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Surface Sulfuration of NiO Boosts the Performance of

Inverted Perovskite Solar Cells
Chen Hu, Yang Bai, Shuang Xiao, Kewen Tao, Wai Kit Ng, Kam Sing Wong,
Sin Hang Cheung, Shu Kong So, Qi Chen, and Shihe Yang*

interface engineering[3] on the perovskite

As one of the most promising hole-transporting materials for perovskite solar charge-transporting layer interface are the
cells (PSC), NiO is widely used in the inverted p–i–n cell structure due to its high main approaches for promoting the PCE
stability, decent hole conductivity, and easy processability for hysteresis-free cells. of PSCs. Due to solution processability,
optoelectronic tunability, and the structural
However, the efficiency of NiO-based PSCs is still low, due largely to the poor
tolerance[4] of perovskite, a large amount of
perovskite/NiO interface. Herein, a sulfur-doping strategy to modify NiO surface materials can be used for the charge-
via ion exchange reaction by a simple and scalable chemical bath deposition transporting layer[5] for efficient solar cell
technique is introduced, which greatly improves the photovoltaic (PV) perfor- devices, and several device architectures
mance of the derived devices. A systematic investigation is shown where sulfur have been extensively studied. For example,
doping leads to favorable interfacial energetics with a reduced Voc loss. Sulfur n–i–p-type PSCs with mesoporous TiO2[6]
or planar SnO2[7] as electron-transporting
doping at the interface also improves the contact between NiO and perovksite
layers have demonstrated outstanding
and facilitates the formation of high-quality perovskite films. Carrier dynamics device performance. As an alternative to
studies demonstrate reduced defect states and trap-assisted recombination with the n–i–p-type PSCs, inverted p–i–n
sulfur doping, which promote the PV performance of the devices. These merits PSCs have drawn increasing attention for
contribute concurrently to low-loss charge transfer across the perovskite/NiO their superior stability, scalability, negligi-
interface and facilitate charge transport through the perovskite films, leading to a ble hysteresis, and simple processing. In
other words, p–i–n PSCs exhibit great
high champion efficiency of 20.43% of the p–i–n structure solar cell devices.
potential in commercialization.[8] These
supreme features were mainly attributed
to hole-transporting materials (HTMs)
used in inverted PSCs (e.g., PEDOT-PSS,
1. Introduction PTAA), among which planar NiO appears to be a promising
choice for its outstanding stability over organic HTMs.[9]
Hybrid organic–inorganic perovskite solar cells (PSCs) have been However, the efficiency for NiO-based PSCs is relatively low
a rising star in solar energy-conversion devices. In five years, the as compared with the n–i–p-type PSCs.[1,10] At least one of the
certified champion power conversion efficiency (PCE) of PSCs reasons is believed to be the imperfect interface between NiO
has leaped to 25.2% in 2020[1] and surpassed that of commercial- and PVK.[3a] There are several approaches to tackle this problem.
ized multicrystalline silicon and copper indium gallium selenide For one thing, doping NiO with metallic elements such as Mg,[11]
(CIGS) solar cells at 22.8% and 23.4%, respectively, approaching Cu,[12] and Cs[13] can improve the hole concentration of NiO and
the record of the single-crystal silicon solar cell at 26%. modify its energy levels near the valence band edge. For another,
Compositional engineering[2] on perovskite material and surface treatment of NiO with organic molecules such as

C. Hu, Prof. S. Yang Prof. S. Xiao, K. Tao, Prof. S. Yang

Department of Chemistry Guangdong Provincial Key Lab of Nano-Micro Materials Research
The Hong Kong University of Science and Technology School of Chemical Biology and Biotechnology
Clear Water Bay, Kowloon, Hong Kong, China Peking University Shenzhen Graduate School
E-mail: chsyang@pku.edu.cn Shenzhen 518055, China
Prof. Y. Bai, Prof. Q. Chen W. K. Ng, Prof. K. S. Wong
Beijing Key Laboratory of Construction Tailorable Advanced Functional Department of Physics
Materials and Green Applications The Hong Kong University of Science and Technology
Experimental Centre of Advanced Materials Clear Water Bay, Kowloon, Hong Kong, China
School of Materials Science & Engineering
Beijing Institute of Technology Dr. S. H. Cheung, Prof. S. K. So
100081 Beijing, China Department of Physics and Institute of Advanced Materials
Hong Kong Baptist University
The ORCID identification number(s) for the author(s) of this article Kowloon Tong, Hong Kong SAR, P. R. China
can be found under https://doi.org/10.1002/solr.202000270.
DOI: 10.1002/solr.202000270

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ethanolamine[14] can chemically bridge NiO and perovskite for
better interfacial contact. Another example is surface doping
with a small molecule F6TCNNQ which can modify the surface
energetics for a better match with the highest occupied molecular
orbital (HOMO) of perovskite.[15] However, doping the bulk NiO
may create undesirable structural defects and modifying the surface
of NiO with organic molecules also has issues regarding long-term
stability of organics under irradiation especially at the front side.[16]
In the present work, we introduced a novel and effective sur-
face modification protocol for doping NiO surface with sulfur via
chemical bath deposition (CBD). By simply immersing NiO film
into the aqueous bath of thioacetamide, S doping on NiO was
obtained from the ion exchange reaction (IER). Systematic stud-
ies have shown the beneficial effect of S doping on photovoltaic
(PV) performance. First, the valance band maximum (VBM) and
work function of S-doped NiO (S-NiO) was modified to reduce
the interfacial energy gap between NiO and perovskite for a bet-
ter energy alignment. Second, depth profiles from secondary ion
mass spectroscopy–time of flight (SIMS–ToF) measurements
demonstrated that sulfur on the surface of NiO is bonded to
Pb of perovskite, thus effectively passivating interface defects
as well as improving the perovskite film quality deposited there-
upon. Charge dynamics studies on the S–NiO solar cell devices
as well as on the NiO/perovskite thin films showed that S-doping
significantly improved charge transfer and transport kinetics at
the interface, with a higher resistance against recombination,
and in the bulk of the high-quality perovskite films. As a result,
PCE was boosted from 18.34% with pristine NiO as the hole-
transporting layer to 20.43% with S–NiO, which is among the
highest reported for inverted PSCs.[15,17]
2. Results and Discussion
2.1. Sulfur Doping on the Surface of NiOx Thin Films
A simple and effective sulfur doping method was adopted in
this work for NiOx films. Figure 1a shows the doping process.
Briefly, a NiOx thin film was dipped into an aqueous solu-
tion of thioacetamide at an elevated temperature of 75
C.
Thioacetamide, as a mild reagent, was first hydrolyzed to release
sulfide slowly,[18] which subsequently reacted with nickel oxide
by IER.[19] NiS was then generated, driven by its much lower sol-
ubility product constant (Ksp,NiS) at 1.3  105 than that of NiO
(Ksp,NiO ¼ 1.5  107).[19] As a result, sulfur was successfully
doped onto the surface of the NiOx thin film. As compared with
other surface modification or bulk doping strategies,[9b,20] this
approach based on CBD is highly scalable[21] and simple with
minimal energy input.
To identify the variation of chemical composition after IER,
depth profiles derived from ToF–SIMS of bare and doped
NiOx thin films were compared (Figure 1b,c). In both cases,
Ni signal (red curve) dominated at the beginning of the sputter-
ing process, demonstrating full coverage of the NiOx thin film.
As the sputtering time elapsed, the intensity of SnO2 from FTO
glass (blue curve) climbed up, signifying that the secondary ion
beam had penetrated through the NiOx layer. Clearly, the black
line that represented the signal from sulfur fragments of S–NiO
film (Figure 1c) was significantly higher than that from the bare
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NiO sample (Figure 1b), affirming the successful S doping at the
NiO/PVK interface.
To understand the compositional and structural variations
after S doping and deposition of the perovskite layer, we also con-
ducted depth profiling of the FTO/NiO/PVK samples, and the
results are shown (Figure 1d,e). The PbI fragment signal (violet
curve), which expresses the perovskite (PVK) layer on top of NiO,
is similar in both profiles as expected. Most notably, the intensity
of S signal (black curve) is much higher in FTO/S-NiO/PVK
film (Figure 1e) than that in FTO/NiO/PVK film (Figure 1d),
authenticating the successful doping of interfacial sulfur and
its intactness against the perovskite spin-coating process.
Moreover, the PbS fragment signal with a relatively high inten-
sity was detected in FTO/S-NiO/PVK (green curve in Figure 1e),
demonstrating the existence of chemically bonded Pb–S as a
result of the interfacial S doping on NiO. It is interesting to note
that the evolution profile of the S signal (black) shows almost the
same pattern as that of PbS (green), and both of them dropped
pronouncedly earlier than the Ni signal (red). Meanwhile,
the S signal increases after the PVK signals drop down. Taken
together, the spatial distribution of PbS is in between the layers
of PVK and NiO. In other words, Pb was bonded with S at the
PVK/S–NiO interface. Therefore, we can conclude that sulfur is
doped onto the surface of the NiO thin film and bonded to Pb in
perovskite after deposition of the perovskite layer. To evaluate
how reaction time is related to the amount of S doped onto
NiO, we carried out energy-dispersive X-ray spectroscopy–scan-
ning electron microscopy (SEM) and presented the mole fraction
of S/Ni for S–NiO thin films that reacted in different durations,
as shown in in Figure S1, Supporting Information. As the reac-
tion time prolonged, the molar ratio of S over Ni increased and
became stable after 30 min. The dense film may help block sub-
sequent contact after 60 min and prevent further reaction.
2.2. Photovoltaic Performance and Characterizations
The PV performances on NiO and S–NiO films were compared
by fabricating solar cell structure FTO/NiO/MAPbI3/PCBM/
PPDIN6/Ag (Figure 2a,b). The champion device from S–NiO
was achieved by optimizing the reaction time of S doping. As
shown in Figure S2, Supporting Information, 5 min is found
to be the optimal time for the best performance. With the
increase in reaction time, the PCE of the related solar cell
decreased mainly due to a lower Jsc. This can be explained by
enhanced light absorption from S–NiO. As shown in
Figure S3, Supporting Information, the absorption of S–NiO thin
film increased as reaction time extended, which seems to reach a
plateau after 10 min. To test the reproducibility of PCE improve-
ment, 30 solar cells of each condition were fabricated under the
same experimental condition. With 5 min of sulfur-modified
NiOx, the champion efficiency boosted to 20.43% as compared
with 18.34% for solar cell based on bare NiOx. In details,
open-circuit voltage (Voc) increased from 1.081 to 1.101 V by
20 meV. Short-circuit current increased to 23.28 mA cm2 from
22.77 mA cm2 and fill factor (FF) improved significantly from
0.75 to 0.80. The shunt resistance Rsh and series resistance Rs
can be obtained by fitting the J–V curve with the Shockley
equation (Equation (1)).[22]
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Figure 1. a) Schematic illustration of the S doping process on the NiO surface. Depth profiles from ToF–SIMS of b) FTO/NiO thin film. c) FTO/S–NiO
thin film. d) FTO/NiO/PVK film and e) FTO/S–NiO thin film. Arrows in (e) show the rise of S signal at the interface as a result of S doping.

"   #
qðV  JRs Þ V  JRs which is slightly lower than that of the NiO device at 5.35 Ω cm2
J sc ¼ J ph  J 0 exp 1  (1) due to improved quality of the perovskite layer and electrical con-
nkT Rsh
ductivity of the transport layer. The hole-only device with the
structure of FTO/NiO/Spiro-OMeTAD/Au were fabricated and
where Jph is photocurrent density. J0 is the reverse bias saturation the I–V test (Figure S4, Supporting Information) consistently
current density, q stands for elementary charge, and n represents shows that S doping promotes the conductivity of the NiO film
the diode ideality factor with k and T represent the Boltzmann’s which contributed to the increase in FF with reduced series resis-
constant and temperature, respectively. The Rsh of the S–NiO tance Rs.[10] Incident photoelectron conversion efficiency (IPCE,
device at 1282 Ω cm2 is much higher than that of the NiO device Figure 2c) also elaborated the improvement with integrated cur-
at 1013 Ω cm2 which indicates smaller leakage current and rent at 23.2 and 22.4 mA cm2 for the device based on S–NiO and
less defect-induced recombination upon S doping, as will be dis- NiO, respectively. As shown in Figure 2d, the efficiency of S–NiO
cussed later. The series resistance Rs of S–NiO cell is 5.19 Ω cm2 devices distributed narrowly from 18.5% to 20.5%, where that of

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Figure 2. a) Schematic representation of solar cell device. b) J–V curves of optimal device on NiO and S–NiO. c) IPCE and integrated current density
curves of NiO and S–NiO cells. d) Statistics on photoconversion efficiencies of 30 cells.
NiO spanned from 15.5% to 18.5%, which demonstrated
excellent reproducibility for sulfur-modified NiOx as the hole-
transport layer. For a more statistical comparison, summaries
on Jsc, Voc, and FF from 30 cells were also presented
(Figure S5 and Table S1, Supporting Information). With surface
treatment, S–NiO devices demonstrated concurrent enhance-
ments on Voc, Jsc, and FF.
For a deeper exploration on the device properties of S–NiO-
and NiO-based solar cells, the transient photovoltage decay of
NiO and S–NiO devices was measured (Figure 3a) at open circuit
where most of the photocarriers recombined via trap states. That
is to say, a longer lifetime indicates less trap states in the device.
As shown in Figure 3a, the photovoltage lifetime for S–NiO device
at 1.06 ms is significantly longer that of the NiO device at 0.15 ms,
which explains the improvement of average Voc, as shown in
Table S1, Supporting Information, from 1.09 V to over 1.11 V.[23]
Less trap-induced charge recombination can also benefit the
photocurrent output which is also consistent with the increase
in average photocurrent output from 21.69 to 22.92 mA cm2
and Rsh. To further validate our findings, intensity-modulated
photovoltage spectroscopy (IMVS) was used to obtain the carrier
lifetime (τn) of devices based on NiO and S–NiO at different inci-
dent light intensities.[24] As clearly shown in Figure 3b, τn of the
S–NiO-based device is significantly higher than the pristine NiO
device within the range of light intensities. A longer carrier life-
time of S–NiO-based cells means less recombination during
charge transport. To study the charge-transport properties of
two devices, electrical impedance spectroscopy (EIS) was taken
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in the dark at open-circuit voltage, as shown in Figure 3c. The
result was fitted into an equivalent circuit, as shown in the inset
of Figure 3c. The middle-frequency zone was reported to be dom-
inated by the junction capacitance and recombination resistance
(Rrec) at the interface.[23] In this case, Rrec of the S–NiO device is
223.4 Ω which is significantly higher than that of the NiO device
at 172.6 Ω, signifying that S doping suppressed the charge recom-
bination at the interface and hence facilitated a higher FF for
S–NiO devices. In addition, light intensity-dependent Voc decay
of S–NiO and NiO devices is recorded in Figure 3d. The slope of
NiO device in the natural logarithm is 1.61 kT q1 whereas that
of S–NiO device is at 1.35 kT q1. As the slope of kT q1 (ideality
factor n ¼ 1) indicates a pure bimolecular recombination pathway
and 2 kT q1 (ideality factor n ¼ 2) represents trap-assisted charge
recombination, the much smaller slope of S–NiO approaching
1 kT q1 again demonstrated the solidity of S doping in minimiz-
ing trap-assisted recombination.[25] As a result, S–NiO-based devi-
ces exhibited a higher shunt resistance Rsh and thus a higher FF,
as proved from dark current measurements. As shown in
Figure S6, Supporting Information, at a low voltage below the first
linear region (less than 0.15 V), the dark current of device is dom-
inated by shunt current whereas above the linear region (higher
than 1.05 V) the total current is mainly affected by diffusion cur-
rent, limited by series resistance. S–NiO devices exhibit a lower
leakage current in the low- and high-voltage regions correspond-
ing to lower shunt and series losses. respectively, under the dark
J–V scans, which can explain the improvement of FF, Jsc, and
Voc.[26] As an interim conclusion, it is now clear that the S doping
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Figure 3. Device characterization of solar cells based on NiO (black curve) and S–NiO (red curve) as the hole-transport layer. a) Normalized transient
photovoltage decay. b) Carrier lifetime plotted against applied voltage measured by IMVS. c) Nyquist plot of the solar cell device measured in the dark at
open-circuit voltage. d) Light-intensity-dependent Voc at the logarithm scale.

on the NiO surface can significantly enhance PV performance by
reducing trap-induced charge recombination and prolonging car-
rier lifetime. As trap states in PSCs mainly arise from interface
contacts and grain boundaries, it is essential to understand how S
doping could affect the device in these two aspects.[4] Hence, to
systematically study the material properties of NiO thin films
upon S doping, we conducted a series of comparative studies
of NiO/PVK thin films with or without sulfur treatment.
2.3. Electronic Effect of S Doping on NiOx Thin Films
The electronic structures of S–NiO and NiO were investigated
with ultraviolet photoelectron spectroscopy (UPS). The UPS
spectra in the secondary electron cut-off regions and around
the Fermi energy level of NiO films are shown in Figure 4a,
and the full UPS spectra are shown in Figure S7, Supporting
Information. As shown in Figure 4a, as the reaction time
increased from 0, 3, 5 to 10 min, the VBM and Fermi level
shifted to deeper levels. A smaller energy-level offset
(ΔE ¼ VBMPVK  VBMNiO ) between HTL and perovskite layer
is generally more favored for efficient interfacial charge trans-
port due to less thermionic loss.[3a,15] A previous study demon-
strated that Voc of a solar cell will decrease with increasing ΔE
due to the free energy loss of charge carriers across PVK/HTL
interface, causing a mismatch between Voc and the quasi Fermi-
level splitting of perovskite with reduced charge transport

Figure 4. a) UPS spectra in the secondary electron cut-off and Fermi energy cut-off regions of the thin-film samples with different sulfuration reaction
times in thioacetamide bath. b) Energy-level diagram for the inverted PSC device structure of FTO/S–NiO(NiO)/PVK/PCBM/Ag.

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efficiency.[27] With a 5 min reaction time for S doping, the
energy difference between perovskite and NiOx reached
a minimum at 0.02 eV as compared with that of 0.28 eV for
bare NiOx, which seems to be a major reason for Voc enhance-
ment from 1.09 V to around 1.11 V, with the highest Voc reach-
ing 1.12 V for S–NiO-based devices (Figure S5b, Supporting
Information). The downshift of Fermi level indicates an increase
in hole density, as shown in Equation (2). Here, p0 is hole den-
sity, Nv is the effective density of states, Ev and Ef stand for
valence-level and Fermi-level energies, k is Boltzmann constant,
and T is temperature. As Ev – Ef of the NiO significantly changed
from –0.45to –0.30 eV with 5 min of S doping, p0 increased by
342 times, assuming constant Nv at room temperature. The
increased hole density (lowered Fermi level) leads to significant
band bending, as shown in the energy diagram in Figure S8,
Supporting Information. Specifically, with S doping for 5 min,
the band bending at the interface is as large as 0.48 eV, which
is to be compared with 0.07 eV with pristine NiO, providing a large
additional driving force for hole extraction from PVK to S–NiO.[28]
Further up, we confirmed the downshift of Fermi level by Kelvin
probe force microscopy (Figure S9, Supporting Information).
 
E  Ef
p0 ¼ N v exp v (2)
kT
2.4. Effect of S Doping on Perovskite Film Growth
The morphology of the perovskite layer is influential on device
performance and can be greatly affected by substrate.[29] Due to
the well-known strong Pb–S bonding (398 kJ mol1[30]), we
Figure 5. Top-view SEM image of a) NiO/PVK and b) S–NiO PVK with a scale bar at 600 nm. XRD spectra of S–NiO and NiO-based perovskite film with
c) 600 nm perovskite layer and d) 50 nm perovskite layer.
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speculate that sulfur on the surface of NiOx substrate could
“hold” undercoordinated Pb centers during the crystallization
of the perovskite layer and passivate this site to prevent the for-
mation of undercoordinated lead cation as the point defect.[28b]
The morphological study by the SEM image shows that with
undoped NiO as the substrate, there are significant amounts
of small crystalline domains the perovskite film grew upon
(Figure 5a). On the other hand, with S–NiO as the substrate,
the crystal grains are larger and more uniform in the resultant
perovskite film (Figure 5b). When the cross-sectional SEM
image is compared (Figure S10a,b, Supporting Information),
stacking of crystal grains appears in the perovskite film grown
on the NiO substrate whereas that on S–NiO exhibits a more
monolithic feature. That is to say, in the perovskite film grown
on S–NiO, there are less grain boundaries that are parallel to the
substrate than that on NiO film. A uniform and monolithic film
with large crystal grains reduces the amount of crystal grain
boundary where deep trap states are accumulated[31] as charge
recombination centers.[25] Also, the crystalline film of the perov-
skite with less grain boundaries and larger grains possesses
higher conductivity which contributes to a smaller series resis-
tance Rs for a higher FF.[32] The thin-film X-ray diffraction
(XRD) of the perovskite deposited on S–NiO shows a higher
degree of orientation, which can be elaborated with a larger rel-
ative ratio of (110) facet over (310).[33] As shown in Figure 5c,
the (110) peak at 14.20o is proven as the preferable orientation
for efficient charge transport.[34] When compared with (310)
peak at 31.95o, the intensity ratio with (110)/(310) of S–NiO/
PVK is 298 which is significantly larger than that of NiO/PVK
at 207. Due to the polycrystalline nature of the perovskite film,
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a higher degree of orientation of the perovskite film by
S doping minimizes the lattice mismatch within the film,
thus suppressing the generation of structural defects in such
regions.
To obtain a more insightful picture of the doping effect on
film growth, a thinner film below 50 nm (SEM in Figure S10c,
Supporting Information) with sufficient interfacial information
was prepared for XRD. As provided in Figure 5d, (110) peak
of the perovskite grown on S–NiO film shifted to a lower
diffraction angle which could possibly be an evidence of lattice
expansion as a result of Pb–S bond.[35] Cross-sectional photolu-
minescence (PL) (Figure S11, Supporting Information) was
conducted to study the PL wavelength at a cross-sectional view.
It is revealed that PL at the PVK/S–NiO interface is red-shifted
which is possibly due to the lattice expansion[35,36] and does not
appear in the case of PVK/NiO interface. Also the PL wavelength
of the bulk perovskite layer deposited on top of S–NiO exhibited a
shorter wavelength (blue shifted) (Figure S11a, Supporting
Information) as compared with that on NiO (Figure S11b,
Supporting Information), which is attributed to better perovskite
film quality with less defect states and smaller band edge
tailing.[37] On the basis of the discussions earlier, it can be con-
cluded that Pb–S interaction at NiO/PVK interface promotes
perovskite film quality by enlarging crystal grain and facilitating
oriented growth. The amount of grain boundaries of perovskite
deposited on S–NiO decreases consequently as compared with
that on bare NiO, which is proven by the blue-shifted PL from
cross-sectional PL mapping. Moreover, the reduced trap states
at the NiO/PVK interface result in reduced bimolecular recom-
bination, as discussed in the device characterization section
earlier.
Figure 6. Cross-sectional PL mapping of a) NiO/PVK and b) S–NiO/PVK with color scale representing the normalized intensity of luminescence.
The scale bar is at 100 nm. c) Time-resolved transient PL decay of PVK/NiO, PVK/S–NiO, and PVK deposited on bare glass. d) PDS of PVK/NiO
and PVK/S–NiO deposited on quartz.
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2.5. Carrier Transfer across the S–NiO(NiO)/PVK Interface
For direct comparison, the carrier transport properties of PVK/NiO
and PVK/S-NiO films were studied. The interface charge-transport
dynamics of thin films were investigated mainly by PL.
First, the cross-sectional PL mapping directly reveals that interfa-
cial charge transfer across S–NiO/PVK is more efficient than that
across NiO/PVK interface. As shown in Figure 6a,b, the color of
mapping is correlated with the normalized intensity of PL with
stronger luminescence corresponding to red and reversely blue.
In detail, the upper parts in Figure 6a,b are caused by lumines-
cence from the perovskite layer, and the area at the bottom indi-
cates luminescence from PVK/NiO, as marked in the graph. By
comparing the PL evolution across PVK/NiO, it is clear that with-
out S doping the PL intensity increases from PVK to PVK/NiO
interface (Figure 6a), whereas with S doping the PL intensity
decreases from PVK to PVK/S-NiO (Figure 6b). A higher PL inten-
sity at the PVK/NiO interface relative to the bulk points out a lower
charge-quenching efficiency with a higher amount of charge car-
rier accumulated at the interface and recombines radiatively. On
the other hand, the PL intensity of PVK/S–NiO evolves in reverse
with a lower intensity near the interface, signifying not only a
higher charge-transport capability but also a bulk perovskite film
quality with less trap-assisted nonradiative recombination. The
enhanced charge quenching with S–NiO was also proven by static-
state PL which confirmed that S–NiO demonstrated more efficient
charge quenching with lower static PL intensity (Figure S12,
Supporting Information). To gain quantitative insights into the
charge-transport dynamics, time-resolved photoluminescence
(TRPL) studies were conducted (Figure 6c). Both NiO/PVK and
S–NiO/PVK decay monoexponentially and was fitted by
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y ¼ Aex=τ þ y0 , where τ is defined as carrier lifetime. S–NiO/PVK
has a much lower τ1 ¼ 58.42  0.20 ns as compared with that of
NiO/PVK where τ2 ¼ 79.21  0.26 ns. According to Equation (3)
1 1 1
¼ þ (3)
τn τPVK τCT
where τn is the PL lifetime of the heterojunction, τPVK is the
PL lifetime of bare perovskite, and τCT is charge carrier transfer
lifetime. τPVK ¼ 187.02  1.75 ns (fitted from blue curves in
Figure 6c), the charge carrier transfer life time τCT and efficiencies
can be calculated (Equation (2)) to be 84.95 ns and 55%, respec-
tively, for S–NiO/PVK and 137.41 ns and 27% for NiO/PVK.[38]
To sum up, enhanced charge quenching across the NiO/PVK inter-
face points to smaller Rsh and higher FF as demonstrated here.
In the process of interface charge transport, sub-band states can
act as defect states trapping charge carriers and thus affecting the
efficiency of carrier transport. Photothermal deflection spectros-
copy (PDS) is a sensitive technique measuring Urbach energy
(Eu) that indicates the degree of energy disorder. From the loga-
rithm plot of PDS (Figure 6d), Eu can be estimated by fitting the
linear region in Figure 6d by Equation (4), according to a previous
report.[39] Details of fitting can be found in Figure S13, Supporting
Information. The result shows that Eu for S–NiO/PVK and
NiO/PVK are 20.2 and 17.9 meV respectively. The reduction of Eu
could be addressed by a smaller structural disorder which points to
a sharper Urbach tail with a smaller density of trap states.[40] This
again emphasizes our previous discussion earlier that S doping
can passivate defect states by bonding Pb cations in a way to pre-
vent the formation of undercoordinated Pb or I vacancies.[41] The
reduction of defect states also benefits from improved perovskite
film quality with S–NiO. Less defect-induced charge recombina-
tion occurred during hole transport and is consistent with our
studies on PV devices. The reduction of defects with the increased
quality of perovskite thin film also contributed to device stability.
As shown in Figure S14, Supporting Information, the reduction of
device performance for S–NiO cell after two months of tracking is
considerably smaller than that of NiO device.
ln a ¼ ln a0 þ ðhv  E g Þ=E u (4)
3. Conclusion
In conclusion, we have demonstrated that doping NiO surface
with sulfur effectively promotes the PV performance of NiO-based
inverted PSCs, leading to a champion efficiency over 20% with the
MAPbI3 perovskite. Systematic studies have shown that the reduc-
tion of trap states at the S–NiO/perovskite interface was one of
the main reasons for the improvement on the interfacial carrier
transfer. Specifically, S doping significantly passivates trap
states at the perovskite/NiO interface by bonding with the under-
coordinated Pb cations of the perovskite layer. Importantly,
the Pb–S interaction also led to the improved quality of perovskite
films with a reduced amount of grain boundaries, reducing the
formation of structural defects and increased conductivity of
the perovskite layer that was directly adjoined. Last but not the
least, doping NiO with sulfur shifted the VBM of NiO negatively
(from 5.12 to 5.38 eV) so that NiO and perovskite (with a
Sol. RRL 2020, 2000270 2000270 (8 of 9)
www.solar-rrl.com
valence band at 5.40 eV) became better matched and reduced
the energy loss of charge carrier at this interface. The improved
perovskite film quality and optimized PVK/S–NiO contact com-
bined reduced trap-assisted charge carrier recombination and pro-
moted device performance. This study provides a simple and
scalable surface modification method to purposely elaborate inter-
facial properties between the layers of the carrier transporter and
perovskite for developing highly efficient PSCs.
4. Experimental Section
Materials: Methylammonium iodide (MAI) was purchased from Dyesol.
Lead iodide (PbI2) and other materials were obtained from Sigma-Aldrich.
Device Fabrication: The patterned FTO glass was washed successively by
water, IPA, ethanol, and acetone under sonication for 15 min, respectively.
After being dried at 70
C for 12 h, 0.01 M of nickel (II) acetylacetonate solu-
tion in acetonitrile was sprayed with homemade ultrasonic spray-coating
equipment onto the FTO substrate heated to 500
C. The film was annealed
for another 30 min followed by air cooling to room temperature. The perov-
skite solution was prepared by dissolving PbI2 and MAI into DMSO/DMF
(7:1, v:v) to obtain a stoichiometric solution of MAPbI3 at 1.4 M. The perov-
skite layer was deposited by the reported method.[33] In brief, 40 μL of
perovskite solution was dropped on to the substrate and went through
a two-step spin-coating program with 2000 rpm for 10 s and 4500 rpm
for 30 s. At the 15th second of the second step, 700μL of toluene was con-
tinuously dropped onto the spinning film. Next, the film was annealed
for 30 min at 100
C followed by spin coating a layer of 20 mg ml1 PCBM
solution of chlorobenzene at 3000 rpm for 30 s. Another buffer layer was
then deposited by spin coating a solution of 2 mg ml1 PPDIN6 dissolved
in trifluoroethanol.[17b] Finally, Ag electrode was thermally evaporated in
vacuum through a shadow mask with thickness of 100 nm.
Characterization: SEM was characterized by JEOL 7100F operated at
5 kV. XRD spectra were obtained by Philips, PW 1830, with Cu Ka radiation.
PCE and other electrical characterizations on devices were measured by a
solar simulator (Oriel, 450 W Xe lamp, AM 1.5 global filter) equipped with an
electrochemical workstation (Zanher, Zennium), with a calibrated light
source at 1 sun (100 mW cm2). PCE was measured with a shadow mask
with an aperture area of 0.1 cm2. Light source calibration was conducted
using an optical power meter (Newport, model 1916-C) equipped with a
Newport818P thermopile detector. IPCE measurements were carried out
with a tunable light source (TLS03) with a frequency of 100 Hz the above
electrochemical workstation. IMVS and IS were taken by the e Zahner
Zennium C-IMPS system with a light-emitting diode (λ ¼ 536 nm). UV–vis
absorption spectra were recorded on a Perkin–Elmer UV–vis spectropho-
tometer (model Lambda 20). UV photoelectron spectroscopy was measured
by Axis Ultra DLD. SIMS–ToF was measured by TOF SIMS V (ION-TOF
GmbH) with Csþ primary ion (3 keV, 30 nA, 300  300 μm2) for erosion
source and Biþ (25 keV, 1 pA, 48  48 μm2) for the analysis. PDS measure-
ments were carried out with a standard setup consisting of a 1 kW Xe arc
lamp and a 1/4 m grating monochromator (Oriel) as the tunable light source.
The perovskite film was deposited on a quartz substrate. Kelvin probe force
microscope was characterized by Bruker (Dimension Icon) with Pt–Ir-coated
Sb-doped Si cantilever. PL mapping was done by a laser scanning confocal
microscope (Enlitech, spcm-1000), equipped with a 470 nm pulse laser.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
Chen Hu and Yang Bai contribute equally to this work. This work was sup-
ported by HKRGC General Research Funds (GRF No. 16312216), the HK
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Innovation and Technology Fund (GHP/079/17SZ), the Natural Science
Foundation of China (21972006, 21905006, 51961165105, 51773230, and
21805010), the Shenzhen Peacock Plan (KQTD2016053015544057), the
Nanshan Pilot Plan (LHTD20170001), HKRGC Areas of Excellence
Scheme (AoE/P-02/12),The Shenzhen & Hong Kong Joint Research
Program (SGLH20180622092406130), and the Guangdong Science and
Technology Program (2017B030314002).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
interface engineering, perovskite solar cells, surface doping
Received: May 29, 2020
Revised: July 7, 2020
Published online:
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