TECHNICALLY

speaking
BY MALTANAVA H.M.1, VRUBLEVSKAYA O.N.2*, VOROBYOVA T.N.1

Electrochemical Deposition
of Gold-Tin Alloy from
Propyleneglycol Electrolyte
ABSTRACT
Stable and simple in composition nonaqueous propyleneglycol (PG) electrolyte containing tetracyanoaurate(III) and tin(IV) chloride pentahydrate in mole ratio 1:14 has
been developed for the electrochemical deposition of goldtin alloy with the elemental, phase composition and microstructure acceptable for soldering in electronics. This
electrolyte provides deposition of AuSn coatings at a rate of 2.4 mg/cm2h (1.8 m/h
accounting the alloy composition) and to obtain alloys which consist of Au5Sn and AuSn
crystalline intermetallics containing 1467 at.% of tin (optimal 39 at.%) in total that
corresponds to the composition of eutectic applicable as a solder. Coatings have a very
uniform tightly packed and ne-grained microstructure and are composed of spherical
grains 0.11.0 m in diameter and average size of 0.2 m. The addition of water or full
change of PG on water fastens the rate of coating deposition and stipulates the formation of coatings with mush less tin content, more coarse-grained microstructure and
predominance of gold or gold-enriched intermetallics in their phase composition. The
effect of the electrolyte composition and the regime of its work on the elemental and
phase composition of coatings, their microstructure and the rate of deposition have
been determined. The role of PG in the process of mutual gold and tin electro-reduction
and intermetallic compounds crystallization has been found out.

INTRODUCTION
Gold is applied in electronics, optoelectronics and instrumentation for
production, not only of electrical contacts, connective elements, protective
and decorative coatings but also of
soldering materials for packaging.
AuSn alloy is the best one for this
purpose. Its usage answers tendencies
to refuse the traditional lead-containing alloys and to extend the spectrum
of the desired functional properties of
solders. AuSn eutectic alloy contains
30 at.% of tin included into (Au5Sn)
and (AuSn) phases1, 2. Its melting
point is 278C and thus it belongs to
high-temperature solders unlike leadfree tin binary and ternary eutectic
1. Belarusian State University
2. Research Institute for Physical-Chemical Problems of
Belarusian State University, Minsk 220030 Belarus
e-mail: vrublevskaya.olga@gmail.com,

alloys with silver, copper, bismuth,

indium, silver and copper, silver and
bismuth. Their melting point is close
to PbSn eutectic and varies from
118C (SnIn) to 220C (SnAg). The
distinction peculiarities of AuSn
alloy provide its usage in high power
devices when much heat is evolved at
functioning. It is indispensable for
integrated circuits, laser diodes and
other devices because it provides hermetic sealing owing to good surface
wettability of the surfaces under connection, low viscosity at melting point
and lling the cracks in a substrate.
Besides, it is compatible with thin
gold and copper lms, has high corrosion stability, good thermal- and
electroconductivity.
Traditionally gold-tin solder is produced by the metallurgical method
with subsequent alloy rolling and

28 | metalnishing | November/December 2013

stamping to obtain wires or preforms

(ribbons, pellets, ring frames)3. This
method is rather chip but it is difcult
to produce preforms with miniature
size, complicated shape, small thickness and strict planarity. The usage of
AuSn solder paste eliminates most
of these lacks. This method includes
the stages of tin and gold alloying,
sputtering the alloy for powder production, mixing the powder with a
ux in a volatile solvent4. Unfortunately, the alloy in pastes is easily oxidized at the storage and soldering that
worsens the quality of a connection.
Traditional for electronic industry
is AuSn alloy sputtering in vacuum.
This technology permits to control
the size and thickness of a soldering
material and to prevent its oxidation5,
but the process is energy-consuming,
requires expensive equipment and
highly trained personnel. Besides, it
is difcult to control Au: Sn ratio and
phase composition in the alloy
because of a great difference in partial
pressure of gold and tin vapors.
The alternative method is electrochemical AuSn alloy deposition. It is
prospective because of potential abilities to control elemental and phase
composition of a solder, the thickness
and planarity of the solder layers and
their size. The alloy can be obtained
by sequential gold and tin lms electroplating, but this technology is
complicated by extra operations of
multiple individual metal layers formation, strict thickness control and
nal thermal treatment for the alloying6, 7. The ordinary simultaneous
electrochemical reduction of gold and
tin from their compounds is performed using aqueous electrolytes of
three types such as acid solutions containing tetracyanoaurate(III) and
tin(IV) ions8, 9; slightly aside solutions
on the base of tetrachloroaurate(III)
and tin(II) ions10; alkaline electrolytes
containing dicyanoaurate(I) and
tin(IV) ions11. Acid and alkaline electrolytes can irritate the surface of the
substrate. Slightly acid electrolytes are
unstable at the exploitation owing to
oxidation-reduction interactions
between gold(III) and tin(II) compounds and hydrolysis of tin compounds in the bulk of solutions. The
www.metalnishing.com

TECHNICALLY
speaking
main difculties of AuSn alloy deposition from aqueous electrolytes are
connected with not sufcient reproducibility of the coatings quality, their
elemental and phase composition
which are stipulated by reactions in
the bulk of solutions. Moreover, the
problem consists in great difference
between electrochemical potentials of
electropositive gold and electronegative tin that greatly impedes their
mutual reduction at a requisite
ratio.
It seems possible to prevent the
hydrolysis of tin compounds and to
facilitate the mutual gold and tin
electrochemical reduction by the
usage of non-aqueous electrolytes.
This idea is conrmed by the results
of the previous work12 in which the
possibility has been shown of electrochemical goldtin alloy deposition

www.metalnishing.com

from a stable electrolyte with ethyleneglycol (EG) as a solvent. The

deposited alloy consisted of Au5Sn
and AuSn crystalline intermetallic
compounds and maintained 2735
at.% of tin that responded to composition of the AuSn solder. Comparing to aqueous baths this EG electrolyte provided a low rate of the coating
deposition equal to 1.31.9 m/h that
was about 5 times lower than in case
of aqueous electrolytes. The lack of
this electrolyte is the toxicity of EG as
a solvent. Its substitution on propyleneglycol (PG) looks attractive.
The purpose of this investigation
was to develop PG electrolyte for electrochemical deposition of goldtin
alloy with the composition and
microstructure acceptable for the
usage in soldering and to detect the
inuence of the current density and
temperature, gold(III) : tin(IV) ratio,
the presence of water on the rate of
plating, elemental, phase composition and surface morphology of the
gold containing coatings.

EXPERIMENTAL
Compositions of electrolytes for
AuSn alloy electroplating which provide the deposition of qualitative
coatings are presented in Table 1.
Potassium tetracyanoaurate(III) and
tin(IV) chloride pentahydrate were
used as gold and tin precursors for
the reason of their high solubility as
in water so in PG and impossibility of
their interaction in the bulk of solution. Concentrations of components
were chosen as recommended in the
previous work of the authors concerning EG electrolyte12. Au(III):
Sn(IV) mole ratio was varied from
1:14 to 1:28.
PG (99,95 %), the mixture of PG
with 1M aqueous HCl solution and
also 1M aqueous HCl solution for
comparison were used as the solvents.
PG electrolytes contained 7 weight %
of water introduced with the crystalline hydrate SnCl4 5H2O. Electrolytes
tested in this work were very simple
in composition and did not contain
any complementary ligands or other

November/December 2013 | metalnishing | 29

TECHNICALLY
speaking
additives that protably distinguish
them from the common aqueous
baths. The used aqueous electrolyte
also had a simplied composition
that was necessary for comparison.
Copper foil (99.9 %) was used as the
substrate (cathode). Platinum foil
(99.9 %) served as the anode. Electroplating was performed at galvanostatic conditions (direct current source
B4-49, Russia) in polypropylene tank
at constant stirring with magnetic
mixer. Current density (ic) was varied
from 1 to 10 mA/cm2. Further raise
of ic in PG electrolytes 14 resulted
in the worsening of coating quality.
The working temperature was varied
in the limits of (2035) 2C.
The coating weight was determined
gravimetrically with the sensitivity of
5105 g. The approximate thickness
of coatings was calculated from the
weight of the deposited alloy accounting the quota of gold and tin in it and
the density of individual metals.
The surface morphology of coatings was studied by scanning electron
microscopy (SEM) with the help of
microscope LEO1420. Elemental
composition of the alloy was determined by energy-dispersive X-ray
microanalysis (EDX) using scanning
electron microscope LEO 1420 supplied with Rontec attachment. X-Ray
Diffraction (XRD) phase analysis of
the alloy was carried out with the help
of X-ray diffractometer DRON-3
(Russia) using CuK rad iation. Card
les of the International Centre for
Diffraction Data were used for phase
identication.
Not less than 35 samples were analyzed for studying the reproducibility
of the results.

RESULTS AND DISCUSSION

General characteristics of electrolytes
and coatings, the rate of deposition. It
was revealed that all six selected electrolytes provided deposition of coatings with satisfactory adhesion to the
substrate. Coatings are shiny when
deposited at low ic equal to 15 mA/

COMPONENTS
1

ELECTROLYTE NUMBER
3
4
5

K[Au(CN)4], mole/l

0.1

0.05

0.1

0.05

0.1

0.05

SnCl45H2O, mole/l

1.4

1.4

1.4

1,4

1.4

1.4

PG volume, %

100

100

1M aqueous HCl solution,

volume, %

50

50

50

50

100

100

Table 1. Compositions of electrolytes for AuSn electrochemical deposition.

cm2. Matte coatings are formed at

higher ic up to 10 mA/cm2. The color
of the alloy depends on tin content.
It is whity-grey platinum-like at
2030 at.% of tin or grey at 3567 at.%
of tin.
Deposition of the alloy at ic 15
mA/cm2 regardless of the solvent is
characterized by the lack of dendrites
(whiskers) formation inherent to tin
and its alloys. The increase in the current density up to 10 mA/cm2 and
more causes the appearance of some
whiskers on the cathode edges noticeable after 30 min of the alloy deposition from the PG electrolyte 2 with
Au : Sn mole ratio equal to 1 : 28. It is
necessary to notice that aqueous electrolytes
5 and
6 are not stable.
After 4 h of their work solutions
become turbid supposedly due to the
hydrolysis of tin(IV) compounds, that
is especially noticeable at ic equal to
10 mA/cm2. Hydrolysis provokes the
deterioration of coatings appearance
and the retardment of coatings
growth. PG and mixed PG-aqueous
electrolytes are stable for some
months. In case of their long-term
exploitation, the slight greenish-yellow precipitate appears in the electrolytes. Most probable, this precipitate
consists of poorly soluble AuCN
which can appear in the result of
incomplete Au(III) to Au(I) reduction.
The increase in the current density
and content of water reduces the life
of electrolytes.
Experimental data characterizing
the rate of the alloy coatings deposition from different electrolytes, elemental and phase composition of the
deposited alloys are presented in
Table 2. According to the results
obtained the rate of coating deposition decreases with the diminution of
water content in a solution in the
6), PG/
row: aqueous ( 5 and

30 | metalnishing | November/December 2013

aqua ( 3 and 4), PG ( 1 and

2) electrolytes. In case of PG electro1 the maximum rate of coatlyte
ing growth is 2.4 mg/cm2h, PG/aqua
electrolyte
3 provides the maximum rate of 5.9 mg/cm2h, and in
5 the rate
aqueous electrolyte
achieves 16.0 mg/cm2h. Accounting
the quota of gold and tin in coatings
their thickness after 1 h deposition
varies in the range of 1.34.5m/h.
These values of the deposition rate
are quite near those, achieved in case
of EG electrolytes12. The rate grows
with the current density and it
mounts with an increase in the water
content in electrolytes.
The increase in the working temperature from 20C to 35C provides
1.61.8 fold growth of the deposition
rate in PG and PG/aqua electrolytes (
13), that can be caused by the
diminution of the solutions viscosity.
The increase in deposition rate with
temperature does not occur in case of
aqueous solutions.
The change in Au(III) : Sn(IV) mole
ratio from 1:14 to 1:28 does not effect
the rate of deposition from PG and
aqueous solutions
1, 2, 5, 6, but it
provides sufcient (up to 1.42.7
times) acceleration of plating in case
of PG/aqua electrolytes 3, 4 noticeable at ic equal to 5mA/cm2.
Current efciency of the plating
process was determined on the base
of gravimetric data and tin and gold
content in coatings. It increased from
15 to 25 % with the rise of temperature and gained maximum values at
current density 5 mA/cm2. Taking
into account the absence of hydrogen
evolution or essential worming-up of
the electrolytes the loss of electricity
can be connected with step-by-step
reduction of Au(III) and Sn(IV). The
presumption on incomplete gold(III)
reduction is in accordance with the
www.metalnishing.com

TECHNICALLY
speaking
fact of a very slow accumulation of
the greenish-yellow precipitate in the
electrolytes during their work.
Elemental and phase composition of
the alloys. Experimental data show
that elemental composition of alloys
essentially depends on the nature of
a solvent in electrolytes, Table 2. The
lowest tin content (not more than 25
at. %) is typical to coatings deposited
from aqueous electrolytes
5 and
6. Coatings enriched with tin up
to 67 at. % are formed from PG electrolyte ( 2) with small gold(III) concentration at high current density of
10 mA/cm2 and room temperature.
According to our results, tin content
in coatings increases with the decrease
in the quantity of water in electrolytes, the growth of current density
and temperature diminution. The
lessening of Au(III) concentration in
PG and PG/aqua electrolytes from 0.1
to 0.05 mole/l causes a distinctive
decrease in gold content in the alloy.
The optimal for a solder tin content
of 2439 at.% is achieved at deposition
in the next conditions: 1) PG and PG/
aqua electrolytes
1 and
3 with
gold(III) : tin(IV) ratio 1 : 14, current
density 5 mA/cm2 and temperature
35C, 2) PG electrolyte
2, current
density 1 mA/cm2, 2035C or current density 10 mA/cm2 and 35C, 3)
PG/aqua electrolyte
4at current
2
and
2035C,
4)
density 1 mA/cm
6
at
current
aqueous electrolyte
density 10 mA/cm2 and 20C.
According to XRD data AuSn
coatings obtained from electrolytes
16 can include crystalline phases
of AuSn, Au5Sn, AuSn2, Au6Sn or
AuSn4 intermetallic compounds, gold,
tin and sometimes amorphous
phases,Table 2, Fig. 1. Their composition depends much on conditions of
the plating. Coatings obtained from
nonaqueous PG electrolytes 1 and
2 contain intermetallic compounds while crystalline gold and tin
are not available. Crystalline gold and
tin together with intermetallic comwww.metalnishing.com

pounds are deposited from mixed

PG/aqua electrolytes 3 and 4 at
low current density and room temperature. Pure crystalline gold is
deposited from aqueous electrolytes
at low current density.
The results testify that the alloy containing crystalline intermetallic compounds is formed in the process of
simultaneous gold(III) and tin(IV)
electrochemical reduction from PG

electrolytes
1 and
2 at current
densities 15 mA/cm2 and no thermal
treatment is needed for the alloying.
Further elevation of the current density up to 10 mA/cm2 accelerates tin(IV)
reduction and promotes the enrichment of coatings with this metal.
Amorphous coatings are deposited in
this case because the rate of crystallization is small in the viscous PG media.
The addition of water into PG electro-

OF
IC,
T, C DEPOSITION PHASE
ELECMA/
RATE
COMPOSITION
TROLYTE CM2
MG/CM2H
1

10
1
2
5

10
1
3
5
10
1
4
5
10
1
5
5
10
1
6

5
10

ELEMENTAL
COMPOSITION,
AT. %

20

0.9

AuSn

Au 53; Sn 47

35

1.0

Au5Sn, AuSn

Au 86; Sn 14

20

1.3

AuSn

Au 53; Sn 47

35

2.4
(1.8 m/h)

Au5Sn, AuSn

Au 61, Sn 39

20

2.3

amorphous

Au 43; Sn 57

20

1.1

Au 63; Sn 37

35

1.3

Au 76 ; Sn 24

20

1.3

AuSn, AuSn2,
AuSn4

Au 37; Sn 63

35

2.1

AuSn

Au 59; Sn 41

20

2.3

amorphous

Au 33; Sn 67

35

2.5

amorphous

Au 64; Sn 36

20

1.2

Au, Sn, AuSn

Au 80; Sn 20

35

1.4

Au5Sn

Au 92; Sn 8

20

2.1

AuSn

Au 57; Sn 43

35

3.9
(3.0 m/h )

Au5Sn, AuSn

Au 61; Sn 39

35

5.9

AuSn

Au 57; Sn 43

20

1.1

Au, Sn, AuSn

Au 63; Sn 37

35

1.2

Au5Sn, AuSn

Au 76 ; Sn 24

20

5.7

AuSn

Au 57; Sn 43

35

5.3

AuSn

Au 57; Sn 43

20

5.8

Au 39; Sn 61

20

1.5

Au5Sn

Au 91; Sn 9

35

1.7

Au

Au 100

20

8.4

Au5Sn

Au 88; Sn 12

35

8.9

Au5Sn, Au

Au 94; Sn 6

20

16.0

Au5Sn, AuSn

Au 78; Sn 22

20

1.7

Au

Au 100

35

2.00

Au

Au 100

20

7.7

Au5Sn, AuSn

Au 92; Sn 8

35

7.8

Au6Sn**

Au 93; Sn 7

20

143
(12.3 m/h )

Au 75; Sn 25

Table 2. The rate of coating deposition, elemental and phase composition of AuSn
alloys in dependence of Au(III) : Sn(IV) mole ratio in electrolyte, current density (ic) and
temperature (T)
November/December 2013 | metalnishing | 31

TECHNICALLY
speaking

and ethyleneglycol was established in

the work15.
The surface morphology of two
types of AuSn coatings which are
characterized by the best for a solder
phase composition and Au : Sn ratio
is presented in Fig. 2, a and b. Both
coatings 1 m thick consist of evenly
distributed spherical tightly packed
grains. In spite of the similar composition coatings deposited from PG
and PG/aqua electrolytes 1 and
3 differ much in the grain sizes. Fine
grains 0.11.0 m in diameter and
average size of 0.2 m are characteristic of the alloy deposited from PG
electrolyte
1. The addition of the
water to PG (electrolyte
3) promotes the formation of much coarser
grains 0.22.5 m in size and average
diameter of 0.5 m. The largest of
them appear to be conglomerates of
the primary particles. They are not so
tightly packed and many of them are
surrounded by narrow canals about
0.1 m in width. SEM data show that
coatings deposited from aqueous
electrolytes in the absence of PG consist of well crystallized particles of
cubical form and are sufciently more
coarse-grained, the average size of the
grains gets 1.2 m.
The comparison of the grains size
and form in coatings of one and the
same thickness deposited in identical
conditions from the electrolytes differing by a solvent gives evidence that
PG retards the grain growth and crystallization (Fig. 2, PG and PG/aqua
solutions
1 and
3; Fig. 3, PG

lyte (see
3 and
4) accelerates as
the rate of tin(IV) reduction and the
process of crystallization.
The experimental data show that the
alloy acceptable as the solder which
consists of AuSn and Au5Sn crystalline
phases with total tin content about
2439 at.% is deposited from PG and
mixed PG/aqueous electrolytes
1
and
3 at gold(III) : tin(IV) ratio
equal to 1 : 14, current density 5 mA/
cm2 and temperature 35C.
It is necessary to underline that
coatings deposited from aqueous
solutions include predominantly
crystalline phases of gold or intermetallics enriched with gold such as
Au5Sn or Au6Sn and sometimes AuSn.
These results are similar to those
obtained for aqueous goldtin electroplating solutions in the works10, 14.
It was determined that the usage of
PG electrolyte instead of aqueous
solution provides deposition of
AuSn alloy enriched with tin. This
fact can be explained by equalization
of electrode potentials of gold and tin
and maybe of overvoltage of their discharge in the PG media as it was
shown for EG electrolyte12. The
change in electrode potential values
can be connected with formation of
complex compounds between the PG
and metal ions. The analogous complexation between some metal halides

(a)

(b)

Intensity, %
2

100

Intensity, %

1 - Au5Sn
1

2 - AuSn
2

1
50

2
22

20

1 - Au6Sn

100

50

and PG/aqua solutions

2 and
4). That could be stipulated by the
adsorption of PG on the growing surface and difculties in the mass transfer owing to the viscosity of PG which
is higher than that of the water.
The analysis of the effect of Au(III)
: Sn(IV) ratio shows that the diminution of tetracyanoaurate(III) concentration in electrolytes promotes the
formation of oblong grains (Fig. 3).
The length and width of the grains in
coatings deposited from the electrolytes
2 and
4 are in the same
limits as it was determined for their
analogues obtained from the electrolytes
1 and
3.
It is difcult to discover any regularity in the dependence between the
coating microstructure and the temperature of an electrolyte. In case of
electrolytes
1 and
4 the temperature elevation from 20 to 35 oC
causes grain sizes diminution. In case
of the electrolyte
3 the increase in
grain sizes with temperature occurs.
Note, that it is observed only at low
current density and small rate of deposition. This fact can be explained by
an acceleration of mass transfer with
the temperature elevation.
The lowering of current density
promotes the formation of more negrained and tightly packed coatings
characterized by the diminished dispersion of grain sizes (Fig 2, d). This
tendency appears to disagree with the
usual for water electrolytes lowering
of grain sizes in metal coatings with
the increase in the current density.

40

1
60

1,2
1

80

20, deg

30

40

50

60

70

20, deg
80

Figure 1. XRD patters of AuSn alloys: a PG electrolyte 1, ic = 1 mA/cm2, 35 C; b PG/aqueous electrolyte 6, ic = 5 mA/cm2, 350C.
32 | metalnishing | November/December 2013

www.metalnishing.com

TECHNICALLY
speaking
This discrepancy is most likely th
result of the diminution of tin content in the alloy with the lowering of
current density.
The data on microstructure of
goldtin coatings together with the
experimental results concerning their
composition and the rate of plating
allowed us to propose the PG electrolyte
1 for electrochemical deposition of AuSn solder owing to its
next useful characteristics. It provides deposition of the alloy with
elemental and phase composition of
the eutectic applicable for soldering.
The deposited AuSn coatings have
a very uniform tightly packed and
ne-grained microstructure that is
especially important in electronics
for production of devices with submicron elements. The rate of coatings plating at optimal conditions
equals to 1.8 m/h that is signicantly lower than in case of mixed
PG/aqua electrolyte
3 and of the
same order as the rate of AuSn deposition from the EG electrolyte12. It
is important to underline the absence
of dendrites formation usually occurring at electrochemical deposition of
tin and its alloys. It deserves attention that the developed electrolyte
has a very simple composition
including only the solvent (PG) and
gold and tin compounds, while aqueous electrolytes contain many additives necessary to control electrode
potentials of metals and over-potentials of their reduction, to prevent
the hydrolysis, to regulate the rate of
coatings deposition and their microstructure.

CONCLUSIONS
Stable and simple in composition
propyleneglycol electrolyte has been
developed for electrochemical deposition of goldtin alloy with the elemental, phase composition and
microstructure acceptable for the
usage in soldering. This electrolyte
includes potassium tetracyanoaurate
(III) and tin(IV) chloride pentahywww.metalnishing.com

Figure 2. SEM micrographs of AuSn coatings 1 m thick deposited from PG

and PG/aqua electrolytes 1 (a, c) and 3 (b, d) with Au(III) : Sn(IV) ratio 1 :
14: a ,b, c current density 5 mA/cm2 and d 1mA/cm2; a, b, d 35 C; c 18 C

Figure 3. SEM micrographs of AuSn coatings 1 m thick deposited from PG

and PG/aqua electrolytes with Au(III) : Sn(IV) ratio 1 : 28 at current density
5 mA/cm2 and 18 C: a electrolyte 2; b electrolyte 4

drate at Au(III) : Sn(IV) mole ratio 1 :

14 dissolved in the PG. Optimal conditions of its operating are current
density of 5 mA/cm2 and temperature
35C, stirring, platinum anode.
The proposed PG electrolyte provides deposition of AuSn coatings at
a rate of 2.4 mg/cm2h (1.8 m/h
accounting the alloy composition)
and to obtain alloys containing 1467
at.% of tin (optimal 39 at.%) included
into Au5Sn and AuSn crystalline
intermetallic compounds that corresponds to the composition of eutectic
applicable as a solder.
The rate of coatings deposition
depends on the nature of the solvent
and increases with the water addition
to PG. Maximal rate of 816mg/
cm2h is achieved in aqueous solutions with the composition analogous to PG electrolyte. The rate grows
with the current density and slightly
increases with the temperature. The
change in Au(III) : Sn(IV) mole ratio

from 1:14 to 1:28 does not effect the

rate of coating deposition from PG
electrolyte.
Tin content in AuSn coatings
strongly depends on the nature of the
solvent and can get up 67 at.% in PG
electrolyte with Au(III) : Sn(IV) mole
ratio lowered to1 : 28. It increases with
the decrease in the quantity of water
in electrolytes, the growth of current
density and temperature diminution.
Phase composition of AuSn alloys
is determined by the nature of a solvent, depends on Au(III) : Sn(IV) mole
ratio in an electrolyte, current density
and temperature. Thus, the alloy
including AuSn and Au5Sn crystalline
phases with total tin content about
2439 at.% is deposited from PG and
mixed PG/aqueous electrolytes at
gold(III) : tin(IV) ratio equal to 1:14,
current density 5 mA/cm2 and temperature 35C. Coatings deposited
from aqueous solutions include predominantly crystalline phases of gold

November/December 2013 | metalnishing | 33

TECHNICALLY
speaking
or intermetallics enriched with gold
such as Au5Sn or Au6Sn and sometimes AuSn with a summary tin
quantity much less than it is necessary for eutectic formation. The current density increase up to 10 mA/
cm2 adduces deposition of amorphous phases from PG and PG/aqua
electrolytes.
At optimal conditions of plating
from PG electrolyte coatings have a
very uniform tightly packed and negrained microstructure and are composed of spherical grains 0.11.0 m
in diameter and average size of 0.2
m. The change of PG on water media
causes the enlargement in the grain
size from 0.2 m to 1.2 m. The diminution of tetracyanoaurate(III) concentration from 0.1 to 0.05 mole/l in
electrolytes promotes the formation
of oblong grains. The lowering of cur-

rent density from 10 to 1 mA/cm2

promotes the formation of more negrained and tightly packed coatings
characterized by the diminished dispersion of grain sizes.

[9]

REFERENCES
[1] Okamoto H. Desk Handbook:
Phase Diagrams for Binary
Alloys, 2nd ed. ASM International, 2010
[2] Chevalier P-Y., Thermochimica
Acta, 130:1; 1988
[3] Tan Q., et al., Gold Bull, 44:27;
2011
[4] Ishikawa M., et al., Electron
Compon Technol Conf, 701;
2005
[5] Lauvernier D., et al., Proc Symp
IEEE/LEOS Benelux Chapter,
79; 2007
[6] Huang B., et al., Proc of SPIE,
6824: 17; 2008
[7] Huang M., et al., Mater Sci Technol, 28: 837; 2012
[8] Bozzini B., et al., J Appl Electrochem, 33:747; 2003

[12]

34 | metalnishing | November/December 2013

[10]
[11]

[13]

[14]

[15]

Bozzini B., et al., J Solid State

Eletrochem, 8: 147; 2004
Doesburg J., Ivey D. Mater Sci
Eng B,78: 44; 2000
Bozzini B., et al., J Appl Electrochem. 32: 165; 2002
Vorobyova T., Vrublevskaya O.
Surf Coat Technol, 204: 1314;
2010.
Eckerlin P, Kandler H Structure
data of elements and intermetallic phases. In: Hellwege K-H
(ed) Landolt-Brnstein, New
Series. III/6, 1971
Zhang Y., Ivey D. International
Conf Compd Semicond Mfg,
GaAsMANTECH; 2003
Knetsch D, Groeneveld W. Inorg
Chim Acta. 7: 81; 1973

* Phase composition was not determined

on the reason of irregular not qualitative coatings
** Phase was identied according to the
data of the work13

www.metalnishing.com