Impact of deposition of indium tin oxide

double layers on hydrogenated amorphous

silicon/crystalline silicon heterojunction
Cite as: AIP Advances 10, 065008 (2020); https://doi.org/10.1063/5.0009994
Submitted: 06 April 2020 . Accepted: 14 May 2020 . Published Online: 02 June 2020

Masanori Semma, Kazuhiro Gotoh, Markus Wilde, Shohei Ogura, Yasuyoshi Kurokawa, Katsuyuki
Fukutani, and Noritaka Usami

ARTICLES YOU MAY BE INTERESTED IN

Hydrogen concentration at a-Si:H/c-Si heterointerfaces—The impact of deposition

temperature on passivation performance
AIP Advances 9, 075115 (2019); https://doi.org/10.1063/1.5100086

Effect of hydrogen plasma treatment on the passivation performance of TiOx on crystalline

silicon prepared by atomic layer deposition
Journal of Vacuum Science & Technology A 38, 022410 (2020); https://
doi.org/10.1116/1.5134720

Passivating contacts and tandem concepts: Approaches for the highest silicon-based solar
cell efficiencies
Applied Physics Reviews 7, 021305 (2020); https://doi.org/10.1063/1.5139202

AIP Advances 10, 065008 (2020); https://doi.org/10.1063/5.0009994 10, 065008

© 2020 Author(s).
 AIP Advances ARTICLE scitation.org/journal/adv

Impact of deposition of indium tin oxide double

layers on hydrogenated amorphous
silicon/crystalline silicon heterojunction
Cite as: AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994
Submitted: 6 April 2020 • Accepted: 14 May 2020 •
Published Online: 2 June 2020

Masanori Semma,1 Kazuhiro Gotoh,1,a) Markus Wilde,2 Shohei Ogura,2 Yasuyoshi Kurokawa,1
2
Katsuyuki Fukutani, and Noritaka Usami1

AFFILIATIONS
1
Department of Materials Process Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku,
Aichi 464-8603, Japan
2
Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Megro-ku, Tokyo 153-8505, Japan

a)
Author to whom correspondence should be addressed: gotoh.kazuhiro@material.nagoya-u.ac.jp

ABSTRACT
We report on the effect of sputtering deposition of indium tin oxide (ITO) as the transparent conductive oxide layer on the passivation
performance of hydrogenated amorphous silicon/crystalline silicon heterojunctions. The influence of sputtering damage on passivation per-
formance is studied by varying the ITO layer thickness from 0 nm to 80 nm. The passivation performance decreases considerably up to 10 nm
and increases gradually from 20 nm to 80 nm, indicating that damage and recovery stages are present during the sputtering process. We
focus on the injection energy as the cause of the recovery phenomenon. To optimize the passivation performance by intentionally enhanc-
ing the effect of the recovery stage while minimizing the initial damage at the heterointerface, we develop a two-step sputtering process
in which the radiofrequency power is changed from 50 W to 100 W during deposition to prepare ITO double layers. Two step sputtering
gives the lower damage, and the properties of ITO double layers are better than those of ITO single layers. These results show that two-
step sputtering can realize greater a-Si:H passivation. Furthermore, better optical properties are obtained in ITO double layers compared
with conventional ITO single layers. Therefore, modulating the radiofrequency power during ITO deposition can offer higher conversion
efficiency.
© 2020 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0009994., s

I. INTRODUCTION electrodes. A representative TCO material is indium tin oxide (ITO).

Silicon heterojunction (SHJ) solar cells with hydrogenated
amorphous silicon (a-Si:H) exhibit high power conversion effi-
ciency.1–3 In an SHJ solar cell, undoped a-Si:H is used as a passiva-
tion layer to suppress the recombination of photogenerated carriers
at the crystalline silicon (c-Si) surface, thereby allowing a high open-
circuit voltage (V OC ).4,5 The hydrogenation of dangling bonds (DBs)
at a-Si:H/c-Si heterointerfaces is regarded as a dominant mechanism
of the passivation effect of a-Si:H.6–11 In general, a transparent con-
ductive oxide (TCO) layer is essential between the electrode and
the doped a-Si:H layer because the conductivity of the a-Si:H layer
is insufficient to deliver the photogenerated carriers to the external
Sputtering is widely used to deposit ITO, but consequent degrada-
tion of the passivation and cell performance is unavoidable (often
called “sputtering damage”). Indeed, the performance of SHJ cells
is degraded due to the generation of DBs during ITO deposition by
sputtering.12–19 To avoid the sputtering damage, other methods for
ITO deposition have been reported such as thermal evaporation and
atomic layer deposition.20–22 However, another approach (e.g., post-
plasma treatment) is necessary for realizing the great electrical and
optical properties.21 Since sputtering is one of the simplest method
to fabricate ITO films with great properties, a lower damage process
that causes minimal sputtering damage is attractive for enhancing
the conversion efficiency and further improving solar cells.

AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994 10, 065008-1

© Author(s) 2020
 AIP Advances
Sputtering damage is attributed to ion bombardment (IB) and
light-induced degradation by the Staebler–Wronski effect in a-Si:H.
Demaurex et al. studied sputtering damage by using glass and quartz
shields to separate the damage into that of IB and vacuum ultra-
violet (VUV) illumination generated by the plasma.12 Konishi and
Ohdaira showed that sputtering damage depends strongly on depo-
sition power.14 Furthermore, the DBs generated by sputtering can be
re-terminated by high deposition temperature and post-annealing.
Although annealing during and after deposition can help us to ter-
minate the DBs and suppress the sputtering damage, the temper-
ature in all processes of SHJ solar cells should be below 200 ○ C to
prevent the a-Si:H layer from crystalizing, which is well known to
degrade passivation performance, leading to low V oc .18,19 However,
Huang et al. reported that better optical and electrical properties of
ITO films could be obtained by using higher deposition power and
temperature.23 Thus, it is crucial to establish a low-damage process
as well as excellent optical and electrical properties under limited
deposition power and temperature to improve the performance of
SHJ solar cells.
In this paper, we study the effect of sputtering damage on pas-
sivation performance by varying the ITO layer thickness from 0 nm
to 80 nm. The passivation performance decreased considerably up
to 10 nm and increased gradually from 20 nm to 80 nm, which
indicates that damage and recovery stages are present during sput-
tering. Based on these results for the passivation performance, we
developed two-step deposition by changing the radiofrequency (RF)
power from 50 W to 100 W during sputtering to minimize the influ-
ence of the initial damage and make effective use of the effect in the
recovery stage. The electrical properties of the ITO double layers
are identical to those of an ITO single layer, and then, the optical
properties of the former are superior to those of the latter. More-
over, two-step deposition offers superior passivation performance
compared with conventional one-step deposition.
II. EXPERIMENTAL METHOD
Double-sided mirror-polished Czochralski (Cz)-grown n-type
c-Si (100) wafers were used in all the experiments. The resistiv-
ity and wafer thickness were 3.0 Ω cm and ∼200 μm, respectively.
These wafers were cleaned with Semicoclean-23 (Furuuchi Chem-
icals) and dipped in a 2.5% HF solution for 1 min to remove the
native silicon oxide. The substrates were immersed in a 1.5% H2 O2
solution for 30 s to form ultra-thin silicon oxide to prevent crystal-
lization of the a-Si:H layer during annealing. Intrinsic a-Si:H (i-a-
Si:H) and n-type a-Si:H (n-a-Si:H) were deposited on the rear side,
TABLE I. Deposition conditions of i-, n-, and p-a-Si:H prepared by PECVD.
Deposition Layer Flow rate
temperature thickness of SiH4
Layer ( ○ C) (nm) (SCCM)
p-a-Si:H 260 4 40
i-a-si:H (front) 260 6 40
i-a-si:H (rear) 275 5 40
n-a-Si:H 275 8 40
AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994
© Author(s) 2020
ARTICLE scitation.org/journal/adv
while i- and p-type a-Si:H (p-a-Si:H) were deposited on the front
side by plasma-enhanced chemical vapor deposition (PECVD) with
a frequency of 27.12 MHz (CME-200J; ULVAC, Inc.). SiH4 , H2 ,
B2 H6 , and PH3 were used for a-Si:H deposition as the process gas.
The deposition conditions of the a-Si:H layers are summarized in
Table I.
After depositing the a-Si:H layers, an ITO layer was deposited
by RF sputtering of an In2 O3 :SnO2 target (Sn 8 wt. %) with Ar sput-
tering gas, the purity of which was 99.999% (5 N). In all depositions,
the Ar gas flow rate, the base pressure, the total process pressure,
and the deposition temperature were 50 SCCM, 4.0 × 10−4 Pa, 0.2 Pa,
and room temperature, respectively. To prepare the ITO single layer,
ITO was deposited on the rear side at an RF power of 50 W [here-
inafter referred to as low-power ITO (LP-ITO)]. The LP-ITO layer
thickness dLP-ITO was varied from 10 nm to 80 nm. To prepare the
ITO double layers, a second ITO layer was deposited on the initial
LP-ITO layer at an RF power of 100 W [hereinafter referred to as
high-power ITO (HP-ITO)]. The HP-ITO layer thickness dHP-ITO
was varied from 40 nm to 70 nm, and the total layer thickness
(i.e., dtotal = dLP-ITO + dHP-ITO ) was 80 nm (supplementary material,
Fig. S1). After ITO deposition, all samples were annealed in air at
200 ○ C for 15 min to cure the sputtering damage.
As shown in detail in Fig. 1, we fabricated four samples with
different structures. For samples A and B, we investigated the life-
time change during ITO deposition until 80 nm thickness, and for
samples C and D, we studied the effect of HP-ITO deposition on
passivation performance and took samples between LP-ITO and
HP-ITO depositions from the process chamber and measured the
effective carrier lifetime τ eff by quasi-steady-state photo conductance
(QSSPC). To investigate the light-induced degradation in samples B
and D, we covered them with glass substrates (EAGLE XG, Corning)
during sputtering to eliminate the IB effect of the sputtering damage,
but the glass substrates were sufficiently transparent to transmit the
plasma illumination.
We measured τ eff by QSSPC (WCT-120 TS; Sinton Instru-
ments) in generalized 1/1, 1/64, and transient modes.24,25 The layer
thickness of the ITO films on glass substrates was determined by
spectroscopic ellipsometry (SE; M-2000DI-Nug; J.A. Woollam Co.).
In the SE analysis, we used the Cauchy, Tauc–Lorentz, Lorentz,
Gauss, and Drude models for the dielectric functions of the samples
based on Ref. 26. To characterize the electrical and optical properties
of the ITO films on glass substrates, we used a Hall-effect measure-
ment system (HMS-3000; ECOPIA), a spectrophotometer (V-570
UV/VIS/NIR; JASCO), and SE analysis. To investigate hydrogen
depth profiles and hydrogen concentration (CH ) in the samples,
Flow rate Flow rate Flow rate
of H2 of 2% PH3 of 1% B2 H6 Pressure Power density
(SCCM) (SCCM) (SCCM) (Pa) (mW/cm2 )
0 0 15 25 32.5
0 0 0 25 32.5
0 0 0 25 32.5
380 20 0 50 32.5
10, 065008-2
 AIP Advances
FIG. 1. Schematic structures of samples using ITO single (samples A and B) or
double layers (sample C and D). Glass substrates were mounted on the a-Si:H/c-
Si heterojunctions during ITO deposition to eliminate ion bombardment (samples
B and D).
resonant 1 H(15 N,αγ)12 C nuclear reaction analysis (NRA), which can
detect H atoms in the near-surface region with nanometer scale
depth resolution, was employed. The details of NRA are given else-
where.27,28 For the Hall measurements, silver electrodes in the Van
der Pauw configuration were deposited on the ITO films by vacuum
evaporation, the layer thickness of all the ITO films was 80 ± 5 nm,
and the sample size was 8 mm2 .
III. RESULTS AND DISCUSSION
A. Effect of depositing an ITO single layer
Figure 2 shows the τ eff of the LP-ITO deposited structure (a)
without and (b) with glass covers as a function of the minority
carrier density (MCD). The results for the samples with dLP-ITO
= 0 (bare glass), 20 nm, and 80 nm are plotted in Fig. 2. The
schematics of the lifetime measurements are illustrated as sam-
ples A and B in Fig. 1. τ eff without glass covers was remark-
ably decreased compared to that with glass covers. These results
mean that IB is the dominant degradation mechanism of sputter-
ing damage, which is in good agreement with the previous work.12,29
Furthermore, we can discuss about the cause of carrier recombi-
nation by the figure of MCD vs τ eff . It is known that the car-
rier recombination at lower and higher MCD regions is mainly
caused by Shockley–Read–Hall (SRH) recombination and Auger
AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994
© Author(s) 2020
ARTICLE scitation.org/journal/adv
FIG. 2. (a) Injection-dependent effective carrier lifetime of the samples A and B
after LP-ITO deposition (a) without and (b) with glass covers.
recombination, respectively.30,31 At the lower MCD region in
Fig. 2(a), the higher τ eff is observed for the samples with 80-nm-
thick ITO in comparison with the sample with 20-nm-thick ITO.
This improved τ eff at lower MCD is probably attributed to sup-
pressed SRH recombination, suggesting that the number of DBs was
decreased by ITO deposition.
Figure 3 shows τ eff at the MCD of 1.0 × 1015 cm−3 as a
function of dLP-ITO . The average value of τ eff at the MCD of
1.0 × 1015 cm−3 was around 1.77 ms before LP-ITO sputtering and
was observed to decrease after LP-ITO deposition. Furthermore, τ eff
for the samples with and without glass covers shows a minimum
at around 10 nm. After initial degradation, a slight increase in τ eff
with dLP-ITO can be seen. Therefore, the sputtering process seems
to be separated into damage and recovery stages. A similar behav-
ior of τ eff up to 80 nm was observed in the previous work,29 and
light soaking has been reported to increase the τ eff of structures
containing a-Si:H.4,32 Note that because all the depositions were car-
ried out at room temperature, there is no influence of heat during
sputtering.
Figure 4 shows the transmittance spectra of LP-ITO layers
of various thicknesses on glass substrates. The plasma light of
pure Ar gas comprises mainly VUV with wavelengths of 100 nm,
160 nm, 220 nm, and 320 nm.33 The values of the transmittance at
220 nm and 320 nm as measured by SE are given in Table II. The
10, 065008-3
 AIP Advances ARTICLE scitation.org/journal/adv

TABLE II. Transmittance of LP-ITO with layer thickness d LP-ITO .

dLP-ITO (nm) 0 (bare glass) 10 20 40 80

T at 220 nm (%) 0.087 0.079 0.071 0.084 0.081

T at 320 nm (%) 66.14 60.84 49.25 44.41 34.67

FIG. 3. Ratio of effective carrier lifetime τ eff after LP-ITO deposition to that before
LP-ITO deposition as a function of layer thickness of LP-ITO. Values of τ eff at
a minority carrier density of 1.0 × 1015 cm−3 are used. Triangles and circles
represent the samples with and without glass covers, respectively.

transmittance at 220 nm ranged from 0.070 to 0.084, whereas that at

320 nm decreased gradually with the ITO thickness. Consequently,
the photon flux density induced by the Ar plasma to the samples
tends to decrease with the thickness of an ITO layer. From these
results, the increase in τ eff in the later sputtering stage may be caused
by (i) changing the band diagram by ITO deposition and (ii) the re-
termination of DBs by hydrogenation. However, the band diagram
for an a-Si:H/c-Si heterointerface does not change much according
to simulations using AFORS-HET (supplementary material, Fig. S2
and Table S1).34 These results mean that the increase in τ eff in the
recovery stage is not due to a changed band diagram and enhanced
carrier selectivity during sputtering but rather due to re-termination

FIG. 5. Hydrogen depth profile of n-a-Si:H/i-a-Si:H/c-Si heterojunctions (a) before

sputtering, (b) after 10- and (c) 80-nm-thick deposition in sample A, and (d) after
FIG. 4. Transmittance spectra of LP-ITO films on glass. The layer thickness of 10- and (e) 80-nm-thick deposition in sample B. For the samples of (b) and (c),
LP-ITO is 0 (bare glass), 10 nm, 20 nm, 40 nm, and 80 nm. ITO was removed by dipping the samples in a 5% HF solution.

AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994 10, 065008-4

© Author(s) 2020
 AIP Advances
of the DBs at the a-Si:H/c-Si heterointerface. Therefore, we con-
sider that the degradation of the passivation performance was due
to the de-hydrogenation of DBs and that the sputtering damage was
partially cured by the re-hydrogenation of interfacial DBs.
Note again that the passivation effect of a-Si:H is believed to
be caused by the hydrogenation of DBs.6–11 In the damage stage, IB
and plasma light induce de-hydrogenation, resulting in the gener-
ation of DBs in the a-Si:H layer and at the a-Si:H/c-Si heteroint-
erface. After depositing 10-nm-thick ITO, the deposited ITO layer
reduces the absorption of VUV in a-Si:H and protects the a-Si:H
layer from IB. In the recovery stage, re-hydrogenation of DBs may
be induced by the energy released from decelerating the incident
ions and by the absorption of VUV. A similar consideration has
been proposed previously.35 Furthermore, we also consider that the
defect gradient from the interface to the surface causes H diffusion
in the a-Si:H layer. It has been stated that hydrogen atoms can move
easily from one site to another due to weakened Si–H and Si–Si
bonds.35,36
NRA was used to analyze the hydrogen distributions in sam-
ples A and B before sputtering and after 10- and 80-nm-thick ITO
deposition, as shown in Fig. 5, where the a-Si:H/c-Si heterointer-
face positions are indicated by vertical lines near 6.40 MeV of 15 N
ion energy. Furthermore, CH at the a-Si:H/c-Si interface and integral
hydrogen concentration (I H ) in the a-Si:H layer are summarized in
Table III. CH and I H mean the hydrogen concentration at the spe-
cific energy and the total hydrogen content at the specific region,
respectively. I H are given from the following equation:
E2
IH = ∫ CH (E)dE,
E1
where E1 and E2 are the energies corresponding to the a-Si:H sur-
face and a-Si:H/c-Si interface. The slightly smaller depth of the
interface in Figs. 5(b) and 5(c) is probably due to slight fluctua-
tion of deposition rate during the fabrication of the a-Si:H layers
and removal of ultrathin silicon oxide by HF treatment (supple-
mentary material, Fig. S3). Regardless of whether or not glass cov-
ers were used, the total hydrogen content in the a-Si layer of all
plasma-exposed samples is identical [Figs. 5(b)–5(f) and Table III).
The very slight reduction of the H content in these samples com-
pared to the condition before sputtering [Fig. 5(a)] may be attributed
to a small loss of H due to VUV-induced desorption of H from
the a-Si layer.37 More importantly, the NRA H profiles reveal that
there are significant changes in the hydrogen concentration near the
a-Si:H/c-Si heterointerfaces. The near-interfacial hydrogen concen-
tration values range from 3.50 × 1021 cm−3 to 4.55 × 1021 cm−3 ,
as given in Table III. In the IB-exposed samples, the near-interfacial
H concentration is decreased by 23% compared to the as-deposited
sample and increases again slightly after the deposition of the
TABLE III. Hydrogen concentration at the a-Si:H/c-Si heterointerface with LP-ITO thickness.
dLP-ITO (nm) 0 10 (w/o glass) 80 (w/o glass) 10 (w/glass) 80 (w/glass)
CH at the a-si:H/c-Si
4.55 ± 0.19
heterointerface (×1021 cm−3 )
I H in the a-Si:H layer (×1019 ) 7.6
AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994
© Author(s) 2020
ARTICLE scitation.org/journal/adv
80 nm LP-ITO layer. These changes in the hydrogen distribu-
tion in Fig. 5 and Table III are entirely consistent with the trend
of the τ eff changes during ITO sputtering (Fig. 3) and the above
described mechanism of de-hydrogenation and re-hydrogenation of
interfacial DBs.
We understand these trends on the basis of the following sce-
nario: Strong IB damage during initial ITO deposition (10–20 nm)
creates de-passivated Si-DBs in the interfacial region that represents
stable trap sites for H, which are not re-populated in this early stage,
however, because the defect gradient drives diffusing H away from
the interface. As the ITO thickness increases, the sputtered ITO ions
can no longer penetrate down to the interface, but their mobiliz-
ing effect on H in the a-Si:H layer by cleaving Si–H bonds persists.
This still generates diffusible H atoms in the a-Si:H layer that may
become trapped at the de-hydrogenated Si-DBs in the interfacial
region in later deposition stages. The resulting back-diffusion of H
to the interface explains the re-passivation of the DBs in the recov-
ery stage. Quantitatively, this slight return of interfacial H is a small
effect compared to the much larger H loss during the initial ITO
deposition step, very similar to the decrease/recovery trend of τ eff
in Fig. 3. Comparison with the glass-covered samples shows that
the influence of VUV radiation on the H-distribution and τeff is
much smaller than that of IB but qualitatively similar. From these
insights into the damaging/recovery mechanisms, we hypothesize
that the residual sputtering damage can be reduced by injecting
more energy into the a-Si:H/c-Si heterostructures in the recovery
stage.
B. Effect of depositing ITO double layers
To verify the aforementioned hypothesis, we performed two-
step deposition by changing the RF power during sputtering.
Figure 6 shows the relative τ eff values of the ITO deposited samples
before [Figs. 6(a) and 6(b)] and after annealing [Fig. 6(c)] normal-
ized by τ eff before ITO sputtering (τ 0 ). The samples used for the
lifetime measurements are illustrated as samples C and D in Fig. 1.
Figures 6(a) and 6(b) show the τ eff /τ 0 values of the samples without
and with glass covers, respectively. The τ eff of all the samples using
the ITO double layers is observed to increase after HP-ITO sputter-
ing. Furthermore, τ eff after HP-ITO sputtering is higher than that of
the sample after 80-nm-thick LP-ITO deposition [the bar graph with
black diagonal lines shown on the right of Fig. 6(a)]. In Fig. 6(b), a
similar behavior was confirmed before and after HP-ITO sputtering.
However, the τ eff of the sample after 10-nm-thick LP-ITO sputtering
was decreased after 70-nm-thick HP-ITO sputtering. We consider
that this difference is due to the absorption of plasma light in the ITO
layer during HP-ITO sputtering. According to the results shown in
Fig. 4 and Table II, the transmittance of 10-nm-thick ITO on glass at
3.50 ± 0.29 3.83 ± 0.32 4.36 ± 0.21 4.31 ± 0.21
8.18 7.87 7.59 7.2
10, 065008-5
 AIP Advances
220 nm and 330 nm is almost the same as that for bare glass. There-
fore, the passivation degradation can be explained by plasma VUV
light irradiation with higher photon flux density during the damage
stage. In the recovery stage, the plasma light reaching the a-Si:H/c-Si
heterointerface was reduced by absorption in the ITO layer on glass
FIG. 6. Ratios of effective carrier lifetime for samples C and D at a minority carrier
density of 1.0 × 1015 cm−3 as a function of the thickness of LP-ITO and HP-ITO. (a)
and (b) show τ eff of samples after sputtering without and with glass covers, respec-
tively, divided by τ eff of samples before sputtering. (c) τ eff of annealed samples
normalized using τ eff before sputtering.
AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994
© Author(s) 2020
ARTICLE scitation.org/journal/adv
covers thicker than 20 nm, whereupon re-termination of DBs can
take place.
Figure 6(c) shows the results of all the samples that were
annealed at 200 ○ C for 15 min. For most samples with the ITO dou-
ble layer, while τ eff at the MCD of 1.0 × 1016 cm−3 was almost com-
parable, that at the MCD of 1.0 × 1015 cm−3 was higher than the sam-
ples with the ITO single layer after annealing regardless of whether
glass covers were used or not. In particular, the τ eff deposited
40-nm-thick LP-ITO and HP-ITO were the highest in all samples.
We attribute these results to the change in the initial stage before
annealing at the a-Si:H/c-Si heterointerface in the recovery stage.
The increased energy of accelerated ions and plasma light irradiation
during HP-ITO sputtering enhances the slight diffusion of hydrogen
atoms toward the a-Si:H/c-Si heterointerface and, thus, aids the re-
termination of the DBs created in the damage stage. The resulting
increase in H atoms near the a-Si:H/c-Si heterointerface then fur-
ther enhances the recovery in the annealing process. These results
show that the improvement of τ eff in the recovery stage is likely
to be enhanced by injecting higher energy generated by two-step
FIG. 7. (a) Electron density, (b) Hall mobility, and (c) resistivity of ITO single and
double layers on glass substrates as a function of the thickness of the ITO layer.
The unfilled and filled circles represent the results of the samples using ITO single
and double layers, respectively.
10, 065008-6
 AIP Advances
sputtering with changing RF power, thereby offering a low-damage
process and high cell performance.
C. Optical and electrical properties of ITO single
and double layers
Figure 7 shows (a) the electron density N e , (b) the Hall mobil-
ity μ, and (c) the resistivity of ITO single and double layers on glass
substrates before and after annealing. For the as-deposited ITO dou-
ble layers, lower μ and higher N e were observed than LP-ITO sin-
gle layers both before and after annealing. Then, a decrease in N e
and an increase in μ are observed by annealing. These are probably
attributable to the effect of oxygen vacancies by HP-ITO deposi-
tion and annealing in air. It is known that oxygen vacancies act
FIG. 8. Optical properties of ITO single and double layers on glass substrates (a)
before and (b) after annealing. Solid and dotted lines represent the transmittance
and reflectance, respectively, of a sample. The layer thickness of each film is 80
± 5 nm.
AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994
© Author(s) 2020
ARTICLE scitation.org/journal/adv
as donors in ITO and, thus, increase N e and decrease μ.38,39 Fur-
thermore, the oxygen vacancies in ITO films are annihilated during
annealing in air, and then, N e decreases and μ increases.40,41 Hence,
in HP-ITO deposition, accelerated negatively charged particles (e.g.,
electrons, oxygen ions, and secondary electrons) with higher energy
could generate many oxygen vacancies by collisions at the growing
ITO surface. Meanwhile, the increase in μ after annealing is consid-
ered to be due to the decreased oxygen vacancies and the crystal-
lization of ITO. In terms of the resistivity, ITO double layers with
40-nm-thick LP-ITO and HP-ITO have the best conductivity after
annealing.
Figure 8 shows the transmittance and reflectance spectra of the
ITO single and double layers (a) before and (b) after annealing. The
reflectance spectra are observed to decrease from 350 nm to 700 nm
by changing the single LP-ITO layer into HP-ITO/LP-ITO double
layers; this is caused by the differences in the refractive index n and
extinction coefficient k for LP-ITO and HP-ITO. Figure 9 shows the
n and k of single LP-ITO and HP-ITO layers on glass substrates
(a) before and (b) after annealing. The values of n and k at 400 nm
and their mean square errors (MSEs) are summarized in Table IV.
Because all the MSE values are small enough, the experimental data
are in good agreement with the model fit curves, confirming the
FIG. 9. Refractive index n and extinction coefficient k for LP-ITO and HP-ITO (a)
before and (b) after annealing.
10, 065008-7
 AIP Advances
TABLE IV. Refractive index n and extinction coefficient k of LP-ITO and HP-ITO at a
wavelength of 400 nm and MSEs before and after annealing.
LP-ITO
n at 400 nm 2.148
Before annealing k at 400 nm 0.028
MSE 2.703
n at 400 nm 2.207
After annealing k at 400 nm 0.028
MSE 6.175
validity of the optical constants and the model. The value of n was
higher for LP-ITO than for HP-ITO (Fig. 9), both before and after
annealing. Because of the difference in n between HP-ITO and LP-
ITO at the interface, the increase in transmittance and the decrease
in reflectance observed for the ITO double layers arose from a bet-
ter anti-reflection effect. Moreover, the single HP-ITO layer after
annealing exhibited high transparency in the near-infrared region,
possibly because of decreased optical loss due to free-carrier absorp-
tion. However, in terms of the TCO layer for SHJ solar cells, the
transparency for the wavelength absorbed by c-Si has much impor-
tance than the near-infrared region. From the above, ITO double
layers are superior to the ITO single layer also in terms of optical
properties.
The results show that the better electrical properties were
obtained by changing ITO single into double layers. Furthermore, in
terms of the transparency in the wavelengths absorbed by c-Si, better
optical properties were also obtained with ITO double layers com-
pared with LP-ITO and HP-ITO single layers due to the difference
in refractive index n in ITO double layers. Regarding the passivation
effect, ITO double layers are superior to an ITO single layer because
of the lower sputtering damage with the ITO double layers. Further-
more, in this work, we did not introduce O2 gas during ITO deposi-
tion at all. Hence, optimization of the process gas flow may improve
some parameters of ITO double layers (e.g., transparency and the
Hall mobility) to realize the further great cell performance. From
the above, ITO double layers deposited with changing RF power can
offer improved performance of SHJ solar cells.
IV. CONCLUSIONS
We investigated the effect of ITO sputtering and two-step depo-
sition on the passivation performance of the a-Si:H/c-Si heterojunc-
tions. The value of τ eff decreased with increasing thickness up to
dLP-ITO = 10 nm and then increased as the ITO sputtering process
proceeded, suggesting that damage and recovery stages were present
in the ITO sputtering process. In the damage stage, IB dominantly
created defects in a-Si:H layers and a-Si:H/c-Si heterointerfaces. In
the recovery stage, the energy of IB and VUV presumably con-
tributed to the increase in τ eff because of re-hydrogenation of DBs
using the energy generated from braking high-energy ions on the
deposited ITO layer and absorption of VUV in ITO.
The ITO double layers gave relatively high τ eff in comparison
with an ITO single layer, presumably because of the injection of a
AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994
© Author(s) 2020
ARTICLE scitation.org/journal/adv
larger amount of energy to enhance re-hydrogenation of DBs dur-
ing HP-ITO deposition. In terms of the electrical properties, the
resistivity of ITO double layers after annealing was approximately
HP-ITO 4.0 × 10−4 Ω cm. The transparency of the ITO double layers in the
wavelengths absorbed by c-Si was superior to that of the ITO single
2.145 layer. From the above, ITO double layers with changing RF power
0.040 can further improve the SHJ solar cell performance. Furthermore,
6.215 the two-step deposition with modulating RF power may be useful
for the materials containing weakly bonded hydrogen.
2.187
0.013
5.478 SUPPLEMENTARY MATERIAL
See the supplementary material for the simulating condition
and results, the schematic procedures of the double layer, and
sample preparation for NRA measurements.
ACKNOWLEDGMENTS
This work was supported by Industrial Technology Develop-
ment Organization (NEDO) and “Hydrogenomics” (Grant Nos.
JP18H05514 and JP18H05518) from the Japan Society for the Pro-
motion of Science (JSPS) in Japan. We would like to thank H. Miura
and A. Shimizu for technical support.
DATA AVAILABILITY
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
REFERENCES
1
S. De Wolf, A. Descoeudres, Z. C. Holman, and C. Ballif, Green 18, 7 (2012).
2
M. A. Green, Y. Hishikawa, W. Warta, E. D. Dunlop, D. H. Levi, J. Hohl-Ebinger,
and A. W. H. Ho-Baillie, Prog. Photovoltaics 25, 668 (2017).
3
L. Korte, E. Conrad, H. Angermann, R. Stangl, and M. Schmidt, Sol. Energy
Mater. Sol. Cells 93, 905 (2009).
4
E. Kobayashi, S. De Wolf, J. Levrat, A. Descoeudres, M. Despeisse, F.-J. Haug,
and C. Ballif, Sol. Energy Mater. Sol. Cells 173, 43 (2017).
5
M. Tanaka, M. Taguchi, T. Matsuyama, T. Sawada, S. Tsuda, S. Nakano, H.
Hanafusa, and Y. Kuwano, Jpn. J. Appl. Phys., Part 1 31, 3518 (1992).
6
S. De Wolf and M. Kondo, J. Appl. Phys. 105, 103707 (2009).
7
A. Descoeudres, L. Barraud, S. De Wolf, B. Strahm, D. Lachenal, C. Guérin, Z. C.
Holman, F. Zicarelli, B. Demaurex, J. Seif, J. Holovsky, and C. Ballif, Appl. Phys.
Lett. 99, 123506 (2011).
8
T. F. Schulze, H. N. Beushausen, C. Leendertz, A. Dobrich, B. Rech, and L. Korte,
Appl. Phys. Lett. 96, 252102 (2010).
9
S. De Wolf, S. Olibet, and C. Ballif, “Stretched-exponential a-Si:H/c-Si interface
recombination decay,” Appl. Phys. Lett. 93, 032101 (2008).
10
S. De Wolf, C. Ballif, and M. Kondo, “Kinetics of a-Si:H bulk defect and
a-Si:H/c-Si interface-state reduction,” Phys. Rev. B 85, 113302 (2012).
11
K. Gotoh, M. Wilde, S. Kato, S. Ogura, Y. Kurokawa, K. Fukutani, and N. Usami,
AIP Adv. 9, 075115 (2019).
12
B. Demaurex, S. De Wolf, A. Descoeudres, Z. C. Holman, and C. Ballif, Appl.
Phys. Lett. 101, 171604 (2012).
13
S. De Wolf, C. Demaurex, A. Descoeudres, and C. Ballif, Phys. Rev. B 83, 233301
(2011).
14
T. Konishi and K. Ohdaira, “Indium tin oxide sputtering damage to catalytic
chemical vapor deposited amorphous silicon passivation films and its recovery,”
Thin Solid Films 635, 73 (2017).
15
D. E. Carlson, Appl. Phys. A: Solids Surf. 41, 305 (1986).
10, 065008-8
 AIP Advances ARTICLE scitation.org/journal/adv

16 30
D. Zhang, A. Tavakoliyaraki, Y. Wu, R. A. C. M. M. van Swaaij, and M. Zeman, C. Leendertz, R. Stangl, T. F. Schulze, M. Schmidt, and L. Korte, Phys. Status
Energy Procedia 8, 207 (2011). Solidi C 7, 1005 (2010).
17 31
T. Kamioka, Y. Hayashi, Y. Isogai, K. Nakamura, and Y. Ohshita, AIP Adv. 7, M. J. Kerr and A. Cuevas, J. Appl. Phys. 91, 2473 (2002).
095212 (2017). 32
E. Kobayashi, S. De Wolf, J. Levrat, G. Christmann, A. Descoeudres,
18
S. De Wolf and M. Kondo, Appl. Phys. Lett. 91, 112109 (2007). S. Nicolay, M. Despeisse, Y. Watabe, and C. Ballif, Appl. Phys. Lett. 109, 153503
19
H. Fujiwara and M. Kondo, Appl. Phys. Lett. 90, 013503 (2007). (2016).
20 33
G. S. Belo, B. J. P. da Silva, E. A. de Vasconcelos, W. M. de Azevedo, and E. F. da Y. Kuang, B. Macco, B. Karasulu, C. K. Ande, P. C. P. Bronsveld, M. A.
Silva, Appl. Surf. Sci. 255, 755 (2008). Verheijen, Y. Wu, W. M. M. Kessels, and R. E. I. Schropp, Sol. Energy Mater.
21 Sol. Cells 163, 43 (2017).
F. Wang, R. Du, Q. Ren, C. Wei, Y. Zhao, and X. Zhang, Appl. Surf. Sci. 426,
34
856 (2017). R. Varache, C. Leendertz, M. E. Gueunier-Farret, J. Haschke, D. Muñoz, and
22 L. Korte, Sol. Energy Mater. Sol. Cells 141, 14 (2015).
Y. Zhou, H. Cheun, W. J. Potscavage, Jr., C. Fuentes-Hernandez, S.-J. Kim, and
35
B. Kippelen, J. Mater. Chem. 20, 6189 (2010). P. Mahtani, R. Varache, B. Jovet, C. Longeaud, J. Kleider, and N. P. Kherani, J.
23 Appl. Phys. 114, 124503 (2013).
M. Huang, Z. Hameiri, S. Venkataraj, A. G. Aberle, and T. Mueller, Energy
36
Procedia 33, 91 (2013). M. Stutzmann, W. B. Jackson, and C. C. Tsai, Phys. Rev. B 32, 23 (1985).
24 37
A. Cuevas and R. Sinton, Prog. Photovoltaics 5, 79 (1997). B. W. Clare, J. C. L. Cornish, G. T. Hefter, P. J. Jennings, C. P. Lund, D. J.
25
R. Sinton and A. Cuevas, Appl. Phys. Lett. 69, 2510 (1996). Santjojo, and M. O. G. Talukder, Thin Solid Films 288, 76 (1996).
26 38
T. Koida, M. Kondo, K. Tsutsumi, A. Sakaguchi, M. Suzuki, and H. Fujiwara, J. W.-F. Wu and B.-S. Chiou, Semicond. Sci. Technol. 11, 196 (1996).
39
Appl. Phys. 107, 033514 (2010). R. B. H. Tahar, T. Ban, Y. Ohya, and Y. Takahashi, J. Appl. Phys. 83, 2631
27
K. Fukutani, Curr. Opin. Solid State Mater. Sci. 6, 153 (2002). (1998).
28 40
M. Wilde and K. Fukutani, Surf. Sci. Rep. 69, 196 (2014). S. Li, Z. Shi, Z. Tang, and X. Li, Vacuum 145, 262 (2017).
29 41
A. H. T. Le, V. A. Dao, D. P. Pham, S. Kim, S. Dutta, C. P. T. Nguyen, Y. Lee, S. Ray, R. Banerjee, N. Basu, A. K. Batabyal, and A. K. Barua, J. Appl. Phys. 54,
Y. Kim, and J. Yi, Sol. Energy Mater. Sol. Cells 192, 36 (2019). 3497 (1983).

AIP Advances 10, 065008 (2020); doi: 10.1063/5.0009994 10, 065008-9

© Author(s) 2020