Ceramics International 44 (2018) 9347–9352

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Solution-processed nickel oxide hole transport layer for highly efficient T

perovskite-based photovoltaics
⁎
Saemon Yoon, Dong-Won Kang
School of Energy Systems Engineering, Chung-Ang University, Seoul, 06974, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Solution processed NiOx is one of the promising hole transport layer (HTL) for planar perovskite solar cells,
Nickel-oxide which can replace hygroscopic poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) HTL. In
Ethylenediamine this study, we investigated effects of ethylenediamine (EDA) additive in NiOx precursor solution (nickel nitrate
Hole-transport hexahydrate dissolved in ethyleneglycol) on optoelectronic and surface morphological properties of resultant
Perovskite
solution processed NiOx films. By varying EDA content (0–10.0 v/v %) in the precursor, we could find out that
Solar cells
adequate EDA additive (~5.0%) provide much reduced electrical resistivity and enhanced optical transmission
compared with control NiOx film (No EDA) by suppressing formation of byproducts (i.e. nickel hydroxide). In
addition, AFM surface topography showed much compact and dense deposition of NiOx film on ITO electrode.
This contributed to improve charge transport properties and suppress charge recombination loss at ITO/per-
ovskite interface, which provided strong enhancement in fill factor from 0.599 to 0.714 in the perovskite solar
cells. As a result, a power conversion efficiency (PCE) was strongly increased from 13.9 (No EDA) to 16.7% (EDA
5.0%). This also outperformed the performance (14.3%) of device using PEDOT: PSS, which indicates that the
adequate control of EDA additive for NiOx HTL could offer much promising photovoltaic performance.

1. Introduction methylammonium iodide (MAI) and ZnO, so variation of coating

Organolead halide perovskite solar cells have been received con-
siderable attention due to its high power conversion efficiency (PCE)
over 22% [1], low materials costs, and simple fabrication using solution
processing [2]. Strong optoelectronic properties of perovskites such as
strong absorption coefficient, long diffusion lengths and good mobility
of charge carriers are fundamentals for achieving such impressive
photovoltaic performances [3–5]. Bandgap tuning with varying com-
position of perovskites can also provide construction of tandem archi-
tecture under proper combination of different bandgaps [6,7]. Besides
of the promising perovskite light absorber, hole transport layer (HTL)
and electron transport layer (ETL) have been widely studied for effi-
cient charge extraction/collection [6]. Recently, organometallic pre-
cursors have been widely employed to form metal-oxide thin film in-
stead of organic charge transport layers due to their low long-term
stability under oxidation and/or relatively high material costs [8]. In
case of conventional n-i-p structure of fluorine-doped SnO2 (FTO)/ETL/
perovskite/HTL/rear metal, TiO2 [1,9] or ZnO [10] have been re-
presentatively used as ETL, however, a high sintering process of TiO2
over 450 °C limits flexible application of the perovskites. Solution-
processed ZnO ETL also has some issues of reaction between
technology is needed [10]. As for inverted planar architecture of in-
dium-tin-oxide (ITO)/HTL/perovskite/ETL/rear metal, on the other
hand, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
(PEDOT: PSS, PVP AI 4083) as a hole transport layer (HTL) has been
used its benefits of low temperature processing and simple fabrication
[11]. In spite of good hole collecting properties of the PEDOT: PSS,
hygroscopic nature could limit long-term stability of organic/perovskite
solar cells [12]. Instead, various metal oxides such as NiOx [8], CuOx
[13], and etc. have been developed as HTL [14,15]. The NiOx showed
satisfactory hole-collecting properties with deeper valence band (− 5.3
– − 5.4 eV) than PEDOT: PSS which can increase open circuit voltage
(Voc) of the solar cells [6].
There have been various fabrication techniques using different
nickel precursors and solvents to form NiOx thin films such as nickel
formate dihydrate with ethylenediamine (EDA) [16], nickel acetate
tetrahydrate complexed with methanolamine [17], nickel nitrate hex-
ahydrate with MEA (monoethanolamine) [18], nickel nitrate hexahy-
drate with ethyleneglycol and EDA [8]. We have also been employing
nickel nitrate hexahydrate with ethyleneglycol solvent and EDA ad-
ditive to form the NiOx thin film as HTLs for inverted planar archi-
tecture of perovskite solar cells. For high performance of solar cells,

⁎
Corresponding author.
E-mail address: kangdwn@cau.ac.kr (D.-W. Kang).

https://doi.org/10.1016/j.ceramint.2018.02.147
Received 14 November 2017; Received in revised form 17 February 2018; Accepted 17 February 2018
Available online 17 February 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S. Yoon, D.-W. Kang
highly conductivity, wide-bandgap, good matching of valence band
level with perovskites, and simple processing (under low temperature)
are required characteristics of the NiOx HTL, which depends on the
fabrication of solution processing with different solvents/additives. On
the other hand, effects of the EDA additive concentration on properties
of formed NiOx thin films and thus their application on perovskite solar
cells have been scarcely reported to date. The solvent/additive analyses
on formation of resultant films are required to obtain high quality metal
oxide HTL. Thus, in this work, we varied relative volume ratio of EDA
additive (0–10% v/v) in precursor composition (nickel nitrate hex-
ahydrate dissolved with ethyleneglycol solvent). From the fabricated
NiOx thin films, optoelectronic and surface morphological analyses
have been made to characterize them. With proper EDA partial con-
centration of ~5%, highly transparent and low resistive NiOx films were
obtained. Also, compact and dense morphology was also found, which
is preferred for low recombination loss for photovoltaic device opera-
tion [19]. As a result, this NiOx HTL contributed to achieve an im-
pressive PCE about 16.7%, whereas the best performing devices using
conventional PEDOT: PSS and NiOx without EDA additive showed
14.3% and 13.9%, respectively. This precursor optimization using
adequate additive for NiOx HTL can be strongly beneficial to achieve
high performance inverted planar perovskite photovoltaics with very
simple solution processing.
2. Experimental detail
2.1. Information of materials
MAI (Methyl ammonium iodide, 99.99%), PbI2 (99.9985%) were
purchased and used as is to make precursors for MAPbI3 perovskites.
DMF (Dimethylformamide, 99.5%), DMSO (Dimethyl sulfoxide,
99.8%), CBZ (chlorobenzene, mono, > 99.5%) were employed as main
solvents and/or anti-solvents. For charge transport materials, poly(3,4-
ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS, PVP AI
4083) as a hole transport layer (HTL) and Phenyl-C61-butyric acid
methyl ester (PCBM, 99.5%, Nano-C) as an electron transport layer
(ETL) were used as is. In addition, NiOx precursor solution was made
using Ni(NO3)2·6H2O (99.999%), ethyleneglycol (99.5%), and ethyle-
nediamine (EDA, 99.0%).
2.2. Preparation of NiOx thin films
For characterization of the solution processed NiOx HTL, it was
coated on bare glass or ITO substrates. First, NiOx precursor solutions
with various EDA additive concentration (0, 2.5, 5.0, 6.7, 7.5, 10.0 v/v
%) were made by dissolving nickel nitrate hexahydrate (Ni
(NO3)2·6H2O) of 0.291 g in ethyleneglycol of 1 mL. The solutions were
stirred at room temperature for 12 h. The image of resultant solutions is
shown in Fig. 1. The NiOx precursor solutions with various EDA con-
centration (0–10.0%) were coated onto each substrate at 4000 rpm for
90 s and annealed at 300 °C for 60 min in air-ambient.
2.3. Device fabrication
ITO glass substrates (15 Ω·sq−1) were cleaned with a sequential step
of acetone, methyl alcohol, and isopropyl alcohol for 10 min, respec-
tively. After drying them in an oven, UV-ozone treatment for hydro-
philic surfaces was made for 20 min. Then PEDOT: PSS (PVP AI 4083)
solution was spin-casted on the substrates at 4000 rpm for 50 s and
annealed at 140 °C in air-ambient. Regarding perovskite precursor,
MAPbI3 (50 wt%) perovskite solution was made by dissolving MAI
(0.286 g) and PbI2 (0.830 g) 1 mL DMF with DMSO (128 μL), and stirred
at 65 °C for 12 h. Afterward, MAPbI3 perovskite precursors (filtered
with a 0.45 µm PVDF filter) were spin-casted on the PEDOT: PSS or
NiOx HTLs in a glovebox. And then, the PC61BM solution was spin-
coated onto the perovskite films at 400 rpm for 1 s and 1500 rpm at 35 s
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Ceramics International 44 (2018) 9347–9352
Fig. 1. Fabricated NiOx precursor solutions with different ethylenediamine (EDA) con-
centration from 0% to 10.0% (v/v).
in the glovebox too. Finally, silver electrode was thermally-evaporated
under high vacuum through a shadow mask. The active area of solar
cells was 4 mm2.
2.4. Characterization of films and devices
Optical transmittance spectra of the various HTLs were character-
ized by ultraviolet-visible (UV–Vis) spectrophotometry (UV-2700;
Shimadzu). Fourier transform infrared (FT-IR) measurement was per-
formed to analyze film components by using the equipment (Vertex
80 v; Bruker) with a detector detector (mercury-cadmium-telluride:
MCT) and a beam-splitter (KBr). The FT-IR was measured with scanning
128 times under a resolution of 2 cm−1. The film thicknesses were
measured by a surface profiler (D-100; KLA Tencor). Surface
morphologies of the various NiOx HTLs were analyzed by using atomic
force microscopy (AFM) (SA-AFM; Proves Inc.). Electrical resistivity of
those NiOx films were estimated by preparing patterned Ag-electrodes
on film surfaces, and following current-voltage sweeping was made
with using a parameter analyzer. All current density-voltage (J-V)
curves of the fabricated perovskite solar cells were measured by a solar
simulator (Polaronix K201; McScience) under an AM 1.5 standard
condition in air-ambient (100 mW/cm2, relative humidity = 20–30%,
25 °C).
3. Results and discussion
In this study, perovskite solar cells were constructed based on p-i-n
type inverted planar structure. On the ITO-glass, PEDOT: PSS or NiOx
hole collectors were deposited before coating of perovskite light har-
vester, which means that optical transmission of those HTL is crucial to
make light in-coupling into perovskite absorber. Thus, we first char-
acterized optical transmittance of fabricated NiOx films with various
EDA additive concentration (0–10.0%) as well as PEDOT: PSS as HTLs,
as shown in Fig. 2. In comparison with the PEDOT: PSS, we could find
the pronounced transmission of the NiOx films regardless of the EDA
additive concentration (0–10.0%) in whole spectral wavelengths. This
can be attributed to wide bandgap (~3.2–3.6 eV) of the NiOx compared
with that (~2.0–2.2 eV) of PEDOT: PSS [16,20–22]. This indicates that
the metal oxide film can further reduce parasitic absorption loss at HTL,
which allows for transmission of more incident light into perovskite
absorber. It is beneficial to improve short circuit current (Jsc) of pho-
tovoltaic cells. As for the NiOx samples with various EDA concentration,
the NiOx films made without EDA additive and made with EDA of 10%
showed slight lower transmission compared with films made using EDA
additive ratio (2.5–7.5%). This can be elucidated with compositional
analyses of the solution processed NiOx films.
Fig. 3 shows FT-IR absorption spectra of the solution processed NiOx
S. Yoon, D.-W. Kang
Fig. 2. Optical transmission of various hole transport layers (HTL) such as PEDOT:PSS
and NiOx films with different EDA concentration from 0% to 10.0% (v/v).
Fig. 3. FT-IR spectra of NiOx films with different EDA concentration from 0% to 10.0%
(v/v).
thin films made with various concentration of the EDA additive. For the
sample made without the EDA additive and small amount of addition
(EDA 2.5%), absorption peaks at 3570 cm−1 which are related with Ni
(OH)2 are found [23,24]. Moreover, the peaks between 3160 and
3300 cm−1 correspond to vibration of O-H stretching [25,26]. These
clues suggest the following chemical reactions (1) and (2) during
thermal annealing of the spin-coated NiOx films.
2{Ni(NO3)2·6H2O} → 2[Ni(H2O)6]2+ + 4NO2 + 2O2
2[Ni(H2O)6] 2+
+O2 → NiO + Ni(OH)2 + 11H2O
2[Ni(H2O)6] 2+
+ 6[C2H2(NH2)2] (EDA) → 2[Ni(NH3)6] 2+
+ 6[C2H2(OH)2]
2[Ni(NH3)6] 2+
+O2 → 2NiO + 12NH3
The formed Ni(OH)2 byproduct would cause additional absorption
loss and also deterioration of electrical properties. Also, the absorption
peak at 1540 cm−1 was originated from N-O stretching of NO2 in re-
action (1). On the other hand, chemical reactions of the nickel oxide
precursors with the EDA additives are suggested as the above reaction
(3) and (4). Using the EDA, possible byproduct formation would be
relatively reduced and higher purity NiOx films could be formed. In the
FT-IR results, the peaks related with Ni(OH)2 and vibration of O-H
stretching decreased with applying adequate EDA additive (5.0–6.7%).
With the increased EDA content (> 7.5%), the absorption peak at
1018 cm−1 was observed, which corresponds to C-N stretching from
EDA [27,28]. When we see the Fig. 1, the NiOx precursor solution
Ceramics International 44 (2018) 9347–9352
Fig. 4. Electrical resistivity of fabricated NiOx films with different EDA concentration
from 0% to 10.0% (v/v).
without EDA has green color due to [Ni(H2O)6]2+. Also, the color
change to blue is shown to be strong with increasing EDA concentration
due to increase in [Ni(NH3)6]2+ content. These indicate that the re-
sidual components related with EDA remained in the NiOx films pre-
sumably due to excess supply of EDA into NiOx precursor for the case of
the EDA (7.5–10.0%). In this point of view, the slight less transmission
shown in Fig. 2 can be ascribed to absorption losses from these un-
desirable byproducts by solution processing.
In order to cross-check these investigations and assess electrical
property of the NiOx films, electrical resistivity of fabricated films were
provided by current-voltage measurements as revealed in Fig. 4. Basi-
cally the NiOx films showed relatively higher resistivity (≥ 104 Ω·cm)
compared with conducting polymer PEDOT: PSS (≥ 103 Ω·cm), since
the prepared NiOx films in this study are non-doped metal oxide with
very thin thickness (~20 nm). Nevertheless, the resistivity decreased
with introducing EDA additive from 0% to 5.0% into precursor solu-
tion. This could be attributed to transformation of NiOx film to high
purity as byproducts (Ni(OH)2 and O-H bonds) were eliminated by EDA
addition as confirmed in FT-IR analysis. After the minimum point at
5.0% EDA, the resistivity began to increase and approached to the level
(6 × 104 Ω·cm) at 7.5% EDA, which is similar to the sample made
without EDA. Further increase of the EDA addition (~ 10.0%) dete-
riorated the resistivity much, which would be affected by residual EDA
in the NiOx film.
In addition to the optoelectronic analyses above, we also tried to
examine AFM surface topography of the various NiOx films as a func-
tion of EDA additive content, as shown in Fig. 5. The surface of ITO
(Fig. 5(a)) and NiOx (EDA 0%) coated on ITO ((Fig. 5(b)) substrate
(1) show regular distribution of crystallites reflecting surface of underlying
ITO material due to conformal deposition of thin NiOx layer (~ 20 nm).
(2)
Here, vacancies/holes were observed through the dark spots in the
images. However, the surface was transformed to much dense and
(3) uniform by increasing EDA additives (5.0–6.7%) as revealed in Fig. 5(d)
and (e). This topography indicates less pinholes and/or compact ad-
(4)
hesion between ITO and NiOx, which is beneficial for construction of
planar thin film devices. With further increase in EDA content over
7.5% (Fig. 5(f) and (g)), the surface became rough again and much
pinholes were found. These results suggest that a high purity film with
suppressed formation of byproduct by proper EDA additives could
allow for highly compact, conformal deposition of the NiOx on under-
lying ITO substrate.
On the basis of the fundamental studies on solution processed NiOx
films with various EDA additives, we have fabricated planar perovskite
solar cells and assessed the performance to observe impacts of the de-
veloped NiOx as a HTL. Fig. 6(a) exhibits the device structure and their
energy level diagram is shown in Fig. 6(b). The NiOx has deeper valence
band energy (− 5.3 eV) compared with PEDOT: PSS of which highest
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Fig. 5. AFM surface topography images of various HTL films such as (a) bare ITO, (b) NiOx (EDA 0%), (c) NiOx (EDA 2.5%), (d) NiOx (EDA 5.0%), (e) NiOx (EDA 6.7%), (f) NiOx (EDA
7.5%), and (g) NiOx (EDA 10.0%). It is noted that the NiOx films were coated on ITO/glass substrates.

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S. Yoon, D.-W. Kang Ceramics International 44 (2018) 9347–9352

characteristics and detail photovoltaic parameters of the best per-

Fig. 6. (a) Device architecture of constructed planar perovskite solar cells, and (b) energy
level diagram of the prepared perovskite solar cells.
forming perovskite solar cell with employing various NiOx films. As a
control device, the results of fabricated cell using PEDOT: PSS were
given, which showed a nice PCE of 14.3% indicating that conventional
PEDOT: PSS works well as a HTL in our experiment. In case of the NiOx
HTL without EDA, it showed slightly less PCE due to low fill factor (FF)
in spite of great increase in Voc and Jsc. The increase in the Voc and Jsc
are attributed to the valence band energy (− 5.3 eV) and high trans-
mission, respectively. The poor FF is reflected by slightly high series
resistance (Rs) and much low shunt resistance (Rsh). The high resistivity
of the non-doped NiOx film shown in Fig. 4 is responsible for the high
Rs. Also, carrier recombination at ITO/perovskite interface via some
pinholes on surface is a possible factor that causes such low Rsh in the
devices. However, when the EDA concentration increased up to 5.0%,
we could find impressive enhancement in the PCE (~16.7%) by re-
markable increase in FF from 0.599 to 0.714. The decrease in Rs and
increase in Rsh are attained by decreased electrical resistivity and much
planar/dense topography of NiOx, respectively. The carrier transfer
process would be much feasible and also recombination between ITO/
perovskite via pinholes could be suppressed. On the other hand, the
excess EDA concentration (7.5–10.0%) made the photovoltaic perfor-
mance drop again due to sacrifice of FF, which is caused by the increase
in the resistivity of NiOx film and worsened surface roughness including
vacancies/pinholes (dark spots in the images). For statistical evaluation
of the fabricated devices, average values of the photovoltaic parameters
(averaging 18 devices for each sample) were provided Table 2. We
could demonstrate that adequate tuning of EDA additive concentration
provides considerable enhancement in PCE from 10.4% (No EDA) to
16.4% (EDA 5.0%) by mainly reinforcing the FF from 0.515 to 0.714.
Furthermore, we also investigated J-V hysteresis of our best performing
device employing the NiOx HTL made with optimized EDA concentra-
tion (5.0%) as displayed in Fig. 8. We could find that there was negli-
gible difference in photovoltaic performance under forward and reverse
scan rate of 0.01 V/s, which reflects intrinsic stability of the perovskite
solar cell employing the NiOx HTL. The demonstrated experimental
results suggest that successful optimization of the EDA additive con-
centration could offer promising photovoltaic properties with an in-
trinsic stability. Also, this NiOx HTL can replace the organic conducting
polymer, PEDOT: PSS, since it is expensive and has hygroscopic nature
that causes problem of long-term reliability [29]. Further enhancement
can be made by doping for NiOx or interface engineering between NiOx/
perovskite to further reduce Rs and improve FF. We believe that this
work can boost further the PCE of perovskite solar cells which is cur-
rently in progress.

Fig. 7. Current density-voltage (J-V) characteristics of perovskite solar cells employing

various HTLs such as PEDOT:PSS and NiOx with different EDA concentration from 0% to
4. Conclusion
10.0% (v/v).
We have prepared high quality solution processed NiOx thin films by
optimizing EDA concentration (0–10.0 v/v %) in the NiOx precursor
Table 1
Photovoltaic parameters of fabricated planar perovskite solar cells employing NiOx hole
solution. With the proper EDA content (~5.0%), the electrical re-
transport layer (HTL) made with various ethylenediamine (EDA) concentration. sistivity could be decreased with maintaining high optical transmission
by suppressing the formation of byproducts such as Ni(OH)2 and O-H
Best Device Voc (V) Jsc(mA/cm2) FF (%) PCE (%) Rs (Ω∙cm2) Rsh (Ω∙cm2) bonding in the resultant NiOx films. This precursor composition with
PEDOT: PSS 0.981 19.65 0.743 14.32 6.7 4397.6
EDA 0% 1.097 21.24 0.599 13.95 16.8 740.0 Table 2
EDA 2.5% 1.116 21.43 0.662 15.84 12.9 1082.5 Statistical evaluation of photovoltaic parameters by averaging 18 devices employing NiOx
EDA 5.0% 1.103 21.28 0.714 16.74 9.4 1345.2 HTLs made with various ethylenediamine (EDA) concentration.
EDA 6.7% 1.080 21.13 0.713 16.28 10.0 1231.2
EDA 7.5% 1.071 20.68 0.705 15.63 10.9 1181.4 Average Voc (V) Jsc (mA/cm2) FF PCE (%) Rs (Ω∙cm2) Rsh (Ω∙cm2)
EDA 10.0% 1.103 20.60 0.627 14.23 17.8 1041.6 Device

EDA 0% 1.054 18.97 0.515 10.40 22.8 417.2

EDA 2.5% 1.088 20.03 0.600 13.17 18.0 709.4
EDA 5.0% 1.091 21.07 0.714 16.41 9.2 1296.7
occupied molecular orbital (HOMO) energy is around (− 5.2 eV) EDA 6.7% 1.090 20.60 0.737 15.77 10.0 1256.5
[16,20–22]. This is helpful to improve Voc of solar cells due to less loss EDA 7.5% 1.087 19.95 0.676 14.64 15.1 1223.4
of potential. Fig. 7 and Table 1 exhibit current density-voltage (J-V) EDA 10.0% 1.086 20.21 0.655 14.35 15.4 1139.5

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S. Yoon, D.-W. Kang
Fig. 8. J-V hysteresis investigation of the best perovskite solar cell made with NiOx (EDA
5.0%) HTL.
the optimized EDA also assisted to deposit very compact and dense
NiOx film on ITO conducting electrode. By applying this promising NiOx
as HTLs for planar perovskite solar cells, we could achieve the best
performing device PCE of 16.7% whereas device made with EDA-free
NiOx showed 13.9% (average 10.4%). This best device also outperforms
the PCE (14.3%) of solar cell using the PEDOT: PSS. We believe that this
impressive experimental result can open up new routes for development
of high performance and long-term stable perovskite solar cells using
very simple solution processing.
Acknowledgements
This work was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korea government (MSIP)
(No.2015R1C1A1A01053624).
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