Solar Energy 201 (2020) 555–560

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Design of hole-transport-material free CH3NH3PbI3/CsSnI3 all-perovskite T

heterojunction efficient solar cells by device simulation
⁎
Qianqian Duana, Junyang Jia, Xin Honga, Yichao Fua, Chenyang Wanga, Kai Zhoua, Xueqin Liua, ,
Hua Yangb, Zhi-Yong Wangc
a
School of Science, Chongqing University of Technology, and Chongqing Key Laboratory of Green Energy Materials Technology and Systems, Chongqing 400054, China
b
State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, Lanzhou 730050, China
c
School of Physical Science and Technology, Southwest University, Chongqing 400715, China

A R T I C LE I N FO A B S T R A C T

Keywords: The hole-transport-material (HTM) free perovskite solar cells (PSCs) have drawn great attentions due to the
HTM-free simple structure, low fabrication cost and long term stability. However, the photoelectric conversion efficiency
CH3NH3PbI3/CsSnI3 heterojunction (PCE) of the HTM-free PCSs are still low comparing with the traditional sandwich type PSCs. In this work, a new
All-perovskite HTM-free PSC is proposed with CH3NH3PbI3/CsSnI3 all-perovskite heterojunction as light-harvester and carbon
Simulation
as back electrode through simulation using the wxAMPS tools. The results are analyzed and compared with the
traditional HTM-free perovskite solar cells. It reveals that the narrow band gap CsSnI3 broadens the absorption
spectrum to near-infrared region and the high hole mobility favors efficient hole transfer. The optimal perfor-
mance is achieved as Voc = 1.08 eV, Jsc = 25.33 mA/cm2, FF = 79.27%, PCE = 21.64%. Comparing to the
bare CH3NH3PbI3 absorbing layer, the device efficiency of CH3NH3PbI3/CsSnI3 heterojunction is improved from
18.29% to 21.64%. This indicates that the proposed HTM-free PSC is promising for future photovoltaic and
optoelectronics applications.

1. Introduction stability in 2014 (Mei et al., 2014). Then Yang et al. modified per-
ovskite precursor solution with cyclohexane, resulting in a 14.34%
In recent years, organic-inorganic hybrid perovskite solar cells structural efficiency of carbon electrodes without HTM in 2016 (Chen
(PSCs) have drawn vast attentions in the photovoltaic community due et al., 2016a, 2016b). Nevertheless, the highest reported PCE of HTM-
to their excellent photoelectric performance, high power conversion free PSCs does not exceed 20% (Xiao et al., 2019; Maniarasu et al.,
efficiency (PCE) and low fabrication cost (Deschler et al., 2014; Liu 2019). Recently, Kong et al. reported one effective method to improve
et al., 2013; Saliba et al., 2016; Wehrenfennig et al., 2014). Since it was PCE of HTM-free PSCs by introducing a organic monomolecular layer
first introduced in dye sensitized cells in 2009 (Kojima et al., 2009), the enable energy level matching of perovskite/electrode, and the PCE ar-
PCE of perovskite based PSCs have been greatly increased and up to rived at 19.42% (Kong et al., 2019).
now reached 25.2% (NCPV) (www.nrel.gov/ncpv). However, the ex- As mentioned, CsSnI3 is an inorganic lead-free perovskite material
pensive organic hole transport materials (such as spiro-OMETAD) have suitable for optical absorption layer due to its narrow energy gap of
limited the PSCs to commercialize due to their heavy fabrication cost 1.3 eV, high optical absorption coefficient of 104 cm−1 and extremely
and reduction in long-term stability (Zou et al., 2018; Hossain et al., high hole mobility of 585 cm2/ V−1s−1 at room temperature (Lee et al.,
2015). To overcome this issue, plenty of pioneering works concentrated 2012; Song et al., 2017). Therefore, halide perovskites based on Sn2+
on the HTM-free PSCs due to their low production cost, simplified have attracted most attentions in the PSCs field due to their excellent
processing steps, and the bipolar transport properties, i.e. they can photoelectric performance and Sn2+ is assumed to be the most poten-
transport electrons and holes (Liu et al., 2017; Etgar et al., 2012; Kong tial candidate of toxicity Pb2+ (Wang et al., 2016a, 2016b; Hao et al.,
et al., 2019; Zeng et al., 2017). Lioz Etgar et al. first reported HTM-free 2014). However, the poor stability of Sn2+ restricts the improvement of
CH3NH3PbI3/TiO2 heterojunction solar cells with PCE of 7.3% in 2012 device PCE since it is easy to be oxidized to Sn4+ in air (Zhang and Liu,
(Etgar et al., 2012). Anyi et al. reported HTM-free PSCs with carbon 2012; Chen et al., 2019). In 2019, Renxing Lin et al. reported a new
electrode which achieved a certified PCE of 12.8% and a long-term effective method to reduce Sn2+ from oxidization using metallic tin

⁎
Corresponding author.
E-mail addresses: [email protected] (X. Liu), [email protected] (Z.-Y. Wang).

https://doi.org/10.1016/j.solener.2020.03.037
Received 8 June 2019; Received in revised form 30 November 2019; Accepted 11 March 2020
0038-092X/ © 2020 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
Q. Duan, et al. Solar Energy 201 (2020) 555–560

Fig. 1. (a) Schematic structure of PSCs and (b) energy level diagram of the FTO/TiO2/CH3NH3PbI3/Carbon.

Table 1
Material properties of PSCs.
Material properties TiO2 DTL1 CH3NH3PbI3 DTL2 CsSnI3 FTO

Thickness (nm) 150 10 350 10 100–900 500

εr 10 10 10 10 9.93 9
Eg (Ev) 3.2 1.5 1.5 1.5 1.30 3.5
χ (eV) 4.0 3.93 3.93 3.93 3.6 4.0
Nc (cm−3) 1021 2.2 × 1018 2.2 × 1018 2.2 × 1018 1 × 1019 2.2 × 1018
Nv (cm−3) 2 × 1020 1.8 × 1019 1.8 × 1019 1.8 × 1019 1 × 1018 1.8 × 1019
un (cm2/v/s) 20 0.5 0.5 0.5 1500 2
up (cm2/v/s) 10 0.5 0.5 0.5 585 1
ND (cm−3) 5 × 1019 0 0 0 0 2 × 1019
NA (cm−3) 0 2.4 × 1014 2.4 × 1014 2.4 × 1014 1014 ~ 1021 0
Nt (cm−3) 1017 1018 1017 1018 1018 1015

CsSnI3 all-perovskite heterojunction as light absorbing layer and carbon

as back contact was reported. Since CH3NH3PbI3 and CsSnI3 have si-
milar perovskite crystalline structures, CsSnI3 growing on CH3NH3PbI3
is possible to obtain high quality films with fewer defects. Meanwhile,
the CH3NH3PbI3/CsSnI3 all-perovskite heterojunction may broaden the
absorption spectrum to the near-infrared region. Moreover, the de-
pendence of thickness of CsSnI3, defect and impurity concentrations on
photoelectric properties of PSCs are investigated numerically. The re-
sults show that the optimal PCE is 21.64% for the PSC of FTO/TiO2/
CH3NH3PbI3/CsSnI3/Carbon structure.

2. Device structure and properties

In this work, the device simulation is curried out using the wxAMPS
software which was improved based on AMPS developed by Professor S.
Fig. 2. The structure of FTO/TiO2/CH3NH3PbI3/carbon HTM-free PSCs simu- Fonash of Pennsylvania State University for theoretical simulation of
lation and experimental J-V curves (Xiao et al., 2019). solar cells (Liu et al., 2012). It can calculate parameters such as J-V
curve, quantum efficiency and carrier lifetime by solving Poisson
Table 2 equation [Eq. (1)], hole continuity equation [Eq. (2)] and electrical
The structure of FTO/TiO2/CH3NH3PbI3/carbon HTM-free PSCs simulation and continuity equation [Eq. (3)] (Lin et al., 2019a, 2019b), which are
experimental optimal results (Xiao et al., 2019). given as
Structure TiO2/CH3NH3PbI3 Voc (v) Jsc (mA/cm2) FF (%) PCE (%)
d ⎛ dψ ⎞
−ε (x ) = q [p (x ) − n (x ) + Nd+ (x ) − Na− (x ) + pt (x ) − nt (x )]
Simulation 1.07 21.7 79.14 18.29 dx ⎝ dx ⎠
Experiment 0.997 21.55 70.83 15.21 (1)

dpn p − pn0 dξ dp d 2pn

(Lin et al., 2019a, 2019b). The proposed method can hence potentially = Gp − n − pn μp − μp ξ n + Dp
dt τp dx dx dx 2 (2)
improve the stability of CsSnI3, and thus promote the future develop-
ment of photovoltaic (PV) and optoelectronics. dnp n p − n p0 dξ dnp d 2np
In this study, a new structural HTM-free PSC with CH3NH3PbI3/ = Gn − − np μn − μn ξ + Dn
dt τn dx dx dx 2 (3)

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Q. Duan, et al. Solar Energy 201 (2020) 555–560

3 30
(a) (b)
2 25

Current density (mA/cm2)

Energy level (ev)
1 CsSnI3
CH3NH3PbI3 20
0 CH3NH3PbI3
15 CH3NH3PbI3/CsSnI3
-1 TiO2
10 Jsc ( mA/
-2 Device Voc (v)
cm2)
FF (%) PCE (%)

CH3NH3PbI 1.07 21.7 79.14 18.29

-3 5
CH3NH3PbI
1.08 25.33 79.27 21.64
3/CsSnI3
-4 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Position (um) Voltage (v)

1.0
(c)
0.8
Quantum efficiency

0.6

0.4 CH3NH3PbI3
CsSnI3/CH3NH3PbI3
0.2

0.0
300 400 500 600 700 800 900 1000
Wavelength (nm)
Fig. 3. (a) The energy band structure diagram of PSCs, (b) J-V curves of CH3NH3PbI3 and CH3NH3PbI3/CsSnI3 heterojunction as absorbing layer and (c) the quantum
efficiency of CH3NH3PbI3 and CH3NH3PbI3/CsSnI3 heterojunction as absorbing layer.

where ε is the permittivity and ψ is the electrostatic potential; q is the higher than the experimentally reported optimal PCE of 15.21% by
electron charge; n, p, nt, pt are the densities of the free electrons, free Xiao et al. (2019). A comparison between experimentally achieved
holes, trapped electrons, and trapped holes; Na is the acceptor doping current density and voltage (J-V) curve and simulated J-V curve for
concentration; Nd is the donor doping concentration; G is the genera- carbon based HTM-free PSCs as show in Fig. 2 (Xiao et al., 2019). The
tion rate; D is the diffusion coefficient; ξ is the electric field. The HTM- calculated results are close to those Xiao et al. reported results, shown
free PSC was simulated with three input layers in illumination condi- in Table 2. It verified the reliability of our numerical simulation. But the
tion of AM1.5, where TiO2 was used as electron transporting layer and fill factor (FF) is obviously higher than the experimental result, possibly
CH3NH3PbI3/CsSnI3 all-perovskite heterojunction was used as light caused by that the series resistance of experiment is larger than the
absorbing layer. What’s more, fluorine-doped tin oxide (FTO) was front calculated one (Devi et al., 2018).
contact and carbon acted as back contact, as shown in Fig. 1. The The energy band structure diagram of CH3NH3PbI3/CsSnI3 hetero-
CH3NH3PbI3 light absorption coefficient comes from Wolf et al. re- junction as absorption layer PSCs is shown in Fig. 3(a). The J-V curves
ported (De Wolf et al., 2014). The simulated parameters of each layer of of the CH3NH3PbI3 and CH3NH3PbI3/CsSnI3 heterojunction separately
PSCs are displayed in Table 1 (Lee et al., 2012; Bi et al., 2014; Elseman as the absorption layer PSCs are shown in Fig. 3(b). The short-current
et al., 2018; Song et al., 2017; Ramli et al., 2017; Wojciechowski et al., density (Jsc) of the all-perovskite heterojunction absorber layer is
2014; Wu et al., 2016; Wang et al., 2016a, 2016b; Minemoto et al., greatly improved, while the open circuit voltage (Voc) and the FF are
2019; Zhang et al., 2014; Minemoto et al., 2019; Yan et al., 2019). Here barely changed. The Jsc is mainly affected by photo-generated minority
εr is dielectric constant, Eg is band gap energy, χ is electron affinity, Nc carrier current (Jeng et al., 2013; Song et al., 2017). The CH3NH3PbI3/
is band effective density of conduction, Nv is band effective density of CsSnI3 heterojunction extends the absorption spectrum to the near-in-
valence, un is electron mobility, up is hole mobility, NA is acceptor frared region, as shown in Fig. 3(c). It effectively promotes the photo-
doping concentration, ND is donor doping concentration and Nt is de- generated carrier concentration significantly increased and the Jsc
fect density. However, the interface defect state density between layers greatly improved. Therefore, the device efficiency of CH3NH3PbI3/
is larger than the internal defect state density. Taking into account the CsSnI3 heterojunction comparing to bare CH3NH3PbI3 absorbing layer
high recombination rate of interfacial carriers, CsSnI3/CH3NH3PbI3 and can be further improved from 18.29% to 21.64%.
CH3NH3PbI3/TiO2 were separately inserted by an absorber layer of The absorber thickness as a key factor of PSCs will affect the light
10 nm thickness with defect state density as 1018 cm−3, as shown in absorption and carrier generation, which takes the dominance in de-
Table 1 (DTL1 and DTL2). termining the PSCs performance. Therefore, the reasonable absorber
thickness played an important role in designing efficient HTM-free
PSCs. The effect of CsSnI3 thickness on J-V curves with the range of
3. Results and discussion
100–900 nm is shown in Fig. 4(a). The Jsc is significantly improved
from 21.86 mA/cm2 to 25.33 mA/cm2 with CsSnI3 thickness increasing
In this work, the structure of FTO/TiO2/CH3NH3PbI3/carbon was
from 100 nm to 500 nm. This variation is attributed to the larger
numerically simulated and an efficiency of 18.29% is obtained, which is

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Q. Duan, et al. Solar Energy 201 (2020) 555–560

30 1.0
(a) (b)
25

Current density (mA/cm2)

0.8

Quantum efficiency
100nm
20 100nm
0.6 200nm
200nm 300nm
15 300nm
400nm
400nm 0.4 500nm
10 500nm
600nm
600nm
700nm
5
700nm 0.2
800nm 800nm
900nm 900nm
0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 300 400 500 600 700 800 900 1000
Voltage (v) Wavelength (nm)

2 (c) Ec 24
(d)
1
Vbi
Energy level (ev)

22
0

PCE(%)
20
-1
100nm 900nm
-2 18

-3 Ev
16
-4
0.0 0.3 0.6 0.9 1.2 1.5 0 200 400 600 800 1000
Position (um) CsSnI3 thickness(nm)

Fig. 4. Effect of CsSnI3 thickness variation on (a) J-V curves, (b) Quantum efficiency, (c) energy band structure and (d) PCE of PSCs.

Fig. 5. Effect of CsSnI3 defect state density on (a) Voc, (b) Jsc, (c) FF and (d) PCE.

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Q. Duan, et al. Solar Energy 201 (2020) 555–560

Fig. 6. Effect of the CsSnI3 doping concentration on (a) J-V curves, (b) energy band structure, (c) PCE and (d) local enlarged energy band structure.

induced photo-generated carrier concentration due to the improved the impact of doping mechanism is very crucial in designing efficient
light absorption. The calculated quantum efficiency illustrated that the solar cells. The effects of CsSnI3 doping concentration (NA) on J-V
absorption spectrum region increases with CsSnI3 thickness, as dis- curves, Energy band structure and PCE are shown in Fig. 6. The CsSnI3
played in Fig. 4(b). When the thickness is more than 500 nm, Jsc in- NA changes from 1014 to 1021 cm−3 . The J-V curves of PSCs with var-
creases slowly and tends to saturation because that a too large CsSnI3 iation of NA of CsSnI3 are plotted in Fig. 6(a). When the doping con-
thickness could cause a great growth in the charge carrier recombina- centration is less than 1016 cm−3, the Voc and Jsc have no evident
tion rate. Fig. 4(c) shows the effect of CsSnI3 thickness variation on changes, as a result that the relatively low doping concentration does
energy band structure diagram, where the built-in electric field (Vbi) not change the intrinsic property of CsSnI3. The Jsc and Voc obviously
hardly changed with CsSnI3 thickness increase. The main factor af- increase with the NA of CsSnI3 increasing from 1016 to 1019 cm−3. The
fecting the Vbi is the doping concentration, as described by the fol- higher Voc is related to the increase of Vbi (as shown in Fig. 6(b), (d)
lowing equation (Wang et al., 2016a, 2016b): and equation (4)) caused by the heavier NA. When the NA of CsSnI3 is
more than 1019 cm−3, the Jsc tends to saturation. The effect of NA of
KT N N
Vbi = ln A 2 D CsSnI3 on PCE is displayed in Fig. 6(c). The PCE rapidly increase along
q ni (4)
with the NA of CsSnI3 increasing from 1016 to 1020 cm−3, and when
where k is Boltzmann constant, T is temperature, q is the electron doping concentration is more than 1020 cm−3, the PCE tends to sa-
charge, ni is intrinsic concentration, NA is acceptor doping concentra- turation. Although the separation of the photon-carriers can be pro-
tion and ND is donor doping concentration. The PCE and current density moted by increasing the doping concentration, a too large doping
have the similar trend in change as shown in Fig. 4 (d). An appropriate concentration reduces carrier mobility and increases carrier re-
thickness 500 nm was used in calculations in this paper. combination (Wang et al., 2016a, 2016b), which will decrease the PCE.
Since defect state density (Nt) is an important parameter affecting Therefore, to obtain moderate PCE of HTM-free PSCs by balancing Jsc
the PSCs performance, the effects of Nt within CH3NH3PbI3 and CsSnI3 and Voc, we recommend that the CsSnI3 NA is better among the range of
layers on Voc, Jsc, FF and PCE are simulated, as shown in Fig. 5. When 1020 to 1021 cm−3.
the Nt within CH3NH3PbI3 and CsSnI3 increases from 1014 cm−3 to 1019
cm−3, the Voc and FF slowly reduce (Fig. 5(a), (c)), but the Jsc and PCE 4. Conclusions
rapidly decrease (Fig. 5(b), (d)) on account of forming many re-
combination centers in interface and interior PSCs, which increases the In summary, a numerical simulation and analysis has been per-
carriers recombination rate. As CsSnI3 is unstable in the air (Chen et al., formed on HTM-free PSCs with CH3NH3PbI3/CsSnI3 all-perovskite
2019; H. Chen et al., 2016; L. J. Chen et al., 2016; Marshall, 2016; Song heterojunction as absorber layer using wxAMPS. By optimizing the
et al., 2017), we set CsSnI3 defect state density as 1018 cm−3 and thickness, defect density and doping concentration of CsSnI3, the device
CH3NH3PbI3 defect state density as 1017 cm−3 in our simulations with a high PCE of 21.64% was obtained. The simulation illustrated
(Elseman et al., 2018). that CH3NH3PbI3/CsSnI3 heterojunction has better photoelectric prop-
The doping concentration is also a crucial parameter, which directly erties than CH3NH3PbI3 absorber layer and the PCE of PSCs are im-
affects many optoelectronic properties, such as Voc, carriers re- proved from 18.29% to 21.64%. CsSnI3 extends absorption spectrum to
combination rate and diffusion length, etc. Therefore, understanding near-infrared region and the insertion of high hole-mobility CsSnI3 can

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Q. Duan, et al. Solar Energy 201 (2020) 555–560

benefit carrier transport. However, the stability of CsSnI3 has great Nano 13 (2), 1625–1634.
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Declaration of Competing Interest Mater. Res. Express 4 (7), 075505.
Lin, R., Xiao, K., Qin, Z., Han, Q., Zhang, C., Wei, M., Li, A., 2019a. Monolithic all-
The authors declare that they have no known competing financial perovskite tandem solar cells with 24.8% efficiency exploiting comproportionation to
suppress Sn (II) oxidation in precursor ink. Nat. Energy 4 (10), 864–873.
interests or personal relationships that could have appeared to influ- Liu, Y., Sun, Y., Rockett, A., 2012. A new simulation software of solar cells—wxAMPS.
ence the work reported in this paper. Sol. Energy Mater. Sol. Cells 98, 124–128.
Lin, Lingyan, Jiang, Linqin, Li, Ping, Baodian Fan, Yu., Qiu, Fengpo Yan, 2019b.
Simulation of optimum band structure of HTM-free perovskite solar cells based on
Acknowledgments
ZnO electron transporting layer. Mater. Sci. Semicond. Process. 90, 1–6.
Minemoto, T., Kawano, Y., Nishimura, T., Chantana, J., 2019. Numerical reproduction of
This research was sponsored by the National Natural Science a perovskite solar cell by device simulation considering band gap grading. Opt.
Foundation of China under Grant No. 11774041 and the Chongqing Mater. 92, 60–66.
Mei, A., Li, X., Liu, L., et al., 2014. A hole-conductor–free, fully printable mesoscopic
Research Program of Basic Research and Frontier Technology under perovskite solar cell with high stability. Science 345 (6194), 295–298.
Grant No. cstc2015jcyjA50033 and No. cstc2015jcyjBX0056. Maniarasu, S., Rajbhar, M.K., Dileep, R.K., et al., 2019. Hole-conductor free ambient
processed mixed halide perovskite solar cells. Mater. Lett. 245, 226–229.
National Center for Photovoltaics (NCPV), National Renewable Energy Laboratory
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