doi.org/10.26434/chemrxiv.12367505.

v1

Energy Level Engineering of Charge Selective Contact and Halide

Perovskite by Modulating Band Offset: Mechanistic Insights
Yassine Raoui1, Hamid Ez-Zahraouy, Samrana Kazim, Shahzada Ahmad

Submitted date: 25/05/2020 • Posted date: 27/05/2020

Licence: CC BY-NC-ND 4.0
Citation information: Raoui1, Yassine; Ez-Zahraouy, Hamid; Kazim, Samrana; Ahmad, Shahzada (2020):
Energy Level Engineering of Charge Selective Contact and Halide Perovskite by Modulating Band Offset:
Mechanistic Insights. ChemRxiv. Preprint. https://doi.org/10.26434/chemrxiv.12367505.v1

Mixed cation and anion based perovskites solar cells (FAPbI3)0.85(MAPbBr3)0.15 gave enhanced stability
under outdoor conditions, however, it yielded limited power conversion efficiency when SnO2 and
Spiro-OMeTAD were employed as electron and hole transport layer (ETL/HTL). The inevitable interfacial
recombination of charge carriers at ETL/perovskite and perovskite/HTL interface diminished the efficiency in
planar (n-i-p) perovskite solar cells. Employing computational approach for uni-dimensional device simulator,
the effect of band offset on charge recombination at both interfaces were investigated. We noted that it
acquired cliff structure when the conduction band minimum of the ETL is lower than that of the perovskite, and
thus maximizes interfacial recombination. However, if the conduction band minimum of ETL is higher than
perovskite, i.e. spike structure is formed, which improve the performance of solar cell up to an optimum value
of conduction band offset allowing to reach performance of 25.21%, with an open circuit voltage (Voc) of 1231
mV, a current density Jsc of 24.57 mA/cm2 and a fill factor of 83.28%. Additionally, we found that beyond the
optimum offset value, large spike structure could decrease the performance. With an optimized, energy level
of Spiro-OMeTAD and the thickness of mixed-perovskite layer performance of 26.56 % can be attained. Our
results demonstrate a detailed understanding about the energy level tuning between the charge selective
layers and perovskite and furthermore how the improvement in PV performance can be achieved by adjusting
the energy level offset.

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 Energy level engineering of charge selective contact and halide perovskite
by modulating band offset: Mechanistic insights
Yassine Raoui1,3, Hamid Ez-Zahraouy3, Samrana Kazim1,2*, Shahzada Ahmad1,2*
1
BCMaterials, Basque Center for Materials, Applications and Nanostructures, Bld. Martina
Casiano, UPV/EHU Science Park, Barrio Sarriena s/n, 48940 Leioa, Spain
2
IKERBASQUE, Basque Foundation for Science, Bilbao, 48013, Spain.
3
Laboratory of Condensed Matter and Interdisciplinary Sciences, Faculty of Sciences,
Mohammed V University, Rabat, Morocco

* E-mail address: [email protected]; [email protected];

Abstract

Mixed cation and anion based perovskites solar cells (FAPbI3)0.85(MAPbBr3)0.15 gave enhanced
stability under outdoor conditions, however, it yielded limited power conversion efficiency
when SnO2 and Spiro-OMeTAD were employed as electron and hole transport layer
(ETL/HTL). The inevitable interfacial recombination of charge carriers at ETL/perovskite and
perovskite/HTL interface diminished the efficiency in planar (n-i-p) perovskite solar cells.
Employing computational approach for uni-dimensional device simulator, the effect of band
offset on charge recombination at both interfaces were investigated. We noted that it acquired
cliff structure when the conduction band minimum of the ETL is lower than that of the
perovskite, and thus maximizes interfacial recombination. However, if the conduction band
minimum of ETL is higher than perovskite, i.e. spike structure is formed, which improve the
performance of solar cell up to an optimum value of conduction band offset allowing to reach
performance of 25.21%, with an open circuit voltage (Voc) of 1231 mV, a current density Jsc of
24.57 mA/cm2 and a fill factor of 83.28%. Additionally, we found that beyond the optimum
offset value, large spike structure could decrease the performance. With an optimized, energy
level of Spiro-OMeTAD and the thickness of mixed-perovskite layer performance of 26.56 %
can be attained. Our results demonstrate a detailed understanding about the energy level tuning
between the charge selective layers and perovskite and furthermore how the improvement in
PV performance can be achieved by adjusting the energy level offset.

Keywords: Device modelling, Electron Affinity, Conduction band offset, Valence band offset,
Charge recombination, Perovskite solar cell.
1. Introduction

1
Over the past years, hybrid organic-inorganic lead halide perovskite was subject to intense
investigation due to its astonishing opto-electrical properties, which led to the fabrication of
efficient solar cells that are cost effective and easy to process. One of the seminal scientific
events of 2009 was the report of perovskite solar cells (PSCs) fabrication which gave 3.8%
power conversion efficiency (PCE) [1]. After a decade of highly intense efforts by researchers
across the globe, PSCs has reached the certified PCE of 25.2% [2], while theoretical approach
for this has also been reported [3].
The rapid evolution in the field of PSCs was ensued due to the radical approach in materials
compositions and device architect engineering. The first report, employed it as a sensitizer in a
solid state dye-sensitized solar cell [4], followed by as absorber in insulating alumina scaffold
structure, and subsequently in a planar heterojunction PSC [5]. The planar heterojunction has
attracted significant attention, due to its ease of processing and the existing knowledge
borrowed from organic photovoltaics. The PSCs based on n-i-p planar configuration consists
of transparent conducting oxide (TCO) / electron transport layer (ETL) / perovskite / hole
transport layer (HTL)/metal contact; where, ETL act as n-type, HTL as p-type and perovskite
as intrinsic layer. In recent year, we have witnessed surge of interest in utilizing SnO2 as ETL
for PSCs fabrication, due to its numerous merits. Compared to conventional TiO2, SnO2 exhibits
a wider band gap due to deeper conduction band, shows high transmittance over a wide spectral
range with high electron mobility, which in turn can fasten electron transfer from perovskite to
the ETL and minimize the charge accumulation at the ETL/perovskite interface. Moreover,
SnO2 is stable than TiO2 under UV illumination and ideally suited with low temperature
fabrication process, all these properties make tin oxide as a favorable candidate as ETL for
PSCs [6–12]. The best efficiency using SnO2 as ETL were reported with different perovskite
such as MAPbI3, (FAPbI3)0.97(MAPbBr3)0.03 and (FAPbI3)0.85(MAPbBr3)0.15 [13–17]. Among
them, (FAPbI3)0.85(MAPbBr3)0.15 demonstrated higher stability under outdoor conditions as
well as in the laboratory [18,19]. You’s group reported 21.6% room-temperature processed
SnO2 and passivated FAPbI3 [20], this improvement in PCE was made possible due to increased
electron extraction as a result of optimized perovskite film fabrication process, to allow the
carriers rational interface between the ETL/perovskite. The conduction band of SnO2 depends
on various factors, such as the method and fabrication condition, oxygen vacancies that directly
affects the energy level alignment at ETL/perovskite. Among many factors which cause lower
Voc in PSCs, the interface recombination at ETL/PSK and PSK/HTL influence largely and
affects device performance [21,22]. For planar PSCs, charge injection and recombination
processes depend on the properties of ETL, HTL, energy level alignment for ETL/absorber and

2
absorber/HTL interface and defect density at both interfaces. Thus, an optimized interface is
vital to push the performance of PSCs, that can be achieved by adjusting the conduction band
offset (CBO) and valence band offset (VBO). These band offset are critical for charge transport,
extraction and interface recombination in PSCs, and interface engineering at ETL/perovskite
and perovskite/HTL interface play an important role to influence the carrier recombination and
profoundly the performance of PSCs [23–26]. Takachi et al have reported the effect of
tunnelling the electron affinity of ETL to form spike and cliff structures which has a bearing on
the performance of PSCs, in a n-i-p configuration employing classical TiO2 as ETL, MAPbI3-
xClx as absorber layer with an electron affinity of 3.9 eV, and Spiro-OMeTAD as HTM. The
reported parameters was limited and with the compositional engineering of perovskite, energy
level will change and importantly the ETL used suffer from, lower electron mobility which
causes insufficient charge carrier separation at the interface and hysteresis [27], the UV
instability of TiO2 yields to rapid decrease in the performance [28]. Earlier, we have shown that
(FAPbI3)0.85(MAPbBr3)0.15 as light harvester in PSCs showed improved stability under outdoor
conditions [18], and theoretically we analyzed the performance of PSCs using SnO2 as an
alternative of TiO2 [3]. To overcome intriguing stability and performance issue we undertook
mechanistic study in a configuration of FTO/SnO2/(FAPbI3)0.85MAPbBr3)0.15/Spiro-
OMeTAD/Au which can elucidate the role of spike and spoke with an electron affinity of 4.15
eV for perovskite layer. Doping of SnO2 can shift the level energy by adjusting the alignment
between the layers, also it can enhance the performance of the device by reducing the
recombination rate at ETL/perovskite interface.
To address such challenges, herein, by using solar cell capacitance simulator (SCAPS)
software, we have elucidated the impact of energy level alignment between ETL/absorber
interface using SnO2/(FAPbI3)0.85(MAPbBr3)0.15, and absorber/HTL interface using
(FAPbI3)0.85(MAPbBr3)0.15/Spiro-OMeTAD by varying the conduction band offset
(CBO=Ec= Ec,ETL- Ec,absorber) and valence band offset (VBO = EV = EV,absorber - EV,HTM)
respectively via the electron affinity of selective layers. We noted that changing the electron
affinity of SnO2 and Spiro-OMeTAD leads to a favorable CBO and VBO respectively, and
decreases charge recombination at both interface and improves the external quantum efficiency
(EQE) in the spectral range of 320 − 360 nm. These factors help to enhance the performance of
our modelled PSCs with optimized CBO (+0.35eV) and VBO (-0.41 eV ) which can yield a
PCE of 26.50 % with a Voc of 1.23 V, JSC of 24.88 mA/cm2 and FF around 86.53 %.

2. Experimental Section

3
The normal glass and ITO coated glass substrates were cleaned by a sequential sonication
treatment in hellmanex solution, acetone, distilled water and isopropanol and then treated with
UV-ozone for 1h. For optical measurements, (FAPbI3)0.85(MAPbBr3)0.15 was deposited from a
precursor solution containing FAI (1 M), PbI2 (1.2 M), MABr (0.2 M), and PbBr2 (0.2 M) in
anhydrous DMF:DMSO 4:1 (v:v). The perovskite solution was spin-coated in a two-step
process at 1000 and 4000 rpm for 10 and 30 s, respectively. During the second step, 100 μL of
chlorobenzene was used as an antisolvent and poured on the substrate 15 s prior to the end of
deposition process. The substrates were then annealed at 100 °C for 1 h in a glovebox according
to previous report [29]. Hole transporting layer (HTL) was prepared by dissolving 72.3 mg of
Spiro-OMeTAD in chlorobenzene and mixed with 28.8 µL of 4-tert-butylpyridine, 17.5 µL of
bis(trifluoromethane ) sulfonimide lithium salt (Li-TFSI) from the stock solution(520 mg mL-1
in acetonitrile). The solution was spin-coated on normal glass at 4000 rpm for 20 s. Electron
transporting layer (ETL): SnO2 nanoparticles (2.67 %) solution was spin coated on normal glass
substrates in ambient air at 5000 r.p.m. for 30 s, and was subject to annealing at 150 oC for 30
min.
Device Preparation: The concentration and deposition conditions of absorber and charge
selective layers were same as mentioned above. SnO2 as ETL was deposited on the ITO
substrate using SnO2 nanoparticles (2.67 %) followed by thermal annealing at 150 ℃ for 30
min in air. Subsequently, perovskite was deposited in a one-step deposition method [29].
Followed by the hole transporting layer Spiro-OMeTAD was deposited on top of perovskite at
a spin rate of 4000 rpm for 20 s. Finally, a ~ 70 nm gold electrode was thermally evaporated on
top of the HTL.
Absorption Measurements: The absorption spectra was required to make inputs for SCAPS
simulation (Fig. 1) and the thickness of different layers was determined from cross sectional
SEM image as illustrated in Fig. 2b. For the device simulation, the absorption coefficient (α) of
(FAPbI3)0.85MAPbBr3)0.15 (absorber layer) Spiro-OMeTAD (HTL) and SnO2 (ETL) film was
determined by measuring the absorbance spectra (Fig.1a and b) and the thickness (L) , using
the equation 𝛼 = 𝐴 𝑙𝑛10/𝐿[30]. The absorbance was measured using Cary 60 UV-vis
spectrophotometer. The thickness of the film was determined by cross section SEM as show in
Figure 2b.

4
 Figure 1: (a) UV-Vis absorption spectra of mixed perovskite (FAPbI3)0.85MAPbBr3)0.15 and (b) Spiro-OMeTAD and SnO2.

3. Device simulation parameters

The simulations were performed using SCAPS 3.3.07 software [31] which is based on the
Poisson equation (1) , and the continuity equations for electrons (2) and holes (3) as reported in
our previous work [3].

𝑑 𝑑Ѱ
(𝜀(𝑥) ) = 𝑞[ 𝑝(𝑥) − 𝑛(𝑥) + 𝑁𝐷+ (𝑥) − 𝑁𝐴− (𝑥) + 𝑝𝑡 (𝑥) − 𝑛𝑡 (𝑥) ] (1)
𝑑𝑥 𝑑𝑥
1 ⅆ𝐽𝑝
+ 𝑅𝑝 (𝑥) − 𝐺(𝑥) = 0 (2)
𝑗 ⅆ𝑥
1 ⅆ𝐽𝑛
−𝑗 + 𝑅𝑛 (𝑥) − 𝐺(𝑥) = 0 (3)
ⅆ𝑥

The device architecture of the planar n-i-p type PSCs proposed in the present simulation study
consists of FTO/SnO2/interface layer 1 (IL1) /(FAPbI3)0.85MAPbBr3)0.15 /interface layer2 (IL2)/
Spiro-OMeTAD /Au as illustrated in Figure 2a. The gold (Au) was back contact (cathode) and
fluorine doped tin oxide (FTO) as the front contact (anode). The thickness of the FTO, ETL,
absorber, and HTL were calculated from the cross sectional SEM image of fabricated device
(Fig. 2b) showing an experimentally achieved efficiency of 11.5 % with a Voc of 0.97 V, Jsc of
19.27 % and fill factor (FF) of 61.41%.
Table1 summarizes the input parameters for the FTO, SnO2, mixed perovskite, Spiro-
OMeTAD, IL1 and IL2. In the table, NA and ND denote acceptor and donor densities, εr is
relative permittivity, χ is electron affinity, Eg is the band gap energy, μn and μp are mobilities of
electron and hole, and Nt is defect density, which is the most important parameter to calculate
the efficiency of the PSCs. For mixed perovskite, Nt = 3×1011 cm-3 was taken from the literature.
[19]. The defect type in bulk perovskite is considered to be neutral and capture cross section of

5
electron and hole is 2×10-14 cm2. The electron and hole thermal velocity was 107cm/s. The
simulations were carried out at AM 1.5G illumination.

Figure 2. a) Device architecture of planar type perovskite solar cell used in the present study and b) cross sectional SEM image.

Table 1. Parameters Used in the SCAPS Simulation of Perovskite solar cell.

Parameter FTO SnO2 IL1 Mixed IL2 Spiro-
PSK OMeTAD
thickness (nm) 400 90 10 700 10 150
Band gap, 3.5 3.6[32] 1.56 1.56[33,34] 1.56 3.04[35]
Eg (eV)
Electron affinity 4 Wide- 4.15 4.15[33,34] 4.15 2.11[35]
(χ) ranging
Ɛr 30 100 46.9 46.9 [36] 46.9 3[35]
18 18 18 18 18
Nc (1/cm ) 3
2.2×10 2.2×10 2.2×10 2.2×10 2.2×10 2.2×1018
Nv (1/cm3) 1.8×1019 1.8×1019 1.8×1019 1.8×1019 2.5×1019 1.8×1019
μn(cm /Vs)
2
20 240[37] 5.31 5.31[36] 5.31 0.001[38]

μp 10 240 10.19 10.19[36] 10.19 0.001

NA (1/cm3) -- - - - - 1×1018

ND (1/cm3) 2×1019 1×1017 1×1013 1×1013 1×1013 -

15 15 15 11 15
Nt(1/cm ) 3
1×10 1×10 1×10 3×10 [19] 1×10 1×1015

1. Results and discussion

4.1 Formation of Cliff-CBO (-eV) and Spike-CBO (+eV) structures at ETL/perovskite layer
One of the concern of the PSCs community, is the energy level alignment between the absorber
and charge selective layers. To address such issues, the efforts should be laid to develop link
between the theoretical and experimental studies.
Here, through the theoretical device modelling, by adjusting the electron affinity (χ) of SnO2 as
ETL, we can notice the formation of two structure related to the conduction band offset (CBO)
of SnO2/(FAPbI3)0.85MAPbBr3)0.15 layer, when the electron affinity of ETL (χETL) is larger or
smaller than absorber layer(χabsorber) as illustrated in Figure 3, the energy Cliff with CBO (-)

6
and the energy spike − CBO (+) formed respectively. In other words, if the conduction band of
ETL is lower than that of the absorber, the energy Cliff CBO (−) is formed with no potential
barrier for electrons at the ETL/absorber interface, and if CB of ETL is higher than that of the
mixed perovskite absorber, the energy Spike-CBO (+) is formed at the ETL/absorber interface
acting as barrier for electrons as shown in Fig.4.

Figure 3. Band alignment scheme of SnO2 ETL/IL1/mixed perovskite absorber showing negative and positive conduction band
offset (CBO) by varying the electron affinity of SnO2 with respect to mixed (FAPbI3)0.85(MAPbBr3)0.15. The negative and
positive sign of the CBO were defined by the barrier height of the photo-generated electrons.

The cliff formation can improve the accumulation near to SnO2/perovskite, which in turn
enhances the recombination in this area by back-transfer to the interface of
SnO2/(FAPbI3)0.85MAPbBr3)0.15 heterojunction. On the other hand, the formation of spike
structure act as band bending to reduce the recombination at SnO2/(FAPbI3)0.85MAPbBr3)0.15.
A similar trend has also been reported in perovskite solar cell and other types of thin film solar
cells [22,39–41].

Figure 4. Theoretically calculated energy levels diagram (relative to the vacuum level) of SnO 2 films by varying the electron
affinity of SnO2 with respect to mixed (FAPbI3)0.85(MAPbBr3)0.15.

7
 4.2 Influence of the conduction band offset of ETL/perovskite interface on PV performance
Fig. 5a represents J-V characteristics as a function of conduction band offset ranging from -0.07
to +0.4 eV by controlling the electron affinity of SnO2 and Fig. 5b shows the influence of the
CBO on Voc, Jsc and FF and PCE. With the increase in the CBO value, the cliff structure
transforms into the spike structure (Fig.5d). The Jsc, Voc, FF and PCE of PSCs first increases
with increasing CBO until +0.35eV and then becomes constant. The solar cell with CBOspike=
+0.35eV showed the best performance; with an astonishing PCE of 25.61%, a Voc of 1231 mV,
a Jsc of 24.57 mA/cm2 and a FF of 83.28 %.
To understand the enhancement in the performance by differentiating with cliff and spike
structure, we first analyzed the external quantum efficiency (EQE) using the same variations of
CBO as used for the J-V characteristics and illustrated in Fig.5d, We can notice that increasing
CBO lead to an increase in the EQE value in the spectral range of 300 − 360 nm, and when the
CBO is higher than +0.35, the EQE becomes saturated in this region, this has a positive impact
on the performance of solar cell.
The decrease in the Voc for the lower value of CBO can be assigned to the cliff structure
formation, which is build up at ETL/mixed-perovskite, and leads to high recombination
between the holes and electrons due to small potential difference at this area Fig. 6a. On the
contrary, the formation of spike structure leads to build a barrier at ETL/mixed-perovskite to
facilitate the separation of charge carriers Fig. 6b.
The effect of CBO on Voc can be illustrated according to the equation (4) [42,43].
𝐸𝐴 𝑛𝑘𝑇 𝐽𝑜𝑜
𝑉𝑜𝑐 = − 𝑙𝑛 𝐽𝑠𝑐 (4)
𝑞 𝑞

𝐸𝐴 = 𝐸𝑔 − ∆𝐸𝑐 (5)
Voc is open circuit voltage, EA is activation energy, n is diode ideality factor, K is Boltzmann
constant, T is temperature, J00 is current pre factor and Jsc is short circuit current density. For T
𝐸𝐴
= 0 K , (𝑉𝑜𝑐 = ), as illustrated in Figure 5a and Figure 6a, the formation of “cliff-type” band
𝑞

alignment will break the barrier for transfer of electron leading to decrease EA and this affects
directly the value of Voc.

8
Figure 5: a) J–V curves of perovskite solar cell as a function of CBOs, b) Influence of the CBO on PCE, Voc, Jsc and FF, c)
Energy band diagram of planar perovskite solar cells with variation of conduction band offset showing the formation of cliff
and spike structure and d) effect of conduction band offset on external quantum efficiency.

By analyzing the advantages of spike structure formed at the ETL/absorber layer interface (Fig.
4 and 5), which can act as a barrier for photo-generated electron flow towards to the edge of
ETL/absorber endows to enhance the photo-generation of free charge carriers. This will also
suppress the recombination rate at the interface which is beneficial to increase the PV
performance, suggesting with the spike structure extraction and transport of charges carriers are
efficient. To make further advancement in the performance of solar cell using the spike structure
at ETL/absorber, we suggests optimized CBO value should not be higher than the energetic
alignment of the absorber layer. Avoiding the spike structure will not be effective as it acts as
a barrier to stop the migration of electron to the back contact accelerating the rate of
recombination at interface.

9
Figure 6. Energy band diagram of PSCs using the FTO/SnO2/mixed PSK/Spiro-OMeTAD structure when the conduction band
minimum of SnO2 is a) below {cliff structure} and b) above {spike structure} that of CBM of mixed perovskite.

4.3 Influence of CBO of ETL /Perovskite on charge recombination

The recombination at the interfaces occurred at multiple sites. The majority carrier extracted to
the ETL, then the recombination with the minority carrier generated in the perovskite layer.
This suggests, means to increase the lifetime of free charges by minimizing the capture of hole
by the electron.
The spike structure can act as a barrier to block the flow of injected electrons from the ETL to
the absorber layer. One of the challenges in PSCs is the recombination loss across the interfaces,
especially at the ETL/absorber which can lower the voltage [24]. The issue of recombination at
the interfaces come from the defect state and due to misalignment of the energetic level between
the perovskite and the ETL [44]. To elucidate the improvement in the performance of PSCs
related to the CBO, we investigated the effect of CBO on the recombination rate at
ETL/absorber.
Fig.7 depicts the total recombination rate of FTO/SnO2/(FAPbI3)0.85MAPbBr3)0.15/Spiro-
OMeTAD/Au with the variation of CBO. It can be noted that by decreasing CBO of ETL
/perovskite helps to decrease the interface recombination between SnO2 and mixed perovskite.
This provides the solution to enhance the performance of solar cell with an optimum value of
CBO of +0.35 eV. After achieving this optimum value of CBO, the interface recombination
saturated. The formation of cliff structure between ETL / perovskite facilitates the accumulation
of electrons and holes which contributes to the highest recombination rate. When the spike
structure starts to form, the recombination rate decreases until an optimum spike is formed.

10
Therefore, after reaching to the CBO value of +0.35 eV, the spike structure becomes a barrier
that prevents the back transfer of electrons to the perovskite.

Figure 7: The depth distribution curve showing total recombination rates of the perovskite solar cells with different CBO at 0V
bias.

The design of an optimum CBO can reduce the recombination rate and enhances the extraction
of free charges at ETL/perovskite by forming an optimum spike structure at the interface. This
will allow to build band bending that prevents flow of injected electrons to the interface and
lowers the recombination rate between the majority and minority carriers.
By noting the significance of the interfacial recombination at ETL/perovskite, we can
propose methods that can allow to shift the conduction band of SnO2 and can reduce the
recombination at the interface. Modified SnO2 prepared by various methods can be an approach
to achieve the desired spike structure. Similarly, doping of ETL with optimized concentration
of alkali metals or with Mg, Zn and Y etc. can have great potential to fabricate efficient
conduction band. Recently, graphene quantum dot (GQDs) treatment for SnO2 was shown to
enhance the extraction of the electrons and to reduce the recombination in MAPbI3 [45]. Doping
with cesium carbonate Cs2CO3 to functionalize SnO2 was reported for organic solar cells, by
tuning the amount doping of Cs2CO3 [46] the optimize conduction band of SnO2 (-3.9 eV) can
be reached.
4.4 Influence of the valence band offset of perovskite/HTL interface on PV performance
Suitable energy level alignment between perovskite and the hole transport layer is also a crucial
key to improve the performance of PSCs. We have observed that the valence band maximum
(VBM) of (FAPbI3)0.85MAPbBr3)0.15 is much lower (-5.71 eV) compared to highest occupied
molecular orbital (HOMO) of Spiro-OMeTAD (-5.15 eV), that leads to an increase valence

11
band offset (VBO = − 0.56eV), i.e. the difference between the valence band of the absorber
layer and those of HTM is significantly high. As reported previously, Ev < 0 is prerequisite
to make the valence between all the photovoltaic parameters [25]. Here, we investigated the
effect of VBO, by changing the electron affinity () of Spiro-OMeTAD to make deeper
(HOMO) level of HTM related to mixed perovskite to see which value of VBO can maximize
the efficiency and the electron affinity of absorber and ETL were kept fixed as shown in Figure
8. Figure 9a and 9b shows the influence of valence band offset variation on photovoltaic
parameters of perovskite solar cell using the optimized conduction band offset (0.35 eV) for
ETL/mixed-perovskite as discussed in previous section. When the VBO is increased more than
−0.56 eV (pristine Spiro-OMeTAD), Voc decreases while Jsc remains unchanged, thus FF and
PCE significantly improved until VBO reaches a value of −0.41 eV, after this optimum value
of VBO, we observed reduction in PCE and FF. It has been reported that decreased the VBO
is preferable to reduce the charge recombination at interface but high VBO results in low FF
[24], we speculate this behavior does not originate from the beginning, there is an optimum
value that can activate this processes due to the absorber energy level. In our case we elucidated
the optimum value of VBO, equal to −0.41eV using in the same time the optimized value of
CBO, according to our previous study [3] that deep lowest unoccupied molecule level (LUMO)
of HTM respect to absorber layer allows to push the performance of PSCs. Here we have
achieved this by using the similar HTM, but through optimized electron affinity, theoretically
that can deliver the peak performance of 26.50 %.

12
Figure 8. Band alignments of absorber/IL2/HTL layers with negative VBO when the electron affinity of absorber is greater
than the HTL. Here IL1 and IL2 are inserted to take into account the carrier recombination at the interface.

Figure 9: (a) J–V curves of PSCs as a function of VBOs and (b) the effect of electron affinity of HTM on performance
of PSCs.

4.5 Thickness optimization of mixed perovskite absorber layer

In case of single cation perovskite layer such as MAPbI3, many theoretical and simulation
studies demonstrated that 500 nm can be the optimum thickness of perovskite layer. In case of
13
mixed cation-anion perovskite layer, controlling the optimum thickness has a significant effect
on device performance. Thus, we investigated the effect of perovskite thickness in range of 300
to 1400 nm on PV performance using optimized CBO and VBO at ETM /PSK and PSK/HTM
interface respectively. As illustrated in Fig. 10a, with increasing the perovskite thickness, the
FF drops monotonically related to the increased series resistance. Voc mostly remain unchanged
for up to 500 nm, beyond this Voc dropped because with the thicker absorber layer the
recombination dominates, the voltage can be presented by the equation (5) where 𝑛 is diode
𝑛𝐾𝑇
ideality factor, Io is dark saturation current, IL is light -generated current, and is thermal
𝑞

voltage :
𝑛𝐾𝑇 𝐼
𝑣𝑂𝐶 = ln (𝐼𝑜𝐿 + 1) (5)
𝑞

In case of thick absorber layer, the carriers recombination rate become more high, leads to
increase Io more than 𝐼𝐿 . Due to this reason, Voc decreases with increasing the absorber
thickness. On the other hand, thick layer absorbs more light and thus charge carrier
concentration increases which results into high value of Jsc. Subsequently, the PCE increases
and reaches a maximum of 26.56 % at 641nm thickness, beyond this it saturates and start
decreasing. With high thickness of absorber layer, the transfer of charge carriers become longer,
leading to a higher rate of recombination. It can be deducted from Fig.10 (b), if the thickness
of perovskite layer increases the external quantum efficiency (EQE) dramatically improved in
the range of 641 -700 nm, thereafter it increases slowly which can explain the improvement of
Jsc even for higher thickness.

Figure.10: (a) Influence of mixed perovskite absorber thickness on PV parameters for FTO/SnO2/mixed perovskite/Spiro-
OMeTAD/Au device and (b) external quantum efficiency of PSCs as a function of absorber layer thickness.

14
5. Conclusion
Energy level engineering is paramount to reduce the interfacial recombination in PSCs. We
investigated the influence of the conduction band offset (CBO) in planar PSCs by tuning the
electron affinity of SnO2 as charge selective layer in a mix perovskite environment through
numerical analysis using SCAPS. This was established on the basis of absorption coefficient
which was derived from the experimental data set. We found that the performance of solar cell
is affected by conduction band offset at SnO2/(FAPbI3)0.85(MAPbBr3)0.15, and noted the
formation of “spike-type’’ band alignment, that is favorable as compared to “Cliff-type’’. This,
in turn, decreases the recombination rate at the SnO2/(FAPbI3)0.85(MAPbB3)0.15 interface with
an optimized value of CBO elucidated to be 0.35eV, which will lead to a competitive PCE of
25.61%. The modified valance band of Spiro-OMeTAD was found to attend 5.3 eV, while the
optimum thickness of mixed perovskite layer at 641nm, yielded power conversion efficiency
of 26.56%. Our mechanistic insights demonstrate that band-alignment engineering at
ETL/perovskite and perovskite/HTL is an important strategy to push the performance of PSCs
to their thermodynamic limit, which can be effectively achieved by designing new charge
selective layers or tweaking its intrinsic (physico-chemical) properties.

Acknowledgments
This work has received funding from the European Union H2020 programme under Excellence
research, ERC grant MOLEMAT (726360) and Parasol from Spanish ministry of Science and
Innovation. The authors would like to thank Professor Marc Burgelman, Department of
Electronic and information Systems, University of Gent for the development of the SCAPS
software package and allowing its use.

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