Letter

www.acsami.org

Hexagonal β‑NaYF4:Yb3+, Er3+ Nanoprism-Incorporated Upconverting

Layer in Perovskite Solar Cells for Near-Infrared Sunlight Harvesting
Jongmin Roh, Haejun Yu, and Jyongsik Jang*
School of Chemical and Biological Engineering, College of Engineering, Seoul National University, 599 Gwanak-ro, Gwanak-gu, Seoul
151-742, Korea
*
S Supporting Information

ABSTRACT: Hexagonal β-NaYF4:Yb3+, Er3+ nanoprisms, successfully prepared using a hydrothermal method, were
incorporated into CH3NH3PbI3 perovskite solar cells (PSCs) as an upconverting mesoporous layer. Due to their near-infrared
(NIR) sunlight harvesting, the PSCs based on the upconverting mesoporous layer exhibited a power conversion efficiency of
16.0%, an increase of 13.7% compared with conventional TiO2 nanoparticle-based PSCs (14.1%). This result suggests that the
hexagonal β-NaYF4:Yb3+, Er3+ nanoprisms expand the absorption range of the PSC via upconversion photoluminescence, leading
to an enhancement of the photocurrent.
KEYWORDS: NaYF4:Yb3+, Er3+, upconversion, nanoprism, perovskite solar cell

S ince organolead trihalide perovskite (CH3NH3PbX3, X =

Cl, Br, I) was rediscovered as the sensitizer in solid-state
solar cells,1 perovskite solar cells (PSCs) have increasingly
improved their power conversion efficiency, rising from 9.71 to
20.1%.2 Organolead trihalide perovskite is considered to be a
particularly promising material, because of its unique properties
that include a large absorption coefficient,3 ambipolar charge
transport,4 long electron−hole diffusion lengths,5,6 and facile
solution processability.7−9 To date, there have been numerous
attempts to improve the photovoltaic performance and stability
of PSC devices, such as by controlling the processing
conditions of perovskite films,10,11 engineering the chemical
composition of perovskite,12,13 introducing additives to perov-
skite, 14 and designing interface energy alignments. 15,16
However, the perovskite sensitizer has a bandgap of 1.55 eV
and absorbs only a small portion of incident light in the visible
spectrum (up to 800 nm),1,17 thus resulting in energy loss due
to the nonabsorption of near-infrared (NIR) light. Light
harvesting of low-energy photons below the absorption
threshold of perovskite is required for high-performance PSC
devices.
One interesting approach to solve this NIR energy loss
problem is to broaden the light absorption spectrum using
upconversion materials. In the photon upconversion process,
two or more incident photons are converted into one higher
energy photon,18−20 generating additional photocurrent in solar
cells.21 Among many upconversion materials, ytterbium and
erbium codoped beta-phase sodium yttrium fluoride (β-
NaYF4:Yb3+, Er3+) is well-known as the most efficient
upconversion phosphor for bright green photoluminescence
(PL) and is widely used in lasers,22 solar cells,23,24 and
bioimaging.25 In NaYF4:Yb3+, Er3+ phosphor, Yb3+ ions act as a
NIR sensitizer and Er3+ ions act as a visible photon emitter.26
NaYF4:Er3+ upconversion phosphors, applied to the bottom
layer of silicon solar cells, theoretically increase the power
conversion efficiency of the cells from 20 to 25%.23 In dye-
sensitized solar cells (DSSCs), large NaYF4:Yb3+, Er3+ nano-
plates and nanoprisms have been utilized as upconverting and
light-scattering materials to increase the optical path length of
the incident light and to obtain better NIR response.24,27 It is
expected that upconversion nanomaterials can be used to
improve the photovoltaic performance of PSCs, as well as
silicon solar cells and DSSCs.
Received: April 21, 2016
Accepted: July 29, 2016
Published: July 29, 2016

© 2016 American Chemical Society 19847 DOI: 10.1021/acsami.6b04760

ACS Appl. Mater. Interfaces 2016, 8, 19847−19852
ACS Applied Materials & Interfaces Letter

Figure 1. (a) Schematic configuration and (b) cross-sectional scanning electron microscopy (SEM) image of the perovskite solar cells (PSCs) device
with a hexagonal NaYF4:Yb3+, Er3+ nanoprism upconverting layer.

Figure 2. (a) SEM image and (b) X-ray diffraction (XRD) pattern of hexagonal NaYF4:Yb3+, Er3+ nanoprisms. (c) Upconversion photoluminescence
(PL) spectrum and d) digital photograph of hexagonal NaYF4:Yb3+, Er3+ nanoprisms under 980 nm near-infrared (NIR) laser excitation. (e) Detailed
energy-level diagram and corresponding energy transitions in the NaYF4:Yb3+, Er3+ system.

In this work, we report a novel upconverting mesoporous
layer based on TiO 2 nanoparticles and hexagonal β-
NaYF4:Yb3+, Er3+ nanoprisms for PSCs. NaYF4:Yb3+, Er3+
nanoprisms were introduced to the TiO2 mesoporous layer in
a PSC device as upconverting centers (Figure 1a). Low-energy
NIR light absorbed by NaYF4:Yb3+, Er3+ nanoprism cores can
be converted into high-energy visible light that can be utilized
in PSCs. Thus, the NaYF4:Yb3+, Er3+ nanoprisms expand the
absorption range of the PSC via upconversion PL, resulting in
an enhancement of the photocurrent.
Hexagonal NaYF4:Yb3+, Er3+ nanoprisms were fabricated via
a simple hydrothermal process using an aqueous solution
containing trivalent lanthanide ions (Y3+:Yb3+:Er3+ = 78:20:2),
sodium citrate, and ammonium fluoride.28 TiO2 nanoparticle-
and NaYF4:Yb3+, Er3+ nanoprism-based pastes were prepared
by mixing with ethanol, terpineol, ethyl cellulose, and lauric
acid. To introduce an upconverting mesoporous layer into the
19848
PSC, diluted TiO2−NaYF4:Yb3+, Er3+ mixed paste was spin-
coated onto the compact TiO2 layer and annealed at 500 °C for
30 min. Finally, the upconverting mesoporous film was post-
treated with aqueous TiCl4 solution and heated at 500 °C for
30 min to reduce charge recombination at the perovskite/TiO2
and perovskite/NaYF4:Yb3+, Er3+ interface.29 The surface
morphology of the upconverting mesoporous layer and the
cross-section of the PSC with the upconverting mesoporous
film are shown in Figure S1 and Figure 1b, respectively; in
Figure 1b, the thickness of the TiO2 mesoporous layer is ca.
200 nm and large hexagonal NaYF4:Yb3+, Er3+ nanoprisms are
exposed over the TiO2 mesoporous layer. The amount of
NaYF 4 :Yb 3+ , Er 3+ nanoprisms on the surface of the
upconverting mesoporous layer increases with the concen-
tration of NaYF4:Yb3+, Er3+ nanoprisms in the mixed paste.
The morphology of the NaYF4:Yb3+, Er3+ nanoprisms was
investigated by scanning electron microscopy (SEM). Figure 2a
DOI: 10.1021/acsami.6b04760
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ACS Applied Materials & Interfaces
Figure 3. (a) Photocurrent density−voltage (J−V) characteristics and
(b) Nyquist plots of PSCs using an upconverting mesoporous layer
with varied ratios of NaYF4:Yb3+, Er3+ nanoprisms. Electrochemical
impedance spectroscopy (EIS) measurements were performed under
dark conditions.
shows a representative SEM image of the NaYF4:Yb3+, Er3+
nanoprisms. The fabricated NaYF4:Yb3+, Er3+ nanoprisms have
a uniform hexagonal prism structure with good monodispersity
and well-defined facets. The nanoprisms had an average size of
550 nm in diameter and 600 nm in height. The crystallinity of
the NaYF4:Yb3+, Er3+ nanoprisms was confirmed by X-ray
diffraction (XRD), as shown in Figure 2b. The diffraction peaks
of the NaYF4:Yb3+, Er3+ nanoprisms corresponded exactly to
the pure crystalline hexagonal β-NaYF4 phase (JCPDS No. 16−
0334). Compared with the cubic α-NaYF4 phase, hexagonal β-
NaYF4 is a more efficient host lattice of various lanthanide ions
for upconversion PL, due to its high upconversion quantum
yield.28
Figure 2c shows the upconversion PL spectrum of
NaYF4:Yb3+, Er3+ nanoprisms under 980 nm excitation. In
the upconversion process of the NaYF4:Yb3+, Er3+ system, the
energy in Yb3+ excited by NIR light is transferred to Er3+ ions
and released as high-energy visible light. Four Er3+ emission
peaks at 408, 523, 543, and 655 nm were observed; these peaks
were assigned to 2H9/2 → 4I15/2 (408 nm), 2H11/2 → 4I15/2 (523
nm), 4S3/2 → 4I15/2 (543 nm), and 4F9/2 → 4I15/2 (655 nm)
transitions (Figure 2e).28 Notably, the 4S3/2 → 4I15/2 transition,
a dominant peak in the emission spectrum of NaYF4:Yb3+, Er3+
nanoprisms, corresponds to bright green fluorescence under
980 nm excitation (Figure 2d). This result suggests that the
NaYF4:Yb3+, Er3+ nanoprisms facilitate NIR light absorption by
the perovskite sensitizer as upconversion PL, broadening the
absorption spectrum range of the PSC device.
19849
Letter
Figure 4. (a) Photocurrent density−voltage (J−V) characteristics of
PSCs using TiO2 nanoparticles, NaYF4 nanoprisms, and NaYF4:Yb3+,
Er3+ nanoprisms and (b) their corresponding incident photon-to-
current conversion efficiency (IPCE) spectra. (c) Schematic diagrams
of the energy transfer process in PSCs using an upconverting
mesoporous layer.
Additionally, the Er3+ ions can be directly excited in
broadband NIR by the 4I13/2 state of Er3+, followed by
excited-state absorption from 4I13/2 to 4F9/2 emits visible light
with 650 nm. Furthermore, the three-photon absorption
around 1540 nm also results in same emission wavelength of
light from Er3+. These additional upconversion paths can
increase the emission of NaYF4:Yb3+, Er3+ phosphor, and
contribute the additional photocurrent in the PSCs.26
The upconverting NaYF 4 :Yb 3+ , Er 3+ nanoprisms are
incorporated into the mesoporous layer in CH3NH3PbI3
PSCs, as shown in Figure 1b. To optimize the concentration
of NaYF4:Yb3+, Er3+ nanoprisms in the mesoporous layer, the
photocurrent density−voltage (J−V) characteristics of the
PSCs with different weight ratios of NaYF4 :Yb 3+ , Er 3+
nanoprisms in the TiO2 mesoporous layer were investigated
(Figure 3a); the corresponding photovoltaic properties of the
various samples are summarized in Table S1. The PSC with the
DOI: 10.1021/acsami.6b04760
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ACS Applied Materials & Interfaces
Table 1. Photovoltaic Parameters of the Perovskite Solar Cells (PSCs) Using TiO2 Nanoparticles, NaYF4 Nanoprisms, and
NaYF4:Yb3+, Er3+ Nanoprismsa
devicesb JSCc (mA cm−2)
TiO2 (reference) 18.85 ± 0.69
TiO2 with 75% NaYF4 18.52 ± 0.41
TiO2 with 75% NaYF4:Yb3+, Er3+ 20.23 ± 0.94
a
Measurements were performed under AM 1.5G sunlight intensity of 100 W cm−2. Average values of all parameters were obtained for 15 devices.
b
Active area of the fabricated PSC devices is 0.09 cm2. cShort-circuit current. dOpen-circuit voltage. eFill factor. fPower conversion efficiency.
TiO2 control mesoporous film exhibited a short-circuit current
density (Jsc) of 18.85 mA cm−2 and a power conversion
efficiency (η) of 14.05%. All PSCs with a NaYF4:Yb3+, Er3+
nanoprism-added mesoporous layer exhibited enhanced Jsc and
η, compared with the TiO2 reference PSC. Jsc and η values
increased with the amount of NaYF4:Yb3+, Er3+ nanoprisms, up
to 75 wt % (Figure S2). The best performance was obtained
using a TiO2 mesoporous layer with 75 wt % NaYF4:Yb3+, Er3+
nanoprisms, demonstrating Jsc and η values of 20.23 mA cm−2
and 15.98%, respectively. These results represent a 13.74%
enhancement in efficiency compared with the TiO2 reference
device. This noticeable enhancement in Jsc and η was attributed
to the upconversion luminescence properties of the NaY-
F4:Yb3+, Er3+ nanoprisms from NIR to visible light via the
CH3NH3PbI3 perovskite layer. The performance improvement
by upconversion effect was also identified from J−V character-
istics obtained under 980 nm NIR laser condition. (Figure S3
and Table S2). The Jsc of 0.027 mA cm−2 and Voc of 0.374 V
were estimated from the measurement, respectively. From this
result, it is underpinned that NaYF4:Yb3+, Er3+ nanoprisms
function as upconverting materials in PSCs well.
To investigate the charge transfer characteristics in PSC
devices, we performed electrochemical impedance spectroscopy
(EIS) measurements in the frequency range of 1 Hz to 1 MHz
at −0.8 V bias under dark conditions. Figure 3b shows the
Nyquist plots of the PSCs for various weight ratios of
NaYF4:Yb3+, Er3+ nanoprisms in the TiO2 mesoporous layer.
Typically, two semicircles appear in the Nyquist plots in the
higher- and lower-frequency regions. The small semicircles at
higher frequencies show the charge transfer at the interfaces of
the hole transport layer (HTL)/Au electrode; in this case, the
semicircles were too small to be distinguished in the Nyquist
plots. The large semicircles at lower frequencies are related to
the charge recombination of electrons at the mesoporous film/
perovskite/HTL interfaces.30 The recombination resistance
values of the fabricated PSCs at the mesoporous film/
perovskite/HTL interfaces (Rct) were similar with respect to
the various weight ratios of NaYF4:Yb3+, Er3+ nanoprisms
(Figure 3b); this implies that there is little charge transfer
difference in the TiO2 layer and TiO2 layer with NaYF4:Yb3+,
Er3+ nanoprisms. Thus, the TiCl4 post-treatment that passivates
the recombination sites on the upconverting mesoporous layer
was believed to be responsible for reducing charge recombi-
nation between the mesoporous film/perovskite interface.29 To
meticulously figure out the charge transport resistance at the
interfaces, EIS measurement was also conducted under
illumination conditions. (Figure S4) Actually, there is no
significant difference on the charge transport resistance,
however, the slightly improved charge transport behavior was
observed by replacing pure TiO2 based mesoporous layer with
NaYF4:Yb3+, Er3+ nanoprisms incorporated mesoporous layer.
It is ascribed to the enhanced pore-filling of perovskite in
cramped TiO2 mesoporous layer, since thickness of meso-
19850
Letter
VOCd (V) FFe ηf (%)
1.09 ± 0.01 0.68 ± 0.01 14.05 ± 0.59
1.10 ± 0.01 0.70 ± 0.01 14.26 ± 0.61
1.10 ± 0.01 0.72 ± 0.02 15.98 ± 0.93
porous TiO2 layer was slightly lowered by decreasing
concentration of TiO2 in stock paste. Furthermore, when
some sections of TiO2 based mesoporous layer are occupied by
large NaYF4:Yb3+, Er3+ nanoprisms, the electrons excited in
perovskite have a high chance to be transferred through high
crystalline perovskite phase rather than TiO2 layer. So the
charge migration efficiency would be enhanced.
To elucidate the NIR photovoltaic capability of NaYF4:Yb3+,
3+
Er nanoprisms, the optimal photocurrent density−voltage (J−
V) curves of the PSCs using TiO2 nanoparticles, TiO2
nanoparticles with NaYF4 nanoprisms, and TiO2 nanoparticles
with NaYF4:Yb3+, Er3+ nanoprisms are presented in Figure 4a;
the associated photovoltaic parameters are listed in Table 1.
The PSC with NaYF4 nanoprisms in the mesoporous layer
exhibited a Jsc of 18.52 mA cm−2 and a η of 14.26%, similar to
the TiO2 reference device (Jsc of 18.85 mA cm−2, η of 14.05%).
However, by replacing the NaYF4 nanoprism film with a
NaYF4:Yb3+, Er3+ nanoprism upconverting layer, Jsc increased
from 18.52 mA cm−2 to 20.23 mA cm−2. Consequentially, the
best device performance of 15.98% was achieved, which is a
12.06% enhancements in efficiency compared with the NaYF4
nanoprism film. Figure 4b displays incident photon-to-current
conversion efficiency (IPCE) spectra of the PSCs using TiO2
nanoparticles, TiO2 nanoparticles with NaYF4 nanoprisms, and
TiO2 nanoparticles with NaYF4:Yb3+, Er3+ nanoprisms. A little
change was observed in IPCE result when NaYF4 nanoprisms
were added in the mesoporous layer. However, The IPCE value
over the entire region of 400−750 nm was considerably
enhanced with incorporating NaYF4:Yb3+, Er3+ nanoprisms in
the mesoporous layer. The PSCs using NaYF4:Yb3+, Er3+
nanoprisms exhibits a maximum IPCE value of 85.4% at 525
nm because of the upconversion PL of NaYF4:Yb3+, Er3+
nanoprisms. This result is consistent with the photovoltaic
performance shown in Figure 4b. From this perspective,
application of NaYF4:Yb3+, Er3+ nanoprisms to PSCs represents
a way to supplement the energy loss caused by nonabsorption
of NIR light via photon upconversion. When incident light is
projected to the PSCs, the visible photons for which energies
are higher than the bandgap of perovsksite sensitizer are
converted into a photocurrent directly. Although NIR photons
with energies lower than the bandgap of perovskite are
effectively converted into visible photons by 980 nm NIR
sensitization of Yb3+ followed by energy transfer to Er3+ and
direct excitation of Er3+ by broadband NIR illumination ranged
from 1000 to 1600 nm.26
In conclusion, hexagonal β-NaYF4:Yb3+, Er3+ nanoprisms,
successfully fabricated using a simple hydrothermal method,
were incorporated into a PSC mesoporous layer as upconvert-
ing cores. By optimizing the amount of NaYF4:Yb3+, Er3+
nanoprisms in the TiO2 mesoporous layer, the PSC with a
NaYF4:Yb3+, Er3+ nanoprisms exhibited the best power
conversion efficiency of 15.98, an overall enhancement of
13.74% compared with that of a TiO2-based PSC device. This
DOI: 10.1021/acsami.6b04760
ACS Appl. Mater. Interfaces 2016, 8, 19847−19852
ACS Applied Materials & Interfaces
enhanced PSC performance was attributed to the additional
photocurrent generation via NIR photon upconversion of
NaYF4:Yb3+, Er3+ nanoprisms. This work provides new
possibilities for the introduction of NIR harvesting nanoma-
terials in PSCs, further promoting broad light absorption for
high-performance PSCs.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b04760.
Experimental details, SEM images of upconverting
mesoporous layer and photovoltaic parameters of all
PSC devices. EIS measurements under illumination
condition. Photocurrent density−voltage characteristics
and photovoltaic parameters evaluated under 980 nm
NIR laser (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jsjang@plaza.snu.ac.kr. Tel.: (+82) 2-880-7069 Fax:
(+82) 2-888-1604.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Global Frontier R&D Program
on the Center for Multiscale Energy System funded by the
National Research Foundation under the Ministry of Science,
ICT & Future, Korea (2011-0031573). This work was
supported by Development Fund of Seoul National University
funded by Dongjin Semichem Co., Korea (0458-20130066).
■
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19852 DOI: 10.1021/acsami.6b04760

ACS Appl. Mater. Interfaces 2016, 8, 19847−19852