Optik - International Journal for Light and Electron Optics 217 (2020) 164805

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Optik
journal homepage: www.elsevier.com/locate/ijleo

Original research article

Role of various transport layer and electrode materials in

T
enhancing performance of stable environment-friendly Cs2TiBr6
solar cell
Madhupriya Samantaa,*, Sk Ijaj Ahmeda, Kalyan K. Chattopadhyayb, Chayanika Bosea
a
Department of Electronics and Telecommunication Engineering, Jadavpur University, Kolkata, 700032, India
b
Thin Film and Nanoscience Lab, Department of Physics, Jadavpur University, Kolkata, 700032, India

A R T IC LE I N F O ABS TRA CT

Keywords: To eliminate hazardous effect of lead on environment, titanium based lead-free inorganic per-
Solar cell ovskite solar cells (SCs) have attracted intense contemporary research interest. Advantages of
Lead free perovskite using titanium are its non-toxicity, high durability, low cost and ease of availability compared to
Cesium titanium(IV) bromide other divalent elements. The sole available literature on Cs2TiBr6 published recently has ex-
Copper phthalocyanine
perimentally used it as solar light harvesting material. Design and simulation of such SC are,
Poly(3-hexylthiophene)
therefore, very much essential to enhance its performance. We simulate Cs2TiBr6 SC for the first
Nickel oxide
time and Silvaco ATLAS device simulator is used for that. Different materials are tried as
transport layers to separate carriers and suppress their recombination. Here, titanium dioxide is
used as electron transport material, while copper phthalocyanine, poly (3-hexylthiophene) and
nickel oxide as hole transport material. For the best yield, SC is designed with appropriate
thickness of each of the above layers. Photo conversion efficiency of simulated SC is obtained
here as 5.5% against its experimentally reported value of 3.3%. Efficiency of 8.5% along with a
fill factor of 73.6% is finally achieved from Cs2TiBr6 cell simulated with absorbing material as
thick as commonly used in standard perovskite SCs. Obtained results are quite encouraging and
prove potential of Cs2TiBr6 for efficient environment-benign photovoltaic applications.

1. Introduction

In recent years, halide perovskite (HP) based materials have acquired immense importance as efficient solar light absorber for
photovoltaic applications due to their outstanding optoelectronic properties like large carrier diffusion lengths, moderate carrier
mobility, high visible light absorption coefficients and tunable optical bandgaps [1–4]. Further advances in perovskite solar cells
(PSC), through a combination of innovative steps in material science, chemistry and device technology, are expected to lead to a
revolution in the field of renewable energy.
HPs are of two categories: one is organic-inorganic HP (OIHP) and the other all inorganic HP (IHP). General formula for one type
of HPs are ABX3, where A indicates the monovalent organic cation viz. methylammonium [MA+ (CH3NH3+)], formamidinium [FA+
(HC(CH2)2+)], and inorganic cation like Cs+; B represents divalent cation viz. Pb2+, Sn2+, and X represents halide anion like Cl−,
Br−, I− [5]. Till date, record photo conversion efficiency (PCE) of around 23.2% has been experimentally observed from OIHP based
solar cells with transport layers [6,7]. The major limitation towards proper commercialization of OIHP solar cell is the volatile nature

⁎
Corresponding author.
E-mail address: madhu.ece9@gmail.com (M. Samanta).

https://doi.org/10.1016/j.ijleo.2020.164805
Received 27 February 2020; Accepted 22 April 2020
0030-4026/ © 2020 Elsevier GmbH. All rights reserved.
M. Samanta, et al. Optik - International Journal for Light and Electron Optics 217 (2020) 164805

of organic cations MA+ and FA+, which makes the material thermodynamically unstable. If Cs+, which is not hygroscopic in nature,
replaces MA+, it results in IHPs with very low chance of rapid hydration. Theoretical and experimental results proclaim superior
intrinsic stability of IHPs over OIHPs [8–11]. However, mechanisms such as polymorphic transition, decomposition, oxidation, or
their combinations may cause degradation of IHPs. The most common Lead (Pb) based IHP is CsPbI3, which yields solar cell with PCE
above 15% [12]. But as lead (Pb) is a toxic element, it is hazardous to environment [12]and is being replaced by appropriate elements
like Tin (Sn2+) [13,14], Germanium (Ge2+) [15], Bismuth (Bi3+) [16,17], Palladium (Pd4+) [18]. CsSnI3 is one of the recently
developed lead free all inorganic HPs under investigation. However, Babayigit et al. [19] have reported that Sn-based HPs also
possess certain amount of toxicity. In addition, Sn2+ gets easily oxidized to Sn4+in contact with air. Thus, a special double-perovskite
crystal structure with general formula A2BX6, B being cation of +4 oxidation state, has been proposed for next generation HP solar
cells. Cesium Titanium Bromide (Cs2TiBr6) is one of such double-perovskite materials based on Ti4+ as B-site cation. Due to the earth
abundance, non-toxicity and ultra-stability of Ti, Cs2TiBr6 is expected to emerge as a stable and promising light harvesting material
for IHP solar cells [20].
The sole literature on Cs2TiBr6 based lead-free PSC is the experimental investigation done by Chen et al. in which they obtained
PCE of 3.3%. They also investigated the thermal, optical and moisture stability of Cs2TiBr6 material and found it superior with respect
to OIHP material from the stability point of view. In addition, around 330 h of stable operation has been reported for Cs2TiBr6 based
solar cell [21]. These facts led us to explore an environment-friendly Cs2TiBr6 solar cell with an effort to boost its efficiency by
incorporating additional layers of appropriate material and thickness. The proposed structure will also be tried with different
electrode materials. Simulation of such Cs2TiBr6 solar cell is reported here for the first time. For simulation, we use TCAD from
Silvaco ATLAS Device Simulator.

2. Design

Among several Perovskite Solar Cell (PSC) architectures in use today, the highest PCE is reported from a structure that comprises
of a light-absorbing layer of perovskite, an electron transport layer (ETL) of TiO2 and a hole transporting layer (HTL).Transport layers
(TLs), in general, aid in transportation and segregation of photo-generated carriers of opposite polarities as well as inhibition of
interface charge recombination. Proper choice of material and thickness of above layers is very crucial in determining the overall
performance of designed cell.
In designing Cs2TiBr6 based PSC, we follow the above architecture. The schematic structure and associated energy band diagram
of such PSC are shown in Fig. 1. Fluorine doped Tin Oxide (FTO) is used as the cathode, while the anode material is chosen as Gold
(Au), Silver (Ag) or Copper (Cu). As suggested from the band diagram (Fig. 1), the ETL not only helps electrons to reach the cathode,
but also puts a barrier to flow of generated holes. Similarly, introduction of HTL allows holes to flow to anode but blocks electrons.
For ETL, inorganic metal oxide such as TiO2 [12,16], ZnO [22], SnO2 [23]are commonly used. Organic materials viz. poly-
triarlyamine (PTAA) [12], spiro-OMeTAD [16] and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) were the
initial choice for HTL [24]. But their chemical, thermal instability and high cost are important deterrent towards proper development
of such PSCs. However, poly (3-hexylthiophene) (P3HT) and small molecule organic copper phthalocyanine (CuPc) are expected to be
the potential candidates for HTL. P3HT possesses good optical, electrical properties, low cost and easy fabrication process [25], while
CuPc exhibits good thermal, chemical stability and moisture resistance property, which make it useful for encapsulation layer of PSCs
[26,27]. Along with organic HTLs, inorganic oxide HTLs such as, NiO, CuI may be the potential alternatives for transport layers in
PSCs. However, the properties like large bandgap, suitable work function, deep VB level around 5.3 eV [28] have made NiO more
popular. In this report, three hole transporting materials – two organic (CuPc and P3HT) and the other inorganic (NiO) will be
explored along with TiO2 as the electron acceptor.

Fig. 1. Proposed solar cell: (a) Schematic structure and (b) Energy band diagram.

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M. Samanta, et al. Optik - International Journal for Light and Electron Optics 217 (2020) 164805

3. Simulation

The proposed solar cell structures are simulated using TCAD from Silvaco ATLAS. The existing literatures related to Cs2TiBr6 [21],
TiO2 [29], NiO [29], CuPc [30,31] and P3HT [32] are considered for choosing parameters for simulation. In simulating the cells,
defect assisted Shockley-Read-Hall (SRH) recombination model is considered. Their performances are determined under AM 1.5 G
solar spectrum illumination condition.
Performance of a solar cell is described in terms of four parameters viz. Short circuit current density (Jsc), Open circuit voltage
(Voc), Fill factor (FF) and Power conversion efficiency (PCE). Among them, the FF is difficult to optimize as it is greatly influenced by
resistance loss mechanisms, which however have minor influence on Jsc and Voc. The maximum achievable FF can be determined
from Voc using the following relation [33]:
voc − ln(voc + 0.72)
FF =
voc + 1 (1)
qVoc
with voc = Here, voc is defined as normalized open circuit voltage and η is the ideality factor for diode. For perovskite based
ηKT
.
absorber, Voc exceeds 1, and thus FF may be as large as 0.9 [according to Eq. (1)] for η = 1. Since SRH recombination model is
employed here, we take η = 2 [34] instead of its ideal value 1. Eq. (1) sets the theoretical limit to FF, which can never be realized in
practice.

4. Results and discussion

Our perovskite thickness is taken as 200 nm as per the existing literature [21]. As in addition to efficient electron collection, TiO2
behaves as window layer to allow incident solar radiation to reach the absorber material; its thickness must be chosen properly.
Consequently, in order to investigate influence of one TL, we vary its thickness in presence of the other layer following the scheme
reported in [35]. Thickness of TiO2 is first varied from 10 to 100 nm with a 10 nm thick NiO film. Simulation results presented in
Fig. 2(a) show that FF falls monotonically with thickness of TiO2, whereas slight improvement appears in PCE. It has been experi-
mentally observed that around 10 nm thin TiO2 film yields 75% (approx.) transmittance of incident solar radiation, while thicker
films cause enhanced light scattering and reduce effective utilization of incident illumination [36]. Thus, thickness of ETL is chosen
here as 10 nm. Similarly, NiO layer thickness is varied from in the range of 5–100 nm taking thickness of TiO2 and Cs2TiBr6 layers
respectively as 10 nm and 200 nm. Result in Fig. 2(b) demonstrates the gradual deterioration in FF for the entire range of variation in
NiO thickness. Thick transport layers, however, have a tendency for cracks over large areas [36]. On the other hand, as too thin NiO
and TiO2 layers lack reproducibility and may get affected by the presence of pinholes, at least 10 or 20 nm thickness is recommended
for their pinhole free deposition [35].Thus, we choose a 10 nm thick NiO layer, which also yields the highest FF, as is evident from
Fig. 2(b).
In our study, influences of different HTLs on cell performance are also investigated. For simulation of cell with TiO2 and CuPc,
P3HT [P3HT (S1)] or NiO, we consider the time resolved photoluminescence (PL) decay time of individual material from the existing
literatures. The J–V characteristics (Fig. 3) and a comparison table (Table 1) of various solar cell parameters are presented. Results
indicate NiO outperforms the other two hole transporting materials – CuPc and P3HT. In order to validate our simulated results,
Cs2TiBr6 cell with TiO2 and P3HT [P3HT (E1)] is further simulated taking the PL lifetime of TiO2/Cs2TiBr6 and Cs2TiBr6/P3HT
interfaces as reported by Chen et al. [21].
The simulated results (row 4, Table 1) match reasonably with the experimental results [21]. However, presence of glass substrate
and defect densities in the materials in real solar cell structure may be responsible for the existing difference between the experi-
mental and simulated results.
Next we simulate different cell configurations with undoped and doped transport layers. Existing literatures have reported that
some of the dopants may improve the performance but degrade cell stability in case of P3HT [37]; whereas dopants impose negative

Fig. 2. Variation of FF and PCE with thickness of transport layers: (a) TiO2 and (b) NiO.

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M. Samanta, et al. Optik - International Journal for Light and Electron Optics 217 (2020) 164805

Fig. 3. J-V characteristics with different HTL.

Table 1
Solar cell parameters for different HTL materials.
HTL material Jsc (mA/cm2) Voc (V) FF (%) PCE (%)

CuPc 6.24 1.05 55.30 3.65

P3HT (S1) 6.37 1.14 56.62 4.12
NiO 6.40 1.14 64.57 4.70
P3HT (E1) 6.47 1.10 45.46 3.24

impact on film morphology in case of CuPc [38]. On the other hand, in Fig. 3, NiO has emerged as the most efficient of all the three
hole transport materials considered here. We, therefore, propose different device configurations with TiO2 and NiO layers. The
simulated results are listed in Table 2.
The J–V characteristics of different cell configurations are presented in Fig. 4(a), which reveals the prominent roles of the two
terminal layers n+ TiO2 [Conf. B] and p+ NiO [Conf. C] in improving performance of the basic cell [Conf. A]. Here, TiO2 and NiO
layers are doped with concentration 1016 cm−3 and 1019 cm−3 respectively. NiO with exact stoichiometric form is wide bandgap
semiconductor and possesses very high intrinsic resistivity [39], which results in poor FF of the corresponding cell. Thus, heavier
doping is chosen for NiO. Doping in both TiO2 and NiO layers reduces the interfacial charge transport resistances and facilitates
efficient carrier extraction. This leads to modification in the J–V characteristics through tremendous improvement in FF. Similar
influence of doping in transport materials has also been reported experimentally [35]. Performance of the final cell structure [Conf.
E] with both doped layers is improved synergistically in terms of FF and PCE. It yields 17% and 18% increment in PCE and FF
respectively with respect to the cell with undoped layers [Conf. D]. The maximum limit of FF is calculated using Eq. (1) and is found
to be 82%.The simulated FF appears as around 76%, well below the theoretical limit, as it should be. Thus, to enhance the cell
performance, doping of transport layers can be treated as an effective way to modulate their electrical and optical properties.
The role of different electrode materials is further investigated in the present study. All the above results are reported with Au
with work function (WF) 5.1 eV as anode material. After finalizing the structure of the proposed solar cell, we check its performance
for other two anode materials, such as Ag (WF ∼ 4.52 eV) and Cu (WF ∼ 4.7 eV). Simulated results are presented in Table 3 and
Fig. 4(b). Results indicate that as work function of the metal increases, cell performance improves. So, both the Table and figure prove
that Au outperforms the other two anode materials. Thus, structure of the proposed inorganic lead-free PSC finally comes out to be
FTO/n+ TiO2 (10 nm)/Cs2TiBr6 (200 nm)/p+ NiO (10 nm)/Au.
Experiments based on lead PSC have reported 330 nm as the optimum thickness for absorber materials [40].We finally simulate
our proposed cell with 330 nm thick absorber material (Cs2TiBr6), including both 10 nm thick n+ TiO2 and p+ NiO layers. The J–V
characteristics are shown in Fig. 4(c) and simulated cell parameters are listed in Table 4. The table also includes results of the earlier
Conf. E for easy comparison. Respective enhancements in PCE and Jsc by almost 54% and 61% are clearly evident, along with

Table 2
Solar cell parameters for different cell configurations.
Device configuration Jsc (mA/cm2) Voc (V) FF (%) PCE (%)

(A) FTO/Cs2TiBr6/Au 5.53 0.56 58.20 1.81

(B) FTO/n + TiO2/Cs2TiBr6/Au 5.96 0.59 64.69 2.29
(C) FTO/Cs2TiBr6/p + NiO/Au 5.94 0.91 57.50 3.12
(D) FTO/TiO2/Cs2TiBr6/NiO/Au 6.40 1.14 64.57 4.70
(E) FTO/n + TiO2/Cs2TiBr6/p + NiO/Au 6.33 1.14 76.34 5.50

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M. Samanta, et al. Optik - International Journal for Light and Electron Optics 217 (2020) 164805

Fig. 4. J-V characteristics for (a) different device configurations, (b) different anode materials, and (c) two different absorber thicknesses; (d) final
simulated structure.

Table 3
Solar cell parameters for different anode materials.
Electrode Jsc (mA/cm2) Voc (V) FF (%) PCE (%)

Silver (Ag) 6.27 1.01 66.91 4.26

Copper (Cu) 6.28 1.13 73.48 5.24
Gold (Au) 6.33 1.14 76.34 5.50

Table 4
Solar cell parameters for different absorber thickness.
Thickness (nm) Jsc (mA/cm2) Voc (V) FF (%) PCE (%)

200 6.33 1.14 76.34 5.50

330 10.25 1.12 73.59 8.51

nominal deteriorations in FF and Voc. The simulated structure is presented in Fig. 4(d).

5. Conclusions

The lead free inorganic Cs2TiBr6 PSC has been designed and simulated with TiO2 as the electron transport material, and CuPc,
P3HT and NiO as three different hole transport materials. Three anode materials – Au, Ag and Cu have also been explored. Our
proposed Cs2TiBr6 (200 nm)PSC employing doped TiO2 (10 nm) and NiO (10 nm) layers has resulted in PCE of 5.5% against that of
3.3%, as appeared in the sole available report of Cs2TiBr6 based PSC [21]. The best performing final structure emerges as FTO/n+
TiO2 (10 nm)/Cs2TiBr6 (330 nm)/p+ NiO (10 nm)/Au, which yields 8.5% PCE. However, its efficiency is still quite low compared to
the Pb-based PSCs, but long duration stable operation and most importantly, the environment friendly nature are expected to develop
Cs2TiBr6 PSC as one of the front runners in the field of next generation solar cell.

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Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Acknowledgements

The Authors gratefully acknowledge the Department of Science and Technology, Govt. of India for DST INSPIRE (DST/INSPIRE
Fellowship/2017/IF170868) fellowship scheme and University Grants Commission for ‘University with Potential for Excellence
scheme’ (UPE-II), Government of India for the execution of this work.

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