1 deposits are obtained Replacing sulfate
anions by chloride anions resulted in a decrease of
the inhibition intensity, in agreement with Piontelh's
classification of anions The crystallographic texture
of the BR layer is (110) like in sulfate solutions
• Cobalt from pure chloride solutions[40, 41] .
The cobalt lattice is either h c in its a allotropic
form (stable at room temperature) or face-centered
cubic in its ft allotropic form (metastable at room
temperature) Cobalt is mainly deposited from
sulfate solutions in electrowmning . It shows very low
exchange current densities (10 -10-10 - sAdm -2) in
pure sulfate solutions, and accordingly has a high
charge transfer overvoltage. Metallographic struc-
tures are highly degraded FT and UD, usually
nodular As chloride ions are known to be activating
anions, research was started in the author's labor-
atory to investigate the possibility of achieving better
results in chloride than in sulfate solutions
In pure chloride solutions, exchange current den-
sities were found to be around 10 -5 Adm -2 if the
pH was lower than 3 .5, and around 10' 2 dm -2 if the
pH was between 4 and 5 Cobalt a was found to be Fig 4 Optical micrograph of a deposit obtained from a
the predominant species in every deposit . At high pH 0 7 M CuCI 4 M NaCl, 0 5 M HCl solution at 30°C, 24 h,
(4-4.5), the overvoltage is low, and BR to FT types 25Adm" 2 Thin initial continuous layer partially BR, fol-
deposits were obtained (Fig 5), corresponding to lowed by Ff possibly twinned (from [3g])
1096 R WINAND

Fig 5 BR and FI types observed from cobalt deposited from pure chloride solutions at pH 4-4 5 (from
[41])

medium inhibition instead of strong inhibition agent[42] (Fig 6) At low pH (1), the overvoltage is
observed in sulfate solutions Cobalt a is strongly moderate, with cobalt a again textured (1120) Good
textured (1120) At medium pH (3-3 5) bright depos- deposits could be obtained with good current effi-
its also textured (1120) could be obtained without ciencies even at high current densities (SOAdm' 2)
added inhibitors, and some further research was where UD type deposits were observed
done, aimed to bright cobalt plating without leveling The overall behavior of cobalt in chloride solu-

Fig 6 Reflective power of a bright cobalt deposit Solution I M CoCl z , I M NaCl, 25'C, 32Adm -2
Cobalt deposit 3 pm thick on a copper deposit 3 pan thick Steel substrate (from [42])

Electrodeposition of metals and alloys 1097

tions could be interpreted in terms of secondary inhi- on a full industrial scale (15m width steel strip) in
bition, with two different mechanisms . by CoOH the Hall for testing prototypes of the Centre de
adsorption at high pH, resulting in a horizontal line Recherches Industrielles of UniversitE Libre de Brux-
at medium inhibition in Figs 1 and 2, and by atomic elles in Nivelles (near Brussels) the Flash Cell, This
hydrogen adsorption at low pH, resulting in a hori- cell was designed to achieve two sides deposits on
zontal line at high inhibition intensity in the same the moving steel sheet Current is fed to this sheet
diagram acting as the cathode by means of a large conducting
From these experimental results, it can be con- roll Electrolysis occurs in a very compact cell where
cluded that the behavior of a metal in a pure solu- the steel passes between insoluble perforated anodes,
tion (without organic additive) can be represented on the electrolyte being injected at high speed through
a more or less horizontal line in the diagrams of Figs the holes in the anodes, perpendicular to the steel
1 or 2 whose position along the vertical coordinate sheet This cell was operated satisfactorily up to
depends on the value of the exchange current density 450Adm -2 It is now in continuous use in a full-
Jo the higher the value of J o , the lower the inhibi- scale experimental production line at Cockerill-
non intensity Sambre, in Liege .
Zinc alloys were also studied for high current
The horizontal coordinate J/CM, .- or J/J, (mass density plating[8, 49-51] . It was shown that when
transfer) the current efficiency is low, hydrogen evolution con-
The validity of this coordinate was checked for tributes noticeably to the mass transfer to the
copper in a pure sulfate solution, in a flow through cathode, and could result in inhomogeneous alloy
channel cell[36] Transition from FT to UD was composition on the steel sheet if hydrodynamic con-
shown to occur at a "constant" value of the ratio ditions are not the same over the whole cathode
J/J, (approximately 035) independent of the electro- surface This point will be further emphasized in the
lyte flow rate H,SO, acts as a very weak inhibitor, paragraph dealing with clectrodeposition of alloys
so that surface roughness increases with time accord- Electrocrystalltzation in presence of organic addi-
ing to Despic's theory[43] . tives For silver in nitrate solutions, due to the high
Accordingly, dense deposits showing acceptable exchange current density, the metal was found to be
surface roughness for electrorefining were obtained only slightly sensitive to inhibitors[52, 53] With
in the laboratory up to a maximum thickness of thiourea, it was necessary to add 100mgl - ' of inhib-
-2
2mm at current densities up to 30Adm with the itor (te the solubility limit) to convert the BR struc-
electrolyte flowing at 3ma - t parallel to the cathode ture suddenly into UD, with, however, a huge sulfur
To reach higher thicknesses, organic additives are contamination of the deposit Better results were
needed[44] On the contrary, if plating is considered, obtained with sodium potassium tartrate As
very high current densities (SOAdm -z and beyond) expected, it was also very difficult to improve the
can be used[36] Looking for industrial applications, structure of copper deposits from chloride solutions
zinc plating on steel was considered . Laboratory 03gl - t of gelatin was necessary to obtain good
scale experiments were performed in a flow through dense deposits, of FT to UD types[54]
channel cell, making use of a BOgr - i Zn 2 +, 135 gl - i More research was devoted to copper in sulfate
H,SO, pure sulfate solution, at 50°C, with soluble solutions In an early research, it was found that
zinc anodes and low carbon steel as catbodes[45, polyacrylamides could improve the structure of
46] Very good deposits were obtained up to very electro-won copper cationic ones give FT deposits
high current densities Figure 7 shows that instead of already at 1mg1 -2 [55] It was also found, making
irregular and cratered deposits obtained at low use of a small continuous laboratory experimental
current density, those obtained at high current set-up simulating the electro-winning part of a
density are rather smooth and well crystallized Pro- solvent extraction plant, that at increasing concen-
cesses and equipment were further studied with a tration of Jaguar (commercial name for Guar Gum),
view to their application in continuous plating of a "vertical" line is followed in Figs 1 and 2, leading
steel sheet The Belt Cell was designed to achieve a successively to BR, FT and finally UD types of
one side deposit on the steel sheet in a flow through structures[56] Figure 8 shows a satisfactory FT
channel cell including a clamped anode-soluble or structure
insoluble-and the moving steel sheet as the In the development of a process for high current
cathode The current is fed to the cathode by means density copper electrorefinmg in collaboration with
of electric brushes sliding on a continuous belt Metallurgic Hoboken-Overpelt[44], it was found
moving in the same direction and at the same speed necessary to make use of organic additives in order
as the steel sheet It was scaled up to 03in width to achieve the high deposit thicknesses required for
steel strip and successfully operated in the author's industrial productivity Testing was performed at the
laboratory up to 300Adm -2 and steel sheet speed large laboratory scale, in a closed loop electrolyte
up to 600mmm - t on a large laboratory circwt including a two cathodes-two anodes pseudo-
prototype[47, 48] The process was further tested on bipolar flow through channel cell It was found that
a full industrial scale at Acienes et Laminotrs de very low organic additives concentrations were
Beautor, a French subsidiary to the Belgian group enough This could only be explained on the basis of
Cockerdl-Sambre As it was only possible to test the the hypothesis that these additives are somehow
cell in a production line, research was stopped before consumed at the cathode at their own diffusion limit-
success was achieved . Meanwhile, another simplified ing current density Bockns and Razumney give
cell was developed, tested as a large laboratory some support to this hypotbesis[57] . It was neces-
prototype at UmversitE Libre de Bruxelles and later sary to make use of an experimental strategy to find
1098 R WiNAND

Fig 7 Surface of lOpm thick zinc deposits on steel Pure sulfate solution 80gl - ' Zn", 135gI - '
H 2 SO4 , 50°C Electrolyte flow rate 3ms - ' I lOAdm - i (a) x 100, (b) x 1000 11 200Adm - ' (a) x too,
(b) x 1000

the suitable combination of halogen tons (chloride or gelatin concentration, and on the other hand that
bromide), thiourea and gelatin concentrations The although cysteine (a molecule similar to thiourea)
best conditions in a 396g1 - ' Cue+, 174g1`' gives readily UD types of deposits (re grown under
H 2 SO4 industrial sulfate solution can be sum- three-dimensional nucleation regime), the overvol-
marized as follows 2OAdm -2 , 14-18ms - ' elec- tage is smaller than with gelatm[58, 59] This can
trolyte flow rate, (Br - + C1) ions concentrations only be explained if interfacial tension is taken into
40mg1 - ', Br - ions concentration 15-25mg1 - ' consideration All efforts should be made to derive a
02mg1 - ' thiourea, 01mgl - ' gelatin ASF Deposits method of measurement of the interfacial tension
were satisfactory for electrorefinmg up to 12mm during electrodeposition of the metal
thickness In another investigation[60], it was shown that it
Meanwhile, fundamental research was undertaken is absolutely necessary to add the organic molecules
on the influence of additives on copper deposits in a continuous way to the circuit, instead of adding
under normal electrorefining conditions It was them all at once at the start of the experiment
found on the one hand, that although gelatin alone Moreover, it is necessary to simulate as far as pos-
leads to a high cathode overvoltage, deposits are sible the industrial plant in order to obtain compara-
always of the FT type (ie grown under two- ble results[61, 62] This is due to the fact that gelatin
dimensional nucleation regime) over a wide range of undergoes rapid degradation at 60-65`C in concen-

Electrodeposition of metals and alloys 1099

residence time of the electrolyte m the electrolytic


cell, same current density, industrial electrolyte and
soluble anode) The sensor works under well-defined
hydrodynamic conditions at J/Jd similar to that of
the industrial electrolytic cell, allowing the measure-
ment of the steady-state cathodic overvoltage on a
continuous basis It is also necessary to use a control
monitoring strategy Chloride ion concentration and
the ratio thiourea/glue are kept constant, so that the
measured overpotential depends only on one factor,
ie the global orgamcs flow added to the solution[63]
Despite all these precautions, it was found that the
redox potential of the solution must also be the same
as in the plant, that initial activation of the copper
continuous sheet used as cathode in the sensor was
Fig 8 Metallographic cross-section of cathode obtained m
laboratory Gecammes electrolyte with 4mg1 - ' Jaguar, necessary, and that 30µm thick copper deposits are
55°C, 24A dm - Q, 48h, Fr type (from [56]) necessary before a stable cathode overvoltage can be
measured, comparable with steady-state industrial
conditions This last observation suggests that the
structure of the deposit is influenced by the substrate
trated sulfuric acid solutions, and also to the very up to this thickness, even if some epitaxy occurs at
complex chemistry of thiourea in these solutions the start of the electrolysis This was recently
Thiourea converts immediately to observed in the laboratory when electrodepositing
dithioformatmdme, which forms complexes of Cut copper on anodized titanium without organic
and Cu' Reactions are also possible at the elec- additives[64] Figure 9 shows that the initial layers
trodes are highly disturbed, many twins being visible under
These ideas were used in an attempt to monitor the transmission electron microscope Slow rec-
continuously electrorefimng additives[63] The rystallization at room temperature was even
experimental set-up simulates the industrial plant observed
(same ratio of the electrolyte volume to the cathode Further research on the role of additives in copper
area, same ratio of the bleed flow to the cathode electrorefimng is in progress in the laboratory in col-
area, same hydrodynamic conditions, same laboration with a number of copper refiners It is

Fig 9 TEM observation of a (I11) Flr-UD copper deposit on polished titanium The section perpen-
dicular to the substrate shows a high degree of twinning.

a3 aril
1100 R WINAND

hoped that it will be possible to derive the influence difficult to achieve under these conditions than in a
of each separate additive in a solution containing the simple beaker, introducing the additives all at once
three additives at the same time, making use of the at the beginning of the electrolysis It should be
same principles as for the monitoring research remembered however that one of the reasons of the
New research areas The diagram of structures observed progressive decline of interest for electro-
was derived for deposits shapes conditioned by elec- deposition of metals is linked to the very poor
trolysis parameters The substrate influenced zone, understanding and control of inhibition processes It
however, plays an important role for thin deposits is hoped that well defined experimental conditions
and must be investigated In collaborative research will improve our knowledge in this field
with the University of Rolla, Missouri, nucleation of Secondary inhibition deserves also more detailed
electrodeposited copper was studied on anodized studies In this case, no organic additive is necessary,
titanium in pure sulfate solution[65] It was found which is a very important advantage from an indus-
that the oxide film plays an important role during trial standpoint However, very close control of pH
nucleation It was possible to decrease the diameter and hydrodynamics conditions must be achieved in
and to increase the surface density of copper nuclei order to obtain reproducible results
by increasing the thickness of the anodic film The In order to quantify the diagrams of Figs 1 and 2,
kinetics of nucleation and growth of the copper specific metallographic image analysis computer pro-
deposits were tentatively analyzed according to theo- grams must be developed This work started recently
ries of Thirsk and Harrison[66], the deposits being at Universite Libre de Bruxelles, in the frame of a
examined by SEM Production of thin copper foils research program involving Region Wallonne an
on microporous titanium oxide substrates was also Cockenll-Sambre
studied in an additive-free electrolyte Each pore Finally, adhesion to substrates is another very
seems to act as a nucleation site, leading to a high important topic, presently investigated at Universite
surface density of copper nuclei Stripping of the foil Libre de Bruxelles It is suspected that some inter-
from the substrate was easy[67] mixing of atoms can occur at a substrate/deposit
Recently, Vanden Brande[68, 69] showed that interface, when the substrate has high enough an
under galvanostatic conditions, during the very first exchange current density in the electrolysis solution
stages of copper electrodeposition on amorphous
Elect rodeposirion of alloys
carbon and electrocrystalline silver substrates, an
island growth mode is observed with a higher cluster Electrocrystallization of alloys is more difficult to
density on silver substrates than on carbon sub- study than pure metals, due the the codeposition of
strates Dissolution of some copper clusters occurs a at least two metals, and to the various possible crys-
short time after the onset of electrolysis, and an tallographic structures arising from the phase
exclusion zone appears around the remaining clus- diagram Moreover, phases determined by X-ray dif-
ters (Fig 10) It is suspected that as only these last fraction are often different from thermal equilibrium
ones will continue to grow, most results described in In spite of this, Fischer's main types of deposits are
literature are dealing with these growing crystals observed, including N and RL Almost amorphous
instead of initial nuclei Observations made in the deposits are also obtained
laboratory under the above-mentioned galvanostatic It should be emphasized that adatoms from one
conditions show that the current efficiency, goes species can act as inhibitors or catalysts for the
through a minimum when islands dissolution is fin- deposition of the metal of the other species In the
ished The value of the minimum current efficiency first case, when deposition of the more noble metal is
increases with the current density This is also the inhibited, so-called anomalous codeposition is
case for the islands density at this time It seems observed according to Brenner's classification in the
accordingly possible to achieve a complete coverage second case, when deposition of a metal makes pos-
of the substrate with very small islands correspond- sible the deposition of another one which cannot be
ing to the initial nuclei, without exclusion zone, but obtained alone, so-called induced codeposition
very high current densities are necessary to achieve occurs according to the same classification
this result The laboratory equipment used in this In both cases, current efficiencies can be low, and
research was not designed for such high current den- hydrogen evolution strongly influences J, Uniform
sities It should be mentioned however that the large current density and hydrodynamic conditions are
research and development equipment mentioned necessary to obtain reproducible results The zinc-
above in this paper for continuous steel electro- iron system will be used as an example[8, 50, 51]
galvanizing gives complete coverage of the substrate Zinc strongly inhibits iron deposition in sulfate solu-
with zinc starting from the deposit thickness of 0 1 tions, and the system falls in the anomalous codepo-
micrometer, at 450 A dm - ' sition category (Fig 11) Current efficiencies vary
Further studies in this area should combine SEM, widely between 10% and more than 95% in function
TEM, Auger and the new STM, AFM and LFM of current density and electrolyte composition
investigation methods Hydrogen evolution can be so effective that with an
Organic additives must be studied under plant electrolyte flowing at 2ms - i parallel to the cathode
simulation conditions, with the organics introduced in flow through channel cells, it can enhance mass
continuously throughout the experiment, as already transfer to the cathode more than twice (Fig 12)
explained Moreover, if several additives are to be This can result in very important changes in the
used simultaneously, variations around the set point composition, surface appearance and metallographic
must be studied in order to take into account syn- structure of the deposits as emphasized in Figs
ergetic effects Of course, experiments are much more 13-15 It is very clear from Figs 13 and 15 that

Electrodeposition of metals and alloys 1101

a b

c d
Fig 10 Initial stages of nucleation and growth of a copper electrodeposrt on amorphous carbon 05M
CuSO.20gl - ' H 2 SO, daerated solution at 25°C, 3 Adm -2 Quantities of electricity (a) 0 6Cdm -2 , ( b)
1 C dm -2 , (c) 5 C dm -2 , (d) 9 Cdm -2

surface microscope examination does not allow to characteristic parameters in the vicinity of the
conclude concerning the corresponding metallo- cathode proved recently to be more useful than
graphic cross section global ones like the mean flow velocity or the hydro-
New research areas in alloy elecirodepo- dynamic diameter of the cell[70]
sition Accurate hydrodynamic charactenaation of Another way to unprove deposit quality when
electrolytic cells is essential to allow satisfactory J/J, control is not easily achieved is to make use of
upscahng and to achieve homogeneity of the depos- organic additives This may result in enlarging the
its For high productivity coil coating cells, local field of J/J, values giving constant deposit proper-

R WINAND

the behavior of a binary system (zinc-iron) from


anomalous to normal[71]
Finally, time-dependent structures are sometimes
observed, involving room temperature recrystal-
lization[72] This should be studied carefully, in
order to ensure that functional properties remain
constant during the material life

4. CONCLUSIONS

Although there is no true theory of electro-


crystallization, a pragmatic approach to the problem
has allowed the author to derive a diagram (Figs I
and 2) where the fields of predominance of the main
types of metal deposits according to Fischer's classi-
fication can be shown as a function of two param-
eters J/CM,,- (or J/J,) for mass transfer and the
inhibition intensity The diagram holds for deposit
90 tan shapes conditioned by electrolysis parameters
s Fe e Up to now, the diagram has been largely qualit-
ative, and values can only be attributed to the coor-
Fig 11 Atomic percentage of non in Fe-Zn alloy from dinates for every specific case, depending on the
sulfate electrolyte against Fe/Fe + Zn m electrolyte at 50°C
metal, the type of solution, and the added organic
and electrolyte velocity 2ms - ' with H,S04 02M at (1)
-2 inhibitor, if any However, it can be said that when no
200Adm -2 , (2) 100Adm , ( 3) 50Adm -2 and (4) with
-2 organic inhibitor is added to the solution, the types
20 A dm
of deposit observed follow almost a horizontal line
in the diagram as a function of J/C M,,+ at constant
electrolyte flow rate, the position of this line being
ties However, a considerable research effort is dependent on the charge transfer-exchange current
needed to understand the organic additive chemistry density Jo from the metal in this specific solution
and electrochemistry, in order to be able to maintain the higher J 0 , the lower the inhibition intensity
constant the inhibition intensity, as already Moreover, it was shown for copper in sulphate solu-
explained Monitoring problems should also be tions that transition from FT to UD types occur
solved almost at constant J/J, ratio, independently of the
Nucleation and initial growth must be investi- electrolyte flow rate When an organic inhibitor was
gated in order to achieve uniform and reproducible added to the solution, "vertical" lines were found in
functional properties for thin, ultrathin and multi- the diagram for a few cases However, quite a
layered deposits Adhesion to the substrate is of number of problems remain to be solved before the
special interest in electroplating situation is clearly understood Nevertheless, as such,
Micro- and nanoalloy deposition deserves specific the diagram (as shown in Figs 1 and 2) is very useful
research programs For instance, the presence of as a general guide when searching to improve the
minute amounts of a third codeposited element structure of polycrystalline deposits High current
(antimony) was recently shown to change completely density processes in sulfate solutions and others in

06

D 5 10 15 20 25 30 35

Jg1/2 (mA c1n 2 )

Fig 12 Relation between the mass transfer coefficient for zinc and the square root of the hydrogen
partial current density Zn-Fe sulphate electrolytes 02M H,SO 4 , 50°C, electrolyte velocity
2ms-'[33]( •) Fe 075M .Zn 075M,(0)Fe IM,Zn 05M,(A)Fe 1 M,Zn 01M


Electrodeposmon of metals and alloys 1103

NODULAR (N) RYTHMIC LAMELLAR (RL)

FIELD ORIENTED (FT) UNORIENTED DISPERSED (UD)


Fig 13 Various metallogaphic structures observed in the system Fe-Zn N, RL, FT and pseudo UD
(later shown as BR) structures are observed[32], (a) nodular (N), (b) rythmic lamellar (RL), (c) field
orientated (FT) and (d) unonentated dispersed (UD)

chlorides solutions have been developed in the


. en
author's laboratory, with the scientific background
rioiu sJ being based on this diagram
• nut a
Fe d fs1 Further improvement of the diagram should be
° nL
based on time dependence, including nucleation,
100
r- -71 initial stages of growth and transition from the first
layers of deposits that are influenced by the substrate
e0 -
to the bulk and the surface of the deposit mostly
influenced by the electrolysis conditions
Electrocrystallization of alloys is more difficult to
60 -
study than for pure metals However, Fischer's main
RL
N o
types of deposits are observed, including nodular
and rhythmic lamellar structures Amorphous depos-
40 -
its are also obtained Accurate hydrodynamic char-
acterization of electrolytic cells is of special interest
to allow satisfactory upscaling, taking into account
20 -
0 hydrogen evolution As alloys are mainly used in
FT
0
electroplating, the substrate plays an important role
0 and it should be checked that the deposit thickness is
8
BR high enough to allow use of the diagrams of Figs 1
0
50 100 iso 200
and 2 Further research is accordingly needed in the
Je (A/dn2 ) fields of nucleation and initial growth for thin, ultra-
Fig 14 Cross section metallogaphic structures of alloy thin and multilayered deposits Adhesion to the sub-
deposits as a function of current density and composition strate must be studied Micro- and nanoalloys, and
Channel cell 02 M H 2 SO4 with Fee and Zn2 ' as sulfates time-dependent structures deserve specific research
at 50°C Electrolyte speed 2 in s - 1 [34] programs

1104 R WiNAND

Fed = 1 Fed = 10%

Fe d = 13 Fed = 36

Fed = 54 Fed = 100


Fig 15 Surface mwr pe ex matron of vanous Fe- deposits annel cells 02M H 2 SO 4 with
Fe" and Zn 2 + as sulfates at SO°C Electrolyte velocity 2ms - ' current density IOOAdm"[32], (a)
Fe, = 1 %, (b) Fe, = 10%, (c) Fee = 13%, (d) Fe, = 36%, (e) Fe . = 54%, (1) Fe, = 100

Electrodeposition of metals and alloys 1105

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