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Article
Characteristics of Perovskite Solar Cells Under Low-illuminance Conditions
Itaru Raifuku, Yasuaki Ishikawa, Seigo Ito, and Yukiharu Uraoka
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.6b05298 • Publication Date (Web): 16 Aug 2016
Downloaded from http://pubs.acs.org on August 19, 2016

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Characteristics of Perovskite Solar Cells under Low-
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17 AUTHOR NAMES
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20 Itaru Raifuku†, Yasuaki Ishikawa*, †, Seigo Ito‡, and Yukiharu Uraoka†
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23 †
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Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5
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26 Takayama, Ikoma, Nara 630-0192, Japan
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29 ‡
Department of Materials and Synchrotron Radiation Engineering, Graduate School of
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32 Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan
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AUTHOR INFORMATION
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40 Corresponding Author
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*
43 E-mail: yishikawa@ms.naist.jp
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ABSTRACT
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7 Organic–inorganic perovskite solar cells have attracted much attention as high performance and
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10 low-cost photovoltaic devices. Because it consists of p-type hole transport layer, perovskite layer,
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12 and n-type electron transport layer similar to a p–i–n structure, it works effectively even under
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low-illuminance conditions, such as indoor lighting. In this work, we focused on the characteristics
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17 of perovskite solar cells under low-illuminance conditions, and a detailed investigation was carried
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19 out. The open-circuit voltage yielded at around 70% of AM1.5 at 0.1 mW/cm2 illuminance, which
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22 is similar to that under indoor lighting. From impedance spectroscopy, it was suggested that the
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24 planar-type structure solar cell provided better resistance characteristics than that of
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26 mesostructured cell for indoor applications. Comparing the characteristics of these types of solar
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29 cells, planar-type solar cells show higher voltage than mesostructured cells under low-illuminance
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31 conditions. These results have shown important implications for various applications of perovskite
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solar cells.
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40 INTRODUCTION
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43 Organic–inorganic lead halide perovskite compounds (CH3NH3PbX3, X = I, Br, Cl) have
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attracted much attention as a material for solar cells due to their high absorption coefficient, high
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48 carrier mobility, low binding energy of excitons, and tunable bandgap.1-5 Perovskite solar cells
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50 were first developed in 2009. These cells utilize perovskite compounds as a light absorber and
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53 had a power conversion efficiency (PCE) of 3.8%.6 Over the years, the PCE of perovskite solar
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55 cells has been gradually improved. In 2012, the PCE reached 10% by substituting 2,2 ʹ ,7,7 ʹ -
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tetrakis(N,N-di-p-methoxyphenylamino)-9,9 ʹ -spirobifluorene (spiro-OMeTAD), which a solid-
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state hole transport material for electrolyte.7,8 A PCE more than 20% can be achieved by
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6 improving the fabrication process, composition of perovskite compounds, and interface.9-19
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9 The common structure of perovskite solar cells consists of n-type electron transport materials,
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12 intrinsic perovskite compounds, p-type hole transport materials, and electrodes. Thus, the device
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14 structure of perovskite solar cells is a type of p–i–n junction similar to the structure of
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16 amorphous silicon (a-Si) solar cells. Owing to an internal electrical field, which is formed
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19 between the p and n layer controls carrier transport, recombination of carriers is inhibited even
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21 under low-level injection conditions. Therefore, perovskite solar cells could work under low-
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level injection conditions such as low-illuminance conditions. In addition, the light absorption
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26 area of perovskite compounds, which is utilized in perovskite solar cells, contains luminescence
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28 spectra of indoor lighting such as a typical white LED, fluorescent lamp, etc.1,5 Hence, it is
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31 expected that perovskite solar cells effectively generate electricity under indoor lighting.
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34 Solar cells have attracted attention as a technique of energy harvesting. So far, a-Si and dye
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36 sensitized solar cells have been applied or considered for indoor application, and the low-
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39 illuminance characteristics have been investigated, 20 however, the relatively low efficiency or its
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41 poor stability remain us a technological challenges. Perovskite solar cells have higher efficiency
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than those solar cells, suggesting it is expected that perovskite solar cells open the door to next
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46 generation indoor energy harvesting.
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49 There are few reports on the current–voltage (I–V) characteristics of perovskite solar cells
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52 measured under 0.1 sun condition.9,21 However, the light intensity of common indoor lighting is
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54 around 0.001 sun (100 lux), which is 0.1% of sun light (100 mW/cm2). A detailed investigation
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56 focusing on the characteristics of perovskite solar cells under such conditions has not yet been
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performed. If the low-illuminance characteristics of perovskite solar cells are well defined, the
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6 applications of perovskite solar cells will spread various research fields such as a dispersed
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8 power source for Internet of Things (IoT) applications.
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12 Here, we show the characteristics of perovskite solar cells such as I–V and external quantum
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14 efficiency (EQE) under low-illuminance conditions. In addition, the difference in the internal
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16 state of perovskite solar cells with respect to light intensity is investigated by impedance
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19 spectroscopy to establish an effective device structure model of perovskite solar cells for indoor
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21 applications.
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EXPERIMENTAL SECTION
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28 Device Fabrication
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31 Fluorine-doped tin oxide (FTO) coated glass substrates (AGC Fabritech, t=1.8 mm) were
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34 etched with zinc powder and 2 M HCl. The substrates were then washed with detergent and
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36 acetone in an ultrasonic bath for 10 min. Then, UV/O3 treatment was carried out for 15 min at
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115°C. To prepare the electron transport layer (ETL), 0.15 M titanium diisopropoxide
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41 bis(acetylacetonate) (Sigma–Aldrich, 75 wt% in isopropanol) in 1-butanol was spin-coated on a
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43 FTO glass substrate at 700 rpm for 8 s, 1000 rpm for 10 s, and 2000 rpm for 40 s, which was
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followed by drying at 125°C for 5 min. The mesoporous TiO2 layer was deposited on the ETL by
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48 spin coating a TiO2 paste (JGC Co., PST-18NR) diluted in ethanol (2:7, weight ratio) at 1000
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50 rpm for 5 s and 5000 rpm for 25 s. After drying at 125°C for 5 min, the substrate was annealed at
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53 450°C for 1 h. Before depositing the perovskite layer, UV/O3 treatment was carried out again. In
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55 order to prepare a perovskite precursor solution, 461 mg of PbI2, 159 mg of CH3NH3I, and 78 mg
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of DMSO was mixed in 600 mg of DMF and then stirred at room temperature for 3 h. The
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precursor solution was spin-coated on mesoporous TiO2 layer at 4000 rpm for 25 s and 0.5 mL of
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6 diethyl ether was dripped on the rotating substrate at 6 s after starting the spin-coating. After
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8 spin-coating, the substrate was annealed at 65°C for 1 min and 100°C for 2 min. Spiro-OMeTAD
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solution consisting of 17 mg spiro-OMeTAD, 6.9 µL of 4-tert-butyl pyridine, and 4.2 µL of
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13 lithium bis(trifluoromethanesulfonyl) imide (Li-TFSI) solution (520 mg Li-TFSI in 1mL
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15 acetonitrile) in 240 µL of chlorobenzene was spin-coated on the perovskite layer at 1000 rpm for
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18 4 s and 4000 rpm for 26 s to deposit a hole transport layer (HTL). Finally, an Au electrode was
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20 deposited by thermal deposition on the HTL. Planar-type perovskite solar cells were fabricated
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by same process except spin-coating of mesoporous TiO2 paste.
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26 Characterization
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29 The photocurret–voltage (I–V) characteristics were measured under AM1.5 one sun
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32 illumination (100 mW/cm2) with a solar simulator (Wacom Co., KXL-1000F). The active areas
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34 of the perovskite, c-Si, and a-Si solar cells were 0.09, 0.64, and 1 cm2, respectively. In order to
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36 adjust the light intensity, an ND filter (Opto Sigma) was inserted in AM1.5 illumination. The
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39 external quantum efficiency (EQE) was measured using an EQE system (Bunkoukeiki Co., CEP-
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41 2000RR) under 0.25 and 0.0025 mW/cm2 monochromatic lighting of comparable intensity with
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outdoor and indoor lighting, respectively. The intensity is also adjusted using an ND filter.
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46 Impedance spectroscopy was performed by utilizing potentiostat (BioLogic, SP-150) under light
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48 illumination (from dark to 100 mW/cm2). The measurements were carried out at frequencies
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51 from 1 MHz to 500 mHz with a voltage of 100 mV.
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54 RESULTS AND DISCUSSION
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Figure 1 (a) shows the I–V curves of a mesostructured perovskite solar cell under 100, 50, 10,
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6 1, and 0.1 mW/cm2 illuminance. For comparison, same measurements were carried out for
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8 crystalline silicon (c-Si) and a-Si solar cells as shown in Figure 1 (b) and (c), respectively. The I–
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V characteristics and device structures of each solar cell are shown in Table S1 and Figure S1,
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13 respectively. The short-circuit current density (JSC) of each solar cell decreased in proportion to
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15 light intensity, and the behavior was not different for different types of solar cells as shown in
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18 Figure 2 (a). However, the behavior of open-circuit voltage (VOC) was different depending on the
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20 type of solar cell.
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23 (a) (b) (c)
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Current density (mA/cm )

Current density (mA/cm )

Current density (mA/cm )

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Voltage (V) Voltage (V) Voltage (V)
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39 Figure 1. Illuminance dependency of the I–V characteristics of (a) mesostructured perovskite, (b)
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41 c-Si, and (c) a-Si solar cells. The black, red, blue, green, and orange lines represent the I–V curves
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44 under 100, 50, 10, 1, and 0.1 mW/cm2 illumination, respectively.
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47 Figure 2 (b) shows the VOC of each solar cell under various light intensities. The value was
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normalized by utilizing the VOC value under AM 1.5 (100 mW/cm2) illuminance. At 0.1 mW/cm2
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52 illuminance, which is comparable to the light intensity of indoor lighting, the VOC of the c-Si
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54 solar cell decreased remarkably to about 10% of the initial voltage. On the contrary, the VOC of
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57 mesostructured perovskite solar cells at 0.1 mW/cm2 illuminance remains unchanged at about
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70% of its initial voltage. We also confirmed that I-V characteristics of the perovskite solar cells
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6 did not show any change even after the measurements (Figure S2). The difference on VOC is
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8 probably due to the device structure of each solar cell.
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(a) 100 (b) 100
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13 Perovskite

Normalized V OC (%)
Normalized J SC (%)

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c-Si
a-Si
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Perovskite (meso)
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29 Figure 2. (a) Normalized JSC and (b) normalized VOC of each solar cell under various illuminance
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31 conditions.
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35 The c-Si solar cell is based on the p–n junction. In the p–n junction, the driving force of the
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37 carriers is the build-in-potential, and the carrier transfer depends on the diffusion, which is
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39 strongly related to the carrier injection level. Under high-level injection condition, c-Si shows
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42 better carrier lifetime (τ) by trap saturation effect. By contrast, the τ is strongly affected by
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44 defects in the c-Si and decreases under low-illuminance conditions, which is a low-level
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injection condition.22 As a result, the saturation current (J0) in solar cells becomes higher, which
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49 decreases the VOC of c-Si solar cells under low-illuminance conditions. On the other hand,
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51 perovskite solar cells have a p–i–n structure (n-type electron transport layer, intrinsic perovskite
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54 layer, and p-type hole transport layer). In the p–i–n structure, carrier collection is aided by an
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materials, such as a-Si. Therefore, the decrease in τ is not caused easily even under a low-level
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6 injection condition in p–i–n structure.23 Therefore, the VOC of perovskite solar cells could be kept
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8 at a higher value than that of c-Si solar cells under low-illuminance conditions. Comparing
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11 perovskite solar cells and a-Si solar cells, which also consist of the p–i–n junction, the
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13 normalized VOC of a-Si solar cells is as similar to that of perovskite solar cells. However, the
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15 absolute value of VOC was higher in perovskite solar cells than that of a-Si solar cells. (Perovskite
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18 (mesostructured): 0.71 V, a-Si: 0.58 V.)
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21 The relationship between VOC, J0 and τ is given as follows.
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𝑘𝑇 𝐽-#
25 𝑉"# ≈ ln ( )
26 𝑒 𝐽.
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29 𝑒𝑛2 𝑊
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34 In the above equation, only JSC is changed by light intensity. Because the JSC decreases in
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36 proportional to light intensity, the VOC decreases linearly in semi-log plots. However, when τ
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39 decreases severely with injection level such as c-Si solar cells, the behavior of VOC deviates from
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41 a linear relationship under low-illuminance conditions. On the other hand, the VOC decreases in
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43 proportional to light intensity in the perovskite and a-Si solar cells even under low-illuminance
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46 conditions owing to the τ is not strongly affected by injection level.
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49 The spectral sensitivity characteristics of perovskite solar cells were investigated by utilizing
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52 EQE measurement. Figure 3 (a) shows the normalized EQE spectra of mesostructured perovskite
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54 solar cells under 0.25 and 0.0025 mW/cm2 monochromatic lighting that is the comparable
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56 intensity with outdoor and indoor lightings, respectively. As shown in Figure 3 (a), the EQE
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spectra of mesostructured perovskite solar cells did not show a large shift due to light intensity as
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6 well as a-Si solar cells, which have been used for indoor applications (Figure 3 (b)). In addition,
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400–600 nm, which is included in indoor lighting such as either typical white LED or fluorescent
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13 lamp, it is expected that mesostructured perovskite solar cells can generate current not only
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19 (a) (b)
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21 1 1
Normalized EQE

Normalized EQE
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25 0.5 0.5
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30 0 0
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32 Wavelength (nm) Wavelength (nm)
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36 Figure 3. Normalized EQE spectra of (a) mesostructured perovskite and (b) a-Si solar cells. The
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38 black and red lines represent the normalized EQE under 0.25 and 0.0025 mW/cm2 illumination,
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41 respectively.
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44 Because the spectral sensitivity characteristics of mesostructured perovskite solar cells did not
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show a large shift due to light intensity, it is considered that an improvement in the VOC is
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49 important for indoor applications. Generally, VOC is related to carrier collection, which depends
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51 on the internal resistance of solar cells. Consequently, impedance spectroscopy was performed
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54 for mesostructured perovskite solar cells to investigate the internal resistance. Figure 4 shows the
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56 Nyquist plots of mesostructured perovskite solar cells under various illuminance conditions. The
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highest frequency point shows the resistance from an FTO substrate or external circuit. The
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6 semicircle in the high-frequency range is attributed to the diffusion of holes through the hole
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8 transport layer. The low-frequency part is attributed to the recombination resistance between the
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perovskite layer and the TiO2 layer.24-26 Under 1 sun illumination, a semicircle was also observed
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13 in the low-frequency range. However, under low-illuminance conditions, such as 0.1 mW/cm2
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15 illumination, a transmission-line (TL) behavior was observed in the low-frequency range of
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18 Nyquist plots. It was reported that the TL behavior is because of the electron transport resistance.
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20 Hence, it is considered that the internal resistance of mesostructured perovskite solar cells
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increased under low-illuminance conditions. As a result, the carrier collection efficiency
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25 decreased and thus causing VOC to decrease. A TiO2 layer is suggested to increase the internal
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27 resistance under low-illuminance conditions. TiO2 is naturally an insulator material, but it shows
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30 conductivity by filling the trap sites with carriers.28,29 Therefore, TiO2 acts as a resistance under
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32 low-illuminance conditions that cannot generate enough carriers to fill the trap sites.
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34 Consequently, it is suggested that the planar structure that eliminated the mesoporous TiO2 layer,
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37 which has many trap sites, is suitable for indoor applications. The same measurements were
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39 carried out for planar-type perovskite solar cells. Figure 5 shows Nyquist plots of the
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mesostructured and the planar-type perovskite solar cells under 0.1 mW/cm2 illumination. The
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44 inset of Figure 5 (b) shows low frequency part of Nyquist plot of the planar-type perovskite solar
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46 cell. As shown in Figure 5 (b), the TL behavior was not observed in the planar-type perovskite
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49 solar cell even under 0.1 mW/cm2 illumination. These results indicate the electron transport
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51 resistance of planar-type solar cells is lower than mesostructured cells.
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4 (a)150 (b) 800
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-Im(Z) [Ohm]

-Im(Z) [Ohm]
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-Im(Z) [Ohm]

-Im(Z) [Ohm]
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1000
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31 Re(Z) [Ohm] Re(Z) [Ohm] [×105]
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35 Figure 4. Nyquist plots of mesostructured perovskite solar cells under (a) 100 mW/cm2, (b) 10
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37 mW/cm2, (c) 0.1 mW/cm2, and (d) dark condition by applying voltage of 100 mV.
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-Im(Z) [Ohm]

43
1
-Im(Z) [Ohm]

-Im(Z) [Ohm]

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128 132
47 Re(Z) [Ohm]
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Figure 5. Nyquist plots of planar-type perovskite solar cells under (a) 100 mW/cm2 and (b) 0.1
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6 mW/cm2 illumination by applying voltage of 100 mV.
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9 Therefore, we investigated the I–V characteristics and spectral sensitivity characteristics of
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12 planar-type perovskite solar cells under low-illuminance conditions. Figure 6 (a) shows
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14 normalized VOC of mesostructured and planar-type perovskite solar cells under various light
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16 intensities. The device structure and I-V characteristics of planar-type perovskite solar cells are
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19 shown in Figure S3 and Table S2. Planar-type perovskite solar cells showed clearly higher VOC at
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21 low-illuminance conditions than that of mesostructured solar cells. The mesostructured and
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planar-type perovskite solar cells showed a VOC value of 0.71 V and 0.84 V at 0.1 mW/cm2
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26 illumination, respectively. The JSC of each solar cell are shown in Figure S4. Also, shunt
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28 resistance (Rsh) and series resistance (Rs) of each structure solar cell were compared. Figure S5
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31 shows Rsh and Rs of planar-type and mesostructured perovskite solar cells. As shown in Figure
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33 S5 (a), the Rsh of each solar cell increased with decreasing light intensity. And, the behavior was
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35 not different for each structure. On the other hand, the Rs of the mesostructured solar cell
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38 increased remarkably than that of the planar-type one, indicating mesoporous TiO2 acts as a
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40 resistance under low-illuminance conditions. Figure 6 (b) shows the normalized EQE spectra of
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planar-type perovskite solar cells under 0.25 and 0.0025 mW/cm2 monochromatic lighting. The
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45 EQE spectra of planar-type perovskite solar cells as well as mesostructured solar cells did not
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47 show a large shift due to light intensity. In addition, the EQE spectra of planar-type perovskite
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50 solar cells as well as mesostructured solar cells showed acceptable spectral response in the
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52 wavelength range of 400–600 nm. Therefore, it is considered that planar-type solar cells also
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54 could generate current under indoor lighting.
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5

Normalized V OC (%)
1
Planar

Normalized EQE
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10 80 0.5
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12 Mesostructured
13 70
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0
0.1 1 10 100 300 450 600 750 900
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17 Light intensity (mW/cm 2) Wavelength (nm)
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21 Figure 6. (a) Normalized VOC of planar-type and mesostructured perovskite solar cells under
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23 various illuminance conditions. (b) Normalized EQE spectra of planar-type perovskite solar cells.
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The black and red lines represent normalized EQE under 0.25 and 0.0025 mW/cm2 illumination,
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28 respectively.
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31 CONCLUSIONS
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35 In conclusion, we investigated the characteristics of perovskite solar cells under low
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37 illuminance conditions. From the I–V measurements under various illuminance conditions, it was
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39 suggested that perovskite solar cells can maintain higher VOC value under 0.1 mW/cm2
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42 illumination than a-Si solar cells, which is used for indoor applications. Spectral sensitivity
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44 characteristics of perovskite solar cells were also investigated under low-illuminance conditions
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by EQE measurement. As a result, perovskite solar cells showed acceptable spectral response in
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49 the wavelength range of 400–600 nm, which is included in indoor lighting. To investigate the
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51 method for further improvement of the low-illuminance characteristics of perovskite solar cells,
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54 impedance spectroscopy was performed. As a result, it was considered that the mesoporous TiO2
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56 layer acts as an internal resistance and decreases VOC under low-illuminance conditions.
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Therefore, we investigated the low-illuminance characteristics of the planar-type perovskite solar
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6 cells. As a result, planar-type solar cells showed better characteristics than that of
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8 mesostructured solar cells under low-illuminance conditions. Our results indicate an effective
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structural model for low-illuminance applications and potential of perovskite solar cells for
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13 various applications, such as indoor applications particularly dispersed power sources for IoT
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15 applications. In this work, characteristics of Pb-based perovskite solar cells were investigated.
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18 Although containing of Pb is one of the concern for indoor applications, this problem could be
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20 improved by further progress of perovskite solar cells.
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ASSOCIATED CONTENT
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25
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27 Supporting Information. Fabrication process of c-Si and a-Si solar cells. I–V characteristics
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29 and device structure of perovskite, c-Si and a-Si solar cells. Normalized JSC of planar-type solar
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31
32 cells and normalized FF of each solar cell. This material is available free of charge via the
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34 Internet at http://pubs.acs.org.
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36
37 AUTHOR INFORMATION
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39
40 Corresponding Author
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43 *E-mail: y-ishikawa@ms.naist.jp, TEL: +81-(743)-72-6061.
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46 Notes
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49 The authors declare no competing financial interests.
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51
52 ACKNOWLEDGMENT
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55 The authors would like to thank Dr. Nirmal Peiris for the technical assistance of this study.
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