Thin Solid Films 587 (2015) 156–159

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Thin Solid Films

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Effects of bath composition on the morphology of electroless-plated Cu

electrodes for hetero-junctions with intrinsic thin layer solar cell
Woon Young Lee a, Yu Jin Lee a,b, Min Hyung Lee a,⁎
a
Surface Technology R&BD Group, Korea Institute of Industrial Technology (KITECH), Gaetbeol-ro 156, Yeonsu-gu, Incheon 406-840, Republic of Korea
b
Department of Materials Science & Engineering, Yonsei University, Yonsei-ro 50, Seodaemun-Gu, Seoul 120-749, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Available online 27 February 2015 The morphology of an electroless-plated Cu electrode was investigated as a function of bath composition. To en-
hance the selectivity of Cu electrode deposition on the surface of an indium tin oxide layer, a Ti/Cu multi-layer
Keywords: was deposited as a Cu electrode seed layer by physical vapor deposition, and then electroless plating was
Electroless plating performed using various complexing agents and a surfactant. The degree of selectivity was effectively influenced
Selective plating by the type of complexing agent. The electroless plating solution containing N,N,N′,N′-tetrakis(2-
Copper
hydroxypropyl)ethylenediamine (THPED) as complexing agent showed excellent selective growth of the Cu
Complexing agent
Surfactant
electrode as compared to the solution containing ethylenediaminetetraacetic acid. Even though THPED led to
Heterostructure with intrinsic thin layer solar cell better selective growth of the electroless-plated Cu electrode, the aspect ratio of electrode lateral growth was
about 2.7 times that of vertical growth. By adding a nonionic surfactant, the ratio between vertical growth rate
and lateral growth rate was improved about 4.6 times. The Cu–THPED electroless plating with nonionic surfac-
tant provided a drastic decrease in lateral growth rate, compared with the Cu–THPED electroless plating bath ex-
cluding nonionic surfactant. The Cu–THPED solution including nonionic surfactant is a promising composition of
electroless plating solution for the clear selective plating of Cu electrodes on hetero-junctions with intrinsic thin
layer solar cells.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction of a Cu electrode for HIT cells [6]. Actually, it is difficult to selectively

The photovoltaic market has grown tremendously during the past
decade. Among various solar cell structures, the hetero-junctions with
intrinsic thin layer (HIT) cell has been attracting a growing amount of
attention due to its high conversion efficiency with simple cell structure
[1,2].
Generally, the bus and finger electrodes of the HIT solar cell are
made of resin-bonded silver paste by screen-printing process.
However, the efficiency of the HIT cell can be reduced by the wide
width of the silver paste electrode [3]. Furthermore, the silver paste rep-
resents 25% of the total material costs for the solar cell, which leads to
increased HIT cell manufacturing costs in the event of rising silver prices
[4]. In an effort to increase the conversion efficiency by narrowing the
width of the electrode, and reduce the manufacturing costs of the HIT
cells, some studies have investigated methods of forming Cu electrodes
using electro or electroless Cu plating processes [5,6]. It is already
well known that Cu micro-electrodes formed using the electro- and
electroless-plating copper process have very effectively increased effi-
ciency and reduced manufacturing costs of some solar cells [5]. So far,
however, there has been little study on electro- and electroless-plating
⁎ Corresponding author. Tel.: +82 32 850 0287; fax: +82 32 850 0230.
E-mail address: minhyung@kitech.re.kr (M.H. Lee).
grow the Cu electrode in that application because the surface of the
HIT cell is covered with indium tin oxide (ITO) as a conductive material.
In this study, we investigated the effect of bath composition on the sur-
face morphology of an electroless-plated Cu electrode for the HIT solar
cell, considering the selectivity and plating rate.
2. Experimental details
To form a Cu electrode on the ITO surface via electroless plating pro-
cess, a Ti/Cu multi-layer was deposited as a seed of the Cu electrode by
physical vapor deposition (PVD). The width and thickness of the seed of
the Cu electrode were 55.3 μm and 1.1 μm, respectively.
The HIT cell wafer was diced in a square shape of 2 cm × 2 cm for use
as a substrate. To remove organic matter and debris from the substrate
surface, it was cleaned by acetone, ethanol and deionized water for
10 min each using an ultrasonic cleaner and dried with N2 gas. The so-
lutions were made up of analytical grade chemicals from Sigma-
Aldrich and deionized water treated by reverse osmosis and UV process.
In this study, Cu–ethylenediamine tetra acetic acid complex (Cu–
EDTA) solution and Cu-N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylene-
diamine complex (Cu–THPED) solution were used for the electro-
less plating bath. The Cu–EDTA bath was composed of 15 g/l
CuSO 4 ·5H 2 O as metal salt, 30 g/l Na 2 EDTA as complexing agent,

http://dx.doi.org/10.1016/j.tsf.2015.02.039
0040-6090/© 2015 Elsevier B.V. All rights reserved.
 W.Y. Lee et al. / Thin Solid Films 587 (2015) 156–159 157

0.02 g/l 2,2′-dipyridyl, 0.5 mg/l 2-mercaptobenzothiazole (2-MBT)

as stabilizer, 20 ml/l 37% HCHO as reduction agent and KOH as pH
adjusting agent. The pH of the solution was 12.5, and the tempera-
ture was maintained at 70 °C. The Cu–THPED bath was composed of
12.7 g/l CuSO4·5H2O as metal salt, 48.11 ml/l THPED as complexing
agent, 0.2 g/l 2,2′-dipyridyl, 0.5 mg/l 2-MBT as stabilizer, 10 ml/l
37% HCHO as reduction agent and NaOH as pH adjustment. The pH
of the solution was 13.2, and the temperature was maintained at
47 °C. To improve the selectivity and growth rate in the vertical
direction of the Cu–THPED bath, 1 ml/l Triton X-100 (TX-100)
diluted to 1.8% was used as nonionic surfactant.
The electroless Cu plating process was performed on the substrate in
a 250 ml beaker in a thermostat at steady temperature. During the pro-
cess, the substrates were placed in a vertical position and dipped in the
Cu-complex electroless plating bath for 30 min. After electroless plating,
the substrate was rinsed with DI water in an ultrasonic cleaner.
The morphology of the surface was observed by optical microscopy
(OM, BX51M, Olympus) and the perpendicular thickness of cy (SEM,
JSM-7001F, JEOL) with an accelerating voltage of 15 and 20 kV. A
potentiostat (Versastat3, AMETEK) was used to evaluate the electro-
chemical reaction by linear sweep voltammetry (LSV) in the presence
or absence of TX-100. The working electrode was the 2 cm × 2 cm Cu
substrate with 1 cm2 surface area, the counter electrode was a platinum
mesh, and a Ag/AgCl electrode was used as a reference electrode, re-
spectively. To remove Cu oxide from the working electrode, it was
soaked in 10% sulfuric acid solution for 10 s.
Prior to each test, the electrodes were immersed in the electrolyte
until open circuit potential was reached. Anodic LSV was carried out
from − 0.80 to − 0.35 V at a scan rate of 50 mV/s in Cu–THPED bath,
except for Cu metal ions, to figure out the behavior of HCHO-oxidation.

3. Results & discussion

3.1. Improvement of selectivity of electroless Cu plating

Fig. 1(a) and (b) are OM images of the surface of the HIT cell before
and after electroless plating using the Cu–EDTA solution, respectively.
The dark blue area in Fig. 1(a) is an active area of the HIT cell covered
by ITO and the bright yellow area is the Ti/Cu multi-layer electrode
pattern sputtered by PVD. The non-selective electroless plating on the
surface of the Cu electrode and ITO is shown in Fig. 1(b).
In order to determine the mechanism leading to such non-selective
electroless Cu plating, we considered the reaction stages that occurred
on the surface of the HIT cell as a function of electroless plating time.
These were:

(1) Cu2 + reduction–HCHO oxidation at the surface of the Cu

electrode in the initial stage;
(2) Decrease of Cu2+ concentration at the surface of the Cu electrode
and movement of electrons to the outside of the electrode
through the conductive ITO layer;
(3) Reduction of Cu2 + onto the ITO layer by combination with
moved electrons.

Based on the above scenario, the weak binding strength between

a Cu ion and complexing agent could elevate the degree of non-
selective electroless Cu plating by accelerating the reduction of Cu ions
onto the ITO layer. In the case of the Cu–EDTA bath, it is thought that
Cu ions were readily reduced by electrons at the ITO surface owing to
the weak binding strength of Cu2 +–EDTA, resulting in non-selective
electroless Cu plating.
To investigate the effect of the binding strength of the complexing
agent, EDTA was substituted with THPED as a complexing agent in the
Cu electroless plating bath. As shown in Fig. 1(c), the selectivity of
electroless-plated Cu electrode was certainly improved. The improved
Fig. 1. OM Images of the HIT cell surface: (a) before the electroless plating; (b) after
the electroless plating using Cu–EDTA solution; (c) after the electroless plating using
Cu–THPED solution.
selectivity with Cu–THPED electroless plating is presumed to be due
to the higher binding strength of Cu2+–THPED, as compared to that of
Cu2+–EDTA.
That is, the combination of Cu ions with electrons can be inhibited by
the strong binding strength of Cu2+–THPED, resulting in the suppres-
sion of electroless Cu plating onto the ITO surface. However, after
158 W.Y. Lee et al. / Thin Solid Films 587 (2015) 156–159

Fig. 2. Surface and cross-sectional SEM images of HIT cell showing Cu electrode: (a,c) after electroless plating in Cu-THPED without TX-100; (b,d) after electroless plating in Cu–THPED
with TX-100.

electroless Cu plating using the Cu–THPED bath, the width of the Cu using the Cu–THPED bath in the presence or absence of TX-100. The
electrode was abnormally enlarged to 130.7 μm in comparison with width of the electroless-plated Cu electrode using Cu–THPED bath
the initial width of the Ti/Cu underlayer of 55.3 μm. including TX-100 was measured to be about 71.0 μm, whereas that of
the Cu electrode without TX-100 was about 130.7 μm, as shown in
3.2. Increase of vertical growth rate of electroless-plated Cu electrode versus Fig. 2(a) and (b).
lateral growth At the same time, cross-section SEM images of the Cu electrode
(Fig. 2(c) and (d)) indicate that the thickness of the electroless-plated
The width of a Cu electrode on ITO thin films directly affects the
efficiency of a HIT cell. In other words, by reducing the area of the
light absorbing layer, the lateral growth of the electrode has a negative
influence on the conversion efficiency of the HIT cell. In order to
increase the vertical growth rate relative to the lateral growth rate of
the Cu electrode on an ITO layer, we added TX-100 as a surfactant to
the Cu–THPED bath.
Fig. 2 shows surface and cross sectional SEM images of the
electroless-plated Cu electrode on the surface of the HIT cell after

Table 1
Thickness, width, growth rate and aspect ratio of electroless-plated Cu electrode
using Cu–THPED bath in the presence or absence of TX-100.

Condition Thickness Width Growth rate Aspect ratio

(μm) (μm) (μm/min) (thickness/width)

Vertical Lateral

Before plating 1.1 55.3 – – –

Cu–THPED 1.9 130.7 0.027 1.267 0.0145
Cu–THPED with 2.8 71 0.057 0.262 0.0394
TX-100
Fig. 3. LSV curves for HCHO oxidation in the presence or absence of TX-100.
 W.Y. Lee et al. / Thin Solid Films 587 (2015) 156–159
Fig. 4. OM Images of the HIT cell surface after electroless plating in Cu–THPED bath with
TX-100.
Cu electrode using Cu–THPED bath without TX-100 was 1.9 μm while
that of the Cu electrode with TX-100 was 2.8 μm.
From these results, the vertical and lateral growth rates of the
electroless Cu plating were calculated as shown in Table 1. It shows
that the addition of TX-100 to the bath increases the aspect ratio
(thickness/width) from 0.0145 to 0.0394 as compared to that of the
Cu electrode plated without TX-100.
The cause of the abnormal growth of the Cu electrode in the lateral
direction is considered to be the absorption of hydrogen bubbles on
the Cu electrode. During the electroless plating process, hydrogen bub-
bles are evolved with the recombination of hydrogen radicals [7]. These
bubbles are absorbed on the surface of the Cu electrode and then inhibit
the reduction of Cu ions on the Cu electrode by blocking reaction sites,
which presumably leads to a reduction of Cu ions deposited onto the
ITO layer around the Cu electrode. For this reason, TX-100, a representa-
tive nonionic surfactant, is able to promote the growth of the Cu elec-
trode while simultaneously suppressing its lateral growth by
detaching hydrogen bubbles from the surface of the Cu electrode.
Fig. 3 shows the result of LSV for the anodic polarization curves of the
Cu–THPED bath in the presence or absence of TX-100, respectively.
According to Fig. 3, at the current density of − 0.5 V, the peak of
HCHO oxidation [8] was increased more in the presence of TX-100
than in the absence of TX-100. That means that the TX-100 induces
further activation of HCHO oxidation by detaching hydrogen from the
surface of the Cu electrode.
159
For this reason, the vertical growth of the Cu electrode in the Cu–
THPED electroless plating process can be accelerated by TX-100, as
shown in Fig. 4.
4. Conclusion
The degree of selectivity of electroless plating is related to the bind-
ing strength of the complexing agent. It is considered that the Cu–
THPED bath promotes clearer selective electroless Cu plating on the
Cu electrode of the HIT cell than Cu–EDTA due to the higher binding
strength of Cu2+–THPED. However, during the electroless Cu plating
process using the Cu–THPED bath, the vertical growth of the Cu elec-
trode was suppressed by hydrogen bubbles absorbed on the surface of
the Cu electrode, and the width of the Cu electrode was abnormally en-
larged. For that reason, TX-100 was used to remove the hydrogen bub-
bles on the surface of the Cu electrode. As a result, the growth of the Cu
electrode was enhanced in the vertical direction, while the lateral
growth was suppressed. In conclusion, the electroless Cu–THPED plat-
ing process with TX-100 is considered to be a useful method for forming
a Cu electrode for a highly efficient HIT cell.
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