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Semiconductor plasmon-sensitized broadband upconversion and its

enhancement on power conversion efficiency of perovskite solar cells

Article  in  Journal of Materials Chemistry A · June 2017

DOI: 10.1039/C7TA04943A

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 Journal of
Materials Chemistry A
COMMUNICATION
Semiconductor plasmon-sensitized broadband
Cite this: J. Mater. Chem. A, 2017, 5,
upconversion and its enhancement effect on the
16559 power conversion efficiency of perovskite solar
Published on 30 June 2017. Downloaded by Jilin University on 16/08/2017 02:27:59.
Received 7th June 2017 cells†
Accepted 30th June 2017
Donglei Zhou,a Dali Liu,a Junjie Jin,a Xu Chen,a Wen Xu,*b Ze Yin,a Gencai Pan,a
DOI: 10.1039/c7ta04943a
Dongyu Lia and Hongwei Song *a
rsc.li/materials-a
Photon upconversion (UC) is an attractive strategy to substantially
enhance the power conversion efficiency (PCE) of solar cells via
upconverting unavailable near-infrared sunlight to available visible
light. However, to date, it is almost infeasible to achieve effective PCE
improvement of solar cells with the assistance of UC materials, limited
by their poor UC efficiency and extremely weak and narrowband near-
infrared absorption. Here, we demonstrate the efficient photon energy
UC in semiconductor plasmon mCu2
xS@SiO2@Er2O3 (mCSE) nano-
composites, where the broadband semiconductor plasmon (800–
1600 nm) of mCu2
xS serves as an antenna to sensitize UC of Er2O3
nanoparticles. The overall upconversion luminescence (UCL) of the
composites was dramatically enhanced by a factor of 1000, with
a maximal inner quantum efficiency of 14.3%. The excitation range was
expanded, ranging from 800 to 1600 nm. As a proof-of-concept, the
highly efficient mCSE nanocomposites were utilized to improve the
PCE of perovskite solar cells (PSCs). The expansion of the near-
infrared response (800–1000 nm) and considerable improvement of
the PCE were obtained, with an optimum PCE of 17.8%. The mCSE
composites in PSCs enhanced the photocurrent via electron transfer
from oxygen defects to the conduction band of TiO2 under irradiation
of one sunlight. Under irradiation of 15 suns, the electron transfer and
reabsorption of UCL both contributed to the enhancement of PCE.
Our work can provide an insightful thought on boosting UC efficiency
as well as broadening the PCE of PSCs.
Introduction
Perovskite solar cells (PSCs), the fastest-advancing solar tech-
nology to date,1 have become commercially attractive due to
their low cost,2,3 simple fabrication,4–6 and high efficiency.7–9
However, PSCs are usually unable to utilize light (800–1700 nm)
a
State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and
Engineering, Jilin University, 2699 Qianjin Street, Changchun, 130012, P. R. China.
E-mail: songhw@jlu.edu.cn
b
Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta,
Midori-ku, Yokohama 226-8503, Japan
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c7ta04943a
This journal is © The Royal Society of Chemistry 2017
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beyond the visible region limited by their intrinsic band gap,
which accounts for 55% of the total solar energy.10–12 Conse-
quently, photon energy upconversion has been thought to be
a promising way to harvest of this portion of sunlight and
transform it into available visible light. However the most well-
known upconversion materials13–15 (e.g., bulk b-NaYF4:Yb3+, Er3+
with the UC efficiency of 3%) have been used to improve the
power conversion efficiency (PCE) of other types of solar
cells11,16–19 (e.g., dye-sensitized solar cells and quantum dot
sensitized cells). Nevertheless, the improvements of the power
conversion efficiencies (PCEs) of solar cells based on
upconverters are extremely low and merely serve as a proof of
principle, restricted by the lower UC efficiency, the smaller
absorption cross section and narrower excitation band of 4f–4f
transitions for upconverters.20 Therefore, to enhance the near-
infrared response of PSCs, designing and obtaining a new
class of upconverters with high efficiency as well as broadband
absorption of near-infrared light is of high importance.
Some lanthanide oxides (e.g., Yb2O3 and Er2O3) demon-
strate efficient UC broadband emissions with an estimated UC
efficiency of as high as 10% under the excitation of a 980 nm
laser diode.21–23 More interestingly, differing from the well-
known uoride phosphors encountering concentration
quenching and temperature quenching, lanthanide oxides
even have better performance at high doping concentration
and elevated temperature.24–26 However, the efficient upcon-
version luminescence (UCL) of lanthanide oxides is always
obtained under laser irradiation with higher power density,
which is both much larger than the power density of sunlight
and narrower than the spectral range of sunlight. Noticeably,
Cu2
xS, a kind of heavily doped semiconductor material,
displays an intense localized surface plasmon resonance
(LSPR) absorption band at near-infrared wavelengths, arising
from collective oscillations of excess free carriers associated
with constitutional vacancies in the lattice.27–29 It is expected
that plasmon Cu2
xS nanoparticles could be explored as an
antenna to sensitize the UCL of lanthanide oxides, degrading
J. Mater. Chem. A, 2017, 5, 16559–16567 | 16559

Journal of Materials Chemistry A
the threshold power as well as expanding the spectral
absorption range of lanthanide oxides.
In this work, we fabricated mCu2
xS@SiO2@Er2O3 (mCSE)
nanocomposites, which displayed an efficient broadband
emission in the visible region with an optimum UC efficiency of
14.3% under 980 nm excitation, enabling UC within 800–
1600 nm excitation. Moreover, the mCSE nanocomposites were
successfully applied to improve the PCE (10% enhancement)
of PSCs.
Results
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Structure and optical properties of mCSE nanocomposites
Scheme 1 shows the fabrication process of mCu2
xS@SiO2@-
Er2O3 nanocomposites and the structure of mCu2
xS@SiO2@-
Er2O3-based PSCs. First, spherical Cu2
xS nanoparticles were
synthesized through a hot-injection method,27 which were
mono-dispersed and homogeneous, with an average size of
6.5 nm (Fig. 1a). Cu2
xS nanoparticles were further capsulated
in a SiO2 nanosphere via a modied Stober method,30,31 forming
mCu2
xS@SiO2 with a diameter of 45 nm (Fig. 1b). Then, the
mCu2
xS@SiO2@Er(OH)CO3 composites were prepared by
a urea coprecipitation method.26 Aer being annealed at 400–
700  C for 2 hours, the mCu2
xS@SiO2@Er2O3 nanocomposites
were nally fabricated with a 7 nm Er2O3 shell.
To fabricate mCu2
xS@SiO2@Er(OH)CO3 composite sensi-
tized PSCs, the mCu2
xS@SiO2@Er(OH)CO3 composites were
mixed with mesoporous TiO2 and then annealed at 500  C for
half an hour. The transmission electron microscopy (TEM)
images of mCSE nanoparticles (Fig. 1c and d) show that the
Cu2
xS particles are distributed in a SiO2 sphere and an Er2O3
shell could be clearly distinguished. Meanwhile, the energy-
dispersive X-ray analysis (EDX) spectrum of mCSE nano-
composites (Fig. S1†) demonstrates that the mCSE nano-
composites are indeed formed.
The elemental analysis of EDX mapping was further
employed to identify the internal structure of the mCSE
sample annealed at 500  C (Fig. 1e). It shows that all of the
elements (copper, sulphur, silicon, and erbium elements) are
distributed homogeneously in the sphere and a core–shell
Scheme 1 Fabrication process of mCSE nanocomposites and their
application in PSCs.
16560 | J. Mater. Chem. A, 2017, 5, 16559–16567
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Communication
structure is formed (d(Er) > d(Si) > d(S, Cu)). From the high
resolution transmission electron microscopy (HR-TEM) of
the mCSE nanocomposites (Fig. 1f), two different fringe
spacings are determined, 0.307 nm and 0.196 nm, which
correspond with the spacing of the (2,2,2) plane of cubic
Er2O3 (0.307 nm) (JCPDS no. 77-0464) and the (0,1,20) plane
of rhombohedral Cu2
xS (0.196 nm) (JCPDS no. 47-1748),
respectively. The XRD patterns of Cu2
xS and mCSE nano-
composites annealed at different temperatures ranging from
400 to 700  C were further recorded (Fig. 1g). The peaks of
pure Cu2
xS nanoparticles are indexed to the (0,0,15),
(1,0,10), (0,1,20), and (1,1,15) planes of rhombohedral Cu2
xS
(digenite) with the space group R3 m (JCPDS no. 47-1748),
respectively. The peaks of Cu2
xS and Er2O3 can be identied
in the patterns of mCu2
xS@SiO2@Er2O3 nanocomposites
annealed at 400 and 500  C. While for samples annealed at
600 and 700  C, the peaks of Cu2
xS are quite weak and only
the peak of (0,1,20) plane could be identied. At high
annealing temperatures a part of the Cu2
xS particles were
oxidized to CuO, which is veried by the distinguished peaks
of CuO in the pattern of the sample annealed at 700  C. Note
that no peaks of SiO2 are observed in the XRD patterns owing
to its amorphous phase. Based on the above, mCSE nano-
composites were successfully fabricated.
The UV-Vis-Infrared absorption spectra (Fig. 1h) of Cu2
xS
and mCSE nanocomposites annealed at different temperatures
ranging from 400 to 700  C were recorded. In pure Cu2
xS
nanoparticles, a surface plasmon absorption band centered at
1200 nm can be conrmed. Differing from the free electron
induced localized surface plasmon resonance (LSPR) of novel
metal nanoparticles, the LSPR of Cu2
xS nanoparticles stems
from the Cu defect induced charge carriers. Based on the
modied Mie–Drude theory by Luther et al.,28 the localized
surface plasmon resonance (LSPR) absorption frequency usp
depends on the density of charge carriers (Nh), which can be
expressed as


30 mh ð1 þ 23m Þ usp 2 þ g2
Nh ¼
e2
where 3m is the dielectric constant of the environmental
medium, e is the elemental charge, 30 is the free space permit-
tivity, mh is the hole effective mass, approximated to be 0.8m0,
where m0 is the electron mass, g is the full-width at half
maximum of the LSPR related absorption peak. The density of
charge carriers (Nh) was estimated to be 3.5  1021 cm
3. In the
annealed mCSE nanocomposites, the LSPR absorption
decreases, broadens and shis to the red with increasing the
annealing temperature, which can be attributed to the gradual
oxidation of Cu2
xS nanoparticles.32 When the annealing
temperature is above 600  C, the LSPR absorption becomes very
weak and disappears, suggesting that most of the Cu2
xS
particles are oxidized and even transformed into CuO, which
can be conrmed by the XRD patterns (Fig. 1g). No obvious peak
is observed in the extinction spectrum of Er2O3 NPs (Fig. 1h).
The extinction decrease of Er2O3 nanoparticles with the
increase of wavelength should be attributed to the scattering of
the Er2O3 nanoparticles.
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Fig. 1 (a) TEM image of Cu2
xS nanoparticles. (b) TEM image of mCu2
xS@SiO2. (c and d) TEM images of mCSE nanocomposites. (e) Energy
dispersive X-ray (EDX) mapping of the mCSE sample. (f) HR-TEM images of mCSE nanocomposites. (g) XRD patterns of Cu2
xS and mCSE
nanocomposites annealed at different temperatures. (h) Extinction spectra of Cu2
xS and mCSE nanocomposites annealed at different
temperatures.

UCL of mCSE nanocomposites SiO2@Er2O3 nanocomposites (Fig. 2c). It also demonstrates the
strongest broadband emission intensity illuminated at the
The UCL of all the mCSE and SiO2@Er2O3 composites (Fig. 2a
and S2†) is power-dependent. For the typical mCSE composites same excitation power density of 1.23 W mm
2 (Fig. 2d).
(annealed at 500  C), the green 2H11/2/4S3/2–4I9/2 and red Fig. 2e shows the power density dependence of the integral
UCL intensity of SiO2@Er2O3 and mCSE nanocomposites on the
4
F9/2–4I15/2 inner-shell transitions of Er3+ can be clearly distin-
excitation power density of 980 nm light in logarithmic coor-
guished in a lower excitation power range. Owing to the strong
dinates. In general, UCL intensity (IUC) increases with
cross relaxation of 4F7/2 + 4I11/2–4F9/2 for Er3+ ions, the red
increasing excitation power (P) with a power law of IUC  Pn,
emissions are dominant (Fig. 2b). As the excitation power is
where n represents the number of pumping photons required to
high enough (beyond 0.21 W mm
2), the narrow-line emis-
excite rare earth ions from the ground state.33,34 For SiO2@Er2O3
sions disappear completely and bright white broadband emis-
sions centering around 650 nm appear and dramatically nanocomposites (independent of annealing temperature), the
increase with excitation power, which can be attributed to the power-density dependence of intensity can be divided into three
periods. In the rst period, before the generation of UC
efficient charge transfer from 4F9/2 of Er3+ to oxygen defect states
broadband emission, the slope is 1.26. In the second period,
through the tunneling effect. Electrons in oxygen vacancy states
accompanying by the generation of UC broadband emission,
further recombine with holes in the valence band of Er2O3,
the intensity increases dramatically with a slope of 10.5. This
generating broadband emissions.24,26 The generation of holes
super-large slope suggests the occurrence of a photon avalanche
can be conrmed by the occurrence of photocurrent accompa-
or thermal avalanche.35,36 In the third period, the slope n drops
nying the broadband emissions in SiO2@Er2O3 and mCSE
composites (Fig. S3a†). In contrast to the SiO2@Er2O3 with the to 1.97 again. The power-density dependence of UCL intensity
same size, the threshold power densities for generating broad- for the mCSE composites is similar to that for SiO2@Er2O3,
except that the rst period is not obvious. This is because the
band emissions in mCSE nanocomposites decrease, depending
threshold power density for the broadband emission of mCSE is
on the annealing temperature of the samples. The sample
too low. Fig. 2f shows the enhancement factor (EF), which is
annealed at 500  C has the lowest threshold power density of
dened as the ratio of UCL intensity of the mCSE composites to
90 mW mm
2, which decreases 6 times than that of
that of SiO2@Er2O3 composites as a function of excitation

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Fig. 2 (a) Power-dependent upconversion spectra of mCSE composites annealed at 500  C. (b) Schematic of the mechanism of upconversion
broadband emission in mCSE nanocomposites. (c) Broadband threshold power of SiO2@Er2O3 and mCSE nanocomposites annealed at different
temperatures. (d) Emission spectra of SiO2@Er2O3 and mCSE nanocomposites annealed at different temperatures. (e) Log–log plot of the
upconversion emission intensity against the excitation laser power for mCSE composites. (f) Enhancement factor of mCSE composites
compared to that of the SiO2@Er2O3 composite as a function of excitation power density. (g) Power-dependent upconversion efficiency of
SiO2@Er2O3 and mCSE composites annealed at 500  C. (h) Excitation spectra of SiO2@Er2O3 and mCSE composites annealed at 500  C. The
power density of excitation light was 1.3 W mm
2. (i) Simulated electric field intensity distribution of mCSE nanocomposites. The incident light
wavelengths are 808 nm, 980 nm, 1540 nm and 650 nm, respectively. The jEj2 =jE0 j2 represents the averaged electric field enhancement factor.

power density. With the increase of excitation power, the EFs
rst quickly increase and approach an optimum at the power
density of 0.87 W mm
2 and then drastically decrease for all
the annealed samples. The mCSE sample annealed at 500  C
has the largest EFs (around 1100 times under the excitation
power density of 800 mW mm
2), which is consistent with the
results of Fig. 2b and c. This can be attributed to the stronger
LSPR of mCu2
xS nanoparticles and better crystallinity of the
samples annealed at 500  C. Note that the UC intensity uctu-
ation for the mCSE nanocomposites is within 4% under
980 nm continuous illumination for 160 min (1.23 W mm
2),
which implies their high stability (Fig. S4†).
In SiO2@Er2O3 and mCSE composites (annealed at 500  C),
the power-density-dependent inner quantum efficiency for the
UCL of Er3+ is recorded under 980 nm excitation (Fig. 2g).
Naturally, it gradually increases with increasing power density,
from 0.1% to 6% for SiO2@Er2O3 and from 0.3% to 14.3% for
mCSE in the range of 0.09–1.47 W mm
2. Besides upconversion
induced by blackbody radiation,22 the inner quantum efficiency
of 14.3% in mCSE composites is almost the most efficient
reported until now. Moreover, the absolute brightness of the
sample was determined to be as high as 7778 cd m
2 under the
power density of 1.23 W mm
2. The inner quantum efficiency of
mCSE composites increases 2 fold compared to that of the
SiO2@Er2O3 composites, which can be attributed to the
coupling of Er2O3 emissions with plasmon Cu2
xS nano-
particles and the increased temperature induced by extra pho-
tothermal effects in mCSE composites (Fig. S3b†). In the light of
our previous result,26 the UCL intensity increases with the
increase of temperature in the studied temperature range (<200

C). The excitation spectra of mCSE and SiO2@Er2O3 compos-
ites are compared (Fig. 2h). In the SiO2@Er2O3 composites, two
sharp peaks situated at 800 and 980 nm can be identied,
corresponding to the 4I15/2–4I9/2 and 4I15/2–4I11/2 transitions. It is
interesting to observe that in the mCSE composites, the exci-
tation bands are broadened ranging from 800 to 1600 nm. This
could be attributed to the amplication of LSPR to the excita-
tion eld and the increase of phonon density in the mCSE,
which results in the efficient phonon-assisted transitions of
Er3+.

16562 | J. Mater. Chem. A, 2017, 5, 16559–16567 This journal is © The Royal Society of Chemistry 2017

Communication
In mCSE nanocomposites, on one hand, the LSPR of Cu2
xS
nanoparticles can couple with excitation light/emission light,
leading to excitation eld enhancement or the Purcell effect,
and the improvement of the radiative transition rate as well as
inner quantum efficiency of UCL. On the other hand, the photo-
thermal effect of Cu2
xS nanoparticles should occur, resulting
in an increased temperature, which is benecial to enhance the
broadband emission.26,37 To understand the amplication of the
excitation/emission eld, we simulated the |E|2 surrounding
the mCSE composites using the nite-difference time-domain
(FDTD) solution (Note 1 in the ESI†), as shown in Fig. 2i. It is
clear that the |E|2 of Cu2
xS is concentrated around the mCSE
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composites with a maximum intensity enhancement of 90 times
at the hot spots under the excitation of 980 nm light. When
changing the wavelength of excitation light to 808 nm or
1540 nm, the enhancement of |E|2 at the hot spots decreases
a little. The enhancement decreases to 12 when changing the
wavelength to 650 nm (central emission wavelength), because
the 650 nm wavelength is far away from the LSPR central
wavelength (1200 nm) of Cu2
xS nanoparticles. The averaged
electric eld enhancement factors are obtained by calculating
the average value of the electric eld intensity enhancement in
the mesh range, which shows 15.7 times enhancement at the
excitation of 980 nm and 2.5 times at the emission wavelength
(650 nm). Because the broadband upconversion emission is
a two-photon process, the enhancement of UCL induced by the
excitation eld amplication is calculated to be 220 times
(Fig. 2f). In the light of the result of the inner quantum effi-
ciency, the coupling of LSPR with emission light induces about
2-fold UCL enhancement. As the excitation power increases, the
temperature in mCSE composites (Fig. S3b†) is about 100–250 K
higher than that in SiO2@Er2O3 composites. According to the
previous reports,26 the luminescence enhancement induced by
temperature variation in mCSE composites is about 2–3 folds.
Therefore, the practical UC enhancement is roughly consistent
with the theoretical prediction.
Overall, the intense strength, high inner quantum efficiency
(14.3%) and broad excitation bands (800–1600 nm) of mCSE
composites provide them with the possibility to be an ideal
upconverter in the application of PSCs.
Perovskite solar cell with mCSE upconverter
Scheme 1 illustrates the PSC with the mCSE upconverter, con-
sisting of a compact TiO2 layer (50 nm), mesoporous TiO2
mixed with 0–10 wt% mCSE and a perovskite layer (520 nm),
a hole transport layer (150 nm) and an Au electrode (80 nm)
(Fig. 3a). The cross-sectional image (Fig. S5†) indicates that the
solar cell is at and uniform. The PCEs of four groups of PSCs,
the traditional PSC, the cell containing SiO2@Er2O3, the cell
containing mCu2
xS@SiO2 and the solar cell containing mCSE
composites were compared (Fig. 3b and Table S1†). PSCs with
different proportions of upconverters in weight were prepared
with their efficiencies shown in Table 1. Interestingly, the PSC
with the optimized (5 wt%) mCSE nanocomposites displays
the highest PCE of 17.8% (Fig. 3b and Table S1†), which is
enhanced by 10% compared with that of the solar cell without
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UC nanocomposites (16.2%). The PSC with mCSE composites
maintained a PCE of 16.9% aer being stored in a glovebox for
500 h (Fig. S6†). The average PCE of PSCs with mCSE compos-
ites is 17.1% calculated with y PSC devices (Fig. 3c). The Jsc
and Voc both increase until the proportion of mCSE nano-
composites increases to 5 wt%. The increase of Jsc can be
attributed to the contribution of mCSE composites. The
increase of Voc can be mainly induced by increasing charge
recombination resistance, which is discussed in Fig. 3i. Beyond
5 wt%, PCEs decrease mainly due to the reduction of the lling
factor and photocurrent. Differently, aer introducing the
SiO2@Er2O3 composites, the PCE decreases to 12.6%,
accompanying by the reduction of Jsc and Voc. The PSC con-
taining mCu2
xS@SiO2 composites exhibits a PCE of 16.3%.
The slight increase of the PCE might be ascribed to the LSPR
scattering of mCSE composites. The enhancement of PCE
induced by the LSPR of mCSE composites was quite little
compared to the enhancement induced by noble metal NPs (Au
or Ag NPs).38 As the density of free carriers in Cu2
xS NPs is one-
order lower than that in noble metals, the intensity of LSPR in
Cu2
xS NPs is weaker than that in metal NPs. The introduction
of SiO2@Er2O3 composites alone is disadvantageous to the PCE.
When the Cu2
xS NPs were absent, the light absorption of Er2O3
was quite weak and the contribution to photocurrent was quite
little. In addition, the SiO2@Er2O3 NPs were a poor conductor
and decreased the charge mobility (see EIS results in Fig. 3i and
Table S3†), resulting in a decreased photocurrent.
To elucidate the mechanism of enhancement of PCE, the UV-
Vis-Infrared extinction spectra of the mesoporous TiO2 layer
and perovskite layer were recorded (Fig. 3d). The TiO2 layers
mixed with mCu2
xS@SiO2 and mCSE composites have an
enhanced extinction, especially in the infrared region. The
extinction of the TiO2/perovskite layer mixed with mCSE
composites enhances 40% in intensity in the near-infrared
region compared to that without mCSE composites, while it
only enhances 5% in the visible region, indicating that the
mCSE composites in the solar cell had little inuence on the
light harvesting of the perovskite layer. The incident photon-to-
current conversion efficiency (IPCE) spectra of PSCs without
mCSE composites all demonstrate the generation of photocur-
rent in the range of 370 nm to 820 nm (Fig. 3e). Consistent
with the extinction spectra (Fig. 3d), the generation of photo-
current in the PSC with mCSE composites extends to 1000 nm.
This can be attributed to the fact that mCSE composites
absorbed the near-infrared light and contributed to the photo-
current. The response of photocurrent in the region from 400 to
800 nm was enhanced as well. This can be attributed to the
decreased charge transfer resistance (Fig. 3i) in the presence of
mCSE composites. Although the TiO2 layer mixed with
mCu2
xS@SiO2 exhibits strong absorption in the near-infrared
region (Fig. 3d), it does not effectively contribute to the photo-
current and extend the response region (Fig. 3e), indicating that
the response in the range of 800–1000 nm of PSCs does not
come from the contribution of LSPR absorption of Cu2
xS
directly. Meanwhile, the solar cell containing mCSE composites
exhibits response and the photocurrent (Jsc) increases with the
980 nm power density increasing (Fig. 3f and S7†), indicating
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Fig. 3 (a) Cross-sectional SEM image of the PSC. The mCSE composites were mixed with mesoporous TiO2 5% in weight. (b) Current–density/
voltage curves of the best-performing PSC, solar cell with SiO2@Er2O3, solar cell with mCu2
xS@SiO2 and solar cell with mCSE composites under
simulated AM1.5, 100 mW cm
2 irradiance (simulated sunlight). (c) PCE distribution and the average PCE of PSCs, PSCs with SiO2@Er2O3, PSCs
with mCu2
xS@SiO2 and PSCs with mCSE composites. (d) UV-Vis-Infrared extinction spectra of the mesoporous TiO2 layer and perovskite layer
with/without mCSE composites. (e) IPCE curves of the best-performing PSC. (f) Current–density/voltage curves of the PSC with mCSE
composites under AM1.5G standard sunlight and an additional 980 nm NIR laser. (g) Current–density/voltage curves of the best-performing PSC
under simulated AM1.5, 100 mW cm
2 irradiance (simulated sunlight) with different intensities. The solar irradiance intensity was tuned by using
a convex lens. The photo-current of PSCs under 7 suns or 15 suns was normalized to 1 sun. (h) Emission spectra of mCSE composites,
composites in the TiO2 layer and composites in the PSC irradiated by a concentration of 15 suns with a 900 nm short-pass filter. (i) Electro-
chemical impedance spectroscopy (EIS) of CH3NH3PbI3 PSCs containing mCSE composites. (j) Schematic illustration of the energy transfer
process in CH3NH3PbI3 solar cells using mCSE composites.

Table 1 Open-circuit voltages, short-circuit currents, fill factors and Further experiments demonstrate that solar cells with mCSE
efficiencies of PSCs with 0–10 wt% mCu2
xS@SiO2@Er(OH)CO3 composites have better performance at the higher power irra-
composites
diance of simulated sunlight (Fig. 3g). For the sake of compar-
Proportion (wt%) 0 1 3 5 7 10 ison, the photo-current of PSCs under 7 suns or 15 suns was
Voc (V) 1.07 1.07 1.08 1.1 1.1 1.09 normalized to 1 sun. Note that the efficiency of the PSC without
Jsc (mA) 23.3 24.1 24.7 25.1 24.8 24.5 composites varies little when increasing the solar irradiance
Fill factor (%) 65 64 64 64 59 58 intensity. The irradiance power dependence of the PCEs of the
Efficiency (%) 16.2 16.5 17.1 17.8 16.1 15.5
PSCs with mCSE composites indicates that the contribution of
mCSE composites to the photocurrent is power dependent,
the contribution of the UC process. The current transient vs. which is consistent with the higher quantum efficiency and
time curves (Fig. S8†) showed that the photocurrent of the PSC more effective electronic transition from the valence band to
with mCSE composites was higher than that of the PSC with oxygen defects in mCSE composites at the higher excitation
mCu2
xS@SiO2 when 980 nm light was on. All these results power. The PCE of the best-performing solar cell reached 18.8%
indicate that the infrared light is absorbed by the UC mCSE at a concentration of 15 suns.
composites and further contributes to the enhanced photo- The UC broadband emission of mCSE composites was
current and PCEs of the PSC. observed under a concentration of 15 suns using a 900 nm

16564 | J. Mater. Chem. A, 2017, 5, 16559–16567 This journal is © The Royal Society of Chemistry 2017

Communication
short-pass lter (Fig. 3h), indicating that the infrared light can
be effectively harvested by the mCSE composites by the
upconversion process. The emission intensity decreases
dramatically aer mixing them with the TiO2 layer (FTO/TiO2
(mCSE)), which can be attributed to the luminescence
quenching by the TiO2 layer. The emission intensity of the
mCSE composites decreases further but only a little aer the
introduction of perovskite (FTO/TiO2 (mCSE)/perovskite), which
implies that electrons in the oxygen defects are mainly trans-
ferred to TiO2, leading to the enhanced photocurrent of solar
cells. Considering that the irradiation might induce thermal
effects, the temperature of the PSCs was measured by using
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a thermocouple (Table S2†). Irradiated by the AM1.5G standard,
the temperatures were nearly the same for the PSCs with and
without mCSE composites. Under irradiation of a concentration
of 15 suns, the temperature of the PSC device with mCSE
composites increased from 22 to 31  C. Such a small variation of
temperature should have no inuence on the lifespan and light
harvesting of the perovskite layer. To evaluate the stability of
PSCs continuously working under a concentration of 15 suns,
the PCEs of the PSC with/without mCSE composites were
measured (Fig. S9†). The PCE of the PSC with mCSE composites
decreases by 10% aer irradiation by 15 suns for 10 h contin-
uously, while it decreases by 8% for the PSC without mCSE
composites. The decreases of PCEs are nearly the same, indi-
cating that the introduction of mCSE composites into PSCs had
no effect on the stability and lifespan of PSCs. To ascertain the
location of the oxygen defect level of mCSE composites relative
to the vacuum level, ultraviolet photoelectron spectroscopy
(UPS) studies were performed (Fig. S10†). The results showed
that mCSE composites possess an oxygen defect level near

4.1 eV (Fig. 3j), which matched with the conduction band of
TiO2 (
4.2 eV). Electrons on the oxygen defect level should
transfer to the conduction band of TiO2, leading to the decrease
of UC broadband emission of mCSE composites (Fig. 3h). The
electrochemical impedance spectroscopy (EIS) measurements
(Fig. 3i, S11 and Table S3†) demonstrate that the charge transfer
resistance (Rco  17.4 U) in the PSC with mCSE composites is
much lower than that in the pure PSC (Rco  49.6 U). This
suggests that the mobility of electrons in the PSC with mCSE
composites was enhanced. The charge recombination resis-
tance (Rrec) in the PSC with mCSE composites increased
compared to that of the pure PSC, which resulted in the
enhanced Voc in Fig. 3b.
Fig. 3j shows the schematic illustration of the energy transfer
process of the PSC with mCSE composites. Under irradiation of
one sunlight, as the power density of sunlight is much lower
than the power threshold for generating broadband emission of
mCSE composites, the mCSE composites absorbed the infrared
light and electrons in the ground state of Er3+ were populated to
the oxygen defect level and then transferred to the conduction
band of TiO2, contributing to the charge mobility and photo-
currents. The presence of Cu2
xS NPs can enhance the
absorption of sunlight by Er2O3. At a concentration of 15 suns,
the mCSE composites displayed a broadband upconversion
emission, which was mainly quenched by the TiO2 layer or
reabsorbed by the perovskite layer. In other words, a part of
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Journal of Materials Chemistry A
electrons in the oxygen defects are directly transferred to the
conduction band of TiO2. The other part of electrons are relaxed
by the radiative transition process, which can be reabsorbed by
the perovskite layer. Above all, the incorporation of mCSE
composites provides a promising route to reduce the non-
absorption photon loss in PSCs.
Conclusions
A novel kind of photon energy UC material, semiconductor
plasmon-sensitized mCSE nanocomposites, was prepared,
which could efficiently convert broadband infrared light (800–
1600 nm) to visible beneting from the LSPR of Cu2
xS. The
nanocomposites demonstrated three-order UCL enhancement,
a considerably decreased threshold power density compared to
that of SiO2@Er2O3 and an inner quantum efficiency as high as
14.3% under the excitation of 980 nm light (1.5 W mm
2). The
mCSE upconverter was then applied in a PSC and led to an
expanded response in the range of 800–1000 nm and 10%
enhancement of PCE under standard solar irradiation. The PCE
of the PSC reached 17.8% aer introducing the mCSE
composites, which increased with increasing the irradiating
power, and approached 18.8% at a concentration of 15 suns.
This work displays a highly effective UC material and provides
a method of enhancing the utilization of infrared light via the
upconversion process in PSCs.
Experimental section
Synthesis of Cu2
xS nanoparticles
The Cu2
xS nanoparticles were synthesized via a typical hot-
injection method.27,28 The copper precursor was prepared by
mixing CuCl (0.01 mol) with a mixture of 4 mL of oleic acid (OA)
and 5 mL of oleylamine (OM) at 130  C for 30 min. Then the as-
prepared copper precursor was cooled to room temperature.
Meanwhile, the sulfur precursor was prepared by dissolving
sulfur powder (0.01 mol) in 40 mL of octadecene at 200  C for
30 min. And the sulfur solution was maintained at 180  C, fol-
lowed by swi injection of the copper precursor. Before cooling
to the room temperature, the resulting solution was maintained
at 180  C for 5–15 min. Cu2
xS nanoparticles in the solution
were precipitated by adding excess acetone and collected by
centrifugation of the suspension (two times). Finally, the
precipitate was redispersed in an organic solvent such as carbon
tetrachloride, trichloromethane, or cyclohexane.
Synthesis of mCu2
xS@SiO2@Er2O3 nanocomposites
The as-prepared Cu2
xS nanoparticles (0.2 g), 10 mL cyclo-
hexane, 0.5 mL ammonia, 10 mL Triton X-100, 8 mL hexyl
alcohol, 2 mL water, and 0.1 mL TEOS were mixed together and
stirred for 24 hours at room temperature. Then, the precipitates
were collected and washed three times with alcohol. Aer that,
the precipitates (mCu2
xS@SiO2) were dissolved in deionized
water, added into 0.3 g Er(NO3)3 and 2.5 g urea, heated at 90  C
for an hour and cleaned with alcohol three times. Then, the
obtained sample was annealed at 500  C for 2 hours. Finally, the
J. Mater. Chem. A, 2017, 5, 16559–16567 | 16565

Journal of Materials Chemistry A
mCu2
xS@SiO2@Er2O3 composites were collected. For
comparison, SiO2@Er2O3 NPs were synthesized by a similar
method.
Solar cell fabrication
First, FTO glasses were cleaned in an ultrasonic bath containing
ethanol for 15 min and treated in a UVO cleaner for 15 min. To
make a dense TiO2 blocking layer, the cleaned FTO glasses were
coated with 0.15 M titanium diisopropoxide bis(acetylaceto-
nate) (75% Aldrich) in 1-butanol (Aldrich) solution by a spin-
coating method, which was heated at 125  C for 5 min. FTO
glasses with TiO2 precursor solutions were heated at 500  C for
Published on 30 June 2017. Downloaded by Jilin University on 16/08/2017 02:27:59.
30 min. On the prepared dense TiO2 blocking layer, the nano-
crystalline TiO2 paste mixed with mCu2
xS@SiO2@Er(OH)CO3
composites was prepared and was deposited by spin-coating
and the deposited lm was annealed at 500  C for 30 min to
produce a mesoporous TiO2 lm with mCu2
xS@SiO2@Er2O3
composites. PbI2 was deposited on the surface of the TiO2 layer
by vapor deposition. Then the lm was immersed in a CH3NH3I
solution (10 mg mL
1) to form the (CH3NH3)PbI3 perovskite
layer. The hole transport material spiro-OMeTAD was spin-
coated on the lm at 3000 rpm. For the counter electrode, 100
nm-thick Au was deposited on the top of the HTM over layer by
thermal evaporation.
Characterization
The morphology of the products was recorded with a Hitachi H-
8100IV transmission electron microscope under an acceleration
voltage of 200 kV. The phase structure and purity of the as-
prepared samples were characterized by X-ray power diffrac-
tion with a Rigaku D/max 2550 X-ray diffractometer, using
a monochromatized Cu target radiation source (l ¼ 1.54 Å). UV/
vis-NIR absorption spectra were measured with a Shimadzu UV-
3600PC UV/vis-NIR scanning spectrophotometer in the range
from 300 to 2000 nm. In the measurements of power-dependent
UCL spectra, a continuous 980 nm diode laser was used to
pump the samples. A visible photomultiplier (350–850 nm)
combined with a double-grating monochromator was used for
spectral collection. The photoconduction curves were collected
by a source-measurement unit under the illumination of
a continuous 980 nm diode laser. X-ray photoelectron spec-
troscopy was performed with an ESCALab220i-XL electron
spectrometer from VG Scientic. Monochromatic Al Ka X-rays
(hn ¼ 1486.6 eV) were employed for analysis with an incident
angle of 30 with respect to surface normal. The quantum effi-
ciency was measured by using an Otsuka Electronics QE-2100
with an additional 980 nm laser.
Author contributions
D. Z., W. X. and H. S. conceived the project and designed the
experiments. D. Z. synthesized copper sulphide nanoparticles
and mCu2
xS@SiO2@Er2O3 composites, and performed optical
characterization and the spectra measurement. D. Z., J. J., Z. Y.,
X. C. and D. L. collected the data, performed the measurement
of UCL dynamics and fabricated the perovskite solar cell. D. Z.,
16566 | J. Mater. Chem. A, 2017, 5, 16559–16567
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Communication
D. L., W. X., G. P., and H. S. analyzed the data and discussed the
result. D. Z., W. X. and H. S. were primarily responsible for the
ESI. D. Z. prepared the Figures. H. S. and D. Z. wrote the main
manuscript text. All the authors contributed to data analysis,
discussions and manuscript preparation.
Acknowledgements
This work was supported by the Major State Basic Research
Development Program of China (973 Program) (no.
2014CB643506), the National Key Research and Development
Program (2016YFC0207101), the National Natural Science
Foundation of China (grant no. 61674067, 11304118, 11504131,
11374127, 81201738, and 11674127), the Jilin Province Natural
Science Foundation of China (No. 20160418055FG), Jilin
Provincial Economic Structure Strategic Adjustment Fund
Special Projects (No. 2014Y082), the Jilin Province Natural
Science Foundation of China (No. 20150520090JH,
20170101170JC), the Jilin Province Science Fund for Excellent
Young Scholars (No. 20170520129JH, 20170520111JH) and the
Graduate Innovation Fund of Jilin University (No. 2016191).
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