Department of Physics

Ramjas College
University of Delhi

Janurary 2026

TUNING PHOTOVOLTIC PARAMETRES OF DOUBLE

PEROVSKITE VIA 2-D PASSIVATION & TRANSPORT
LAYER OPTIMATIZAITON

Dissertation submitted in partial fulfilment of the requirements

for the degree of
Bachelor of Science (Honours) in Physics

Submitted by:
Sreejan Rayhan Mahanta*
2022/13/114
22056567004

Supervisor
Dr. Vishnu Chauhan
Department of Physics, Ramjas College, University of Delhi

Co-supervisor
Dr. Manish Kumar
Department of Physics, ARSD College, University of Delhi

*[Link]@[Link]
Declaration

I hereby declare that the research work embodied in this dissertation entitled ”Tuning Photovoltic
Parametres of Double Perovskite via 2-D Passivation &Transport Layer Optimization” is an
authentic record of my own work carried out under the supervision of Dr. Vishnu Chauhan
and co-supervision of Dr. Manish Kumar.
I further declare that this work has not been submitted in part or in full for the award of
any other degree or diploma in this or any other university or institution.

Sreejan Rayhan Mahanta

Roll No: 22056567004
Department of Physics
Ramjas College, University of Delhi
Delhi-110007

Dr. Vishnu Chauhan Dr. Manish Kumar

Supervisor Co-Supervisor
Department of Physics, Ramjas College Department of Physics, ARSD College
University of Delhi University of Delhi

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Acknowledgement

I would like to express my deepest gratitude to my supervisor, Dr. Vishnu Chauhan, and
co-supervisor, Dr. Manish Kumar, for their invaluable guidance, mentorship, and patience
throughout the course of this dissertation. This work would not have been possible without their
insightful feedback and scientific expertise.
I extend my sincere thanks to the Department of Physics, Ramjas College, for providing
the academic framework and necessary resources to carry out this research. I am also grateful
to the Principal and the faculty members for their constant encouragement.

Sreejan Rayhan Mahanta

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Contents

Declaration 1

Acknowledgement 2

1 Introduction 4
1.1 Physics of Perovskite Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.1 Fundamental Working Principle . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.2 The Illuminated Diode Equation . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.3 Key Performance Parameters . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2 Silicon-based Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 Third-Generation Solar Technologies and Perovskite Emergence . . . . . . . . . . 7
1.4 Lead Substitution Strategies in Perovskites . . . . . . . . . . . . . . . . . . . . . 8

2 SCAPS-1D Simulation Methodology 9

3 Simulation Design 11
3.1 Baseline Reproduction and Model Validation . . . . . . . . . . . . . . . . . . . . 15
3.2 Optimization Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.1 Rationale for Sequential Optimization Across Absorbers . . . . . . . . . . 16
3.2.2 Justification for Separating ETL and HTL Optimization . . . . . . . . . . 17
3.2.3 Limits of the Decoupling Approximation . . . . . . . . . . . . . . . . . . . 18

References 19

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Chapter 1: Introduction

Sustainable Energy Research initiatives have reached an important tipping point globally. The
damaging impact of the human-induced climate has been well established and transitioning away
from fossil fuel-based generation, towards renewables, is no longer an ’option’; it is mandatory
[3]. Among the many renewable energy sources available, solar energy has emerged as one of
the most compelling for meeting the dual challenge of global climate change and energy security
because; like all renewable energy sources, no greenhouse gases are produced directly during
the generation of electricity; and after the installation of solar power systems, the negative
environmental impact is limited (1). Developing efficient, stable and cost-effective photovoltaic
(PV) technologies is a critical factor in achieving the transition to sustainable energy systems
globally (2).

1.1 Physics of Perovskite Solar Cells

1.1.1 Fundamental Working Principle

Figure 1.1: (a) PSC device structure (b) Diagrammatic illustration of the electron transport
layers of PSC devices’ working and charge transport mechanism (3)

A Perovskite Solar Cell (PSC) operates on the photovoltaic effect, converting photon energy
into electrical energy through a semiconductor absorber (the perovskite layer) which is placed
between an Electron Transport Layer (ETL) and a Hole Transport Layer (HTL) (4). The process
consists of three stages:

Photogeneration: When sunlight hits the semiconductor, it produces free charge pairs (elec-
trons e− and holes h+ ) due to the absorption of photons with energies greater than the
bandgap (Eg ) which excite electrons within the semiconductor from Valence Band (VB) to
Conduction Band (CB). The low binding energy of excitons (< 50 MeV) in the perovskites
allows thermal dissociation into free carriers at room temperature.

Charge Separation: The work function difference between the n-type contact ETL and p-type
contact HTL establishes a built-in electric field (Vin ) which is essential to separate charge

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 carries before recombination. This electric field, via drift-diffusion transport, drifts the
electrons towards ETL and holes towards HTL.

Charge Collection: The ETL and HTL perform complementary functions of selectively ex-
tracting electrons and holes respectively, while blocking the other charge carrier. The
extracted carriers are subsequently collected at FTO anode and metal cathode electrodes,
which generate current through the external circuit.

1.1.2 The Illuminated Diode Equation

Mathematically, the electrical behaviour of illuminated solar cells is given by the Illuminated
Diode Equation, which superimposes light-generated current with the reverse saturation current
of the p-n junction:
 qV 
J = Jph − J0 e nkB T − 1 (1.1)

Physical Interpretation of Terms:

• J (Total Current Density): The net current density flowing out of the solar cell under
load.

• Jph (Photocurrent Density): The current density generated by light absorption, which
represents the maximum available current from photoexcitation and carrier collection. It
depends on the absorption spectrum, quantum efficiency, and transport properties.

• J0 (Saturation Current Density): This represents recombination losses through radia-

tive and non-radiative pathways. A low J0 indicates superior device quality with fewer de-
fects and reduced non-radiative recombination via trap-assisted Shockley-Read-Hall (SRH)
processes.
qV
• (e nkB T ): This describes the diode junction’s forward-bias diffusion current. As applied
voltage V increases, this term grows exponentially, which represents the reverse current
opposing the photocurrent.

• q: Elementary charge (1.602 × 10−19 C).

• V: Applied voltage across the cell terminals.

• n (Ideality Factor): n = 1 indicates ideal band-to-band recombination, while n ≈ 2

indicates trap-assisted recombination via mid-gap defect states which is caused by point
defects or grain boundaries. Perovskites typically exhibit n between 1 and 1.5 in high-
quality samples.

• kB T (Thermal Energy): Product of the Boltzmann constant and Temperature. At 300

K, kB T /q ≈ 0.0259 V .

1.1.3 Key Performance Parameters

Solar cells are evaluated using four standard metrics extracted from the J-V curve:

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Short-Circuit Current (ISC )

• Definition: The maximum current density when the cell operates at zero voltage (V = 0).

• Physical Measure: At short circuit, the exponential term vanishes (e0 − 1 = 0), giving:

JSC ≈ Jph (1.2)

• Significance: JSC quantifies the light-harvesting efficiency and carrier collection capabil-
ity. It is limited by the bandgap energy (narrower bandgaps absorb more photons) and the
external quantum efficiency (EQE), which is the fraction of incident photons converted to
collected electrons. Modern perovskites achieve JSC values of 23-26 mA cm−2 , subject to
the AM1.5G solar spectrum and thermalization loss of hot carriers.

Open-Circuit Voltage (VOC )

• Definition: The voltage at which the net current is zero (J = 0).

• Physical Measure: Solving the diode equation for V when J = 0 yields:

 
nkB T Jph
VOC = ln +1 (1.3)
q J0

• Significance: Voc represents the maximum voltage the cell can generate and is funda-
mental to determining power output. It increases logarithmically with photocurrent-to-
saturation-current ratio and is highly sensitive to recombination losses. Defects in the
perovskite layer increase J0 because of trap-assisted recombination, causing Voc to de-
crease logarithmically. This connection emphasizes how crucial defect passivation is to
maximizing device performance.

Fill Factor (FF)

• Definition: A measure of the ”squareness” of the J-V curve, which quantifies the ideality
of power extraction.

• Formula:
Vmp × Jmp
FF = (1.4)
VOC × JSC
where Vmp and Jmp are the voltage and current density at the maximum power point.

• Physical Measure: The performance of a perovskite solar cell is negatively affected by

series resistance (Rs ) arising from contact resistance, ETL/HTL conductivity limitations,
and metal electrode impedance, and also by shunt resistance (Rsh ) resulting from leak-
age pathways such as pinholes and grain-boundary defects. When optimally produced,
laboratory-made perovskite solar cells have a FF of greater than 80%, with FF values
nearing 85%.

Power Conversion Efficiency (PCE)

• Definition: The fraction of incident solar power converted to electrical power.

• Formula:
VOC × JSC × F F
P CE = (1.5)
Pin

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 where Pin = 1000 W m−2 under standard AM1.5G test conditions.

• Significance: The maximum efficiency for photovoltaic devices is found using the PCE.
Optimization of PCE requires simultaneous optimization of three competing factors: (i)
JSC must be maximized through improved light absorption and carrier collection efficiency,
(ii) Voc must be maximized by reducing defects and providing optimal band alignment at
ETL/absorber and absorber/HTL interfaces, and (iii) FF must be maximized by suppress-
ing resistive losses and leakage currents.

1.2 Silicon-based Solar Cells

Most of the energy produced in solar power is made up of silicon solar cells (more than 90%
of installed capacity), indicating that they comprise a significant portion of the total installed
capacity of photovoltaic technology around the world (5). Despite this market dominance, effi-
ciency of silicon solar cells is limited by physical and thermodynamic laws, governing radiative
recombination in semiconductors, known as the Shockley-Queisser (S-Q) limit, which sets a
theoretical maximum PCE of approximately 29.4% for single-junction devices operating under
standard terrestrial illumination conditions (AM 1.5G spectrum). This represents an insur-
mountable barrier for conventional silicon photovoltaic architectures. At present, commercially
available monocrystalline silicon solar cells typically have efficiencies between 25 to 27%, while
cutting-edge R&D prototypes have achieved maximum efficiencies of 26.81% in the laboratory
(6). Consequently, because commercial silicon solar cells already operate at or near the Q-S
limit, further improvements in single-junction silicon solar cell efficiencies are unlikely.
Silicon-based solar cells, beyond the efficiency constraint, present significant environmental
and cost-based challenges due to the manufacturing process. The process of purifying silicon to
meet the rigorous requirements for solar cell production is highly energy-intensive and requires
extensive amounts of electricity to perform high-temperature reduction of the silicon dioxide
(quartz) material in electric arc furnaces. For every metric tonne of metallurgical-grade silicon
produced directly from quartz, approximately 4.7 to 5 tonnes of CO2 (carbon dioxide) equivalents
are released into the atmosphere (7).

1.3 Third-Generation Solar Technologies and Perovskite

Emergence
The photovoltaic research community has shifted much of its focus away from traditional solar
technologies towards developing ”third generation” forms of solar energy systems as a direct
result of the limitations placed upon these systems by silicon (8). Third generation solar tech-
nologies consist of a variety of new and innovative materials and structures that are being
explored as potential solutions for generating solar power (8). Third-generation solar cells in-
clude organic photovoltaics (OPVs), quantum dot solar cells (QDSCs), dye-sensitized solar cells
(DSSCs), and, most prominently, metal-halide perovskite solar cells (PSCs) (9).
The efficiency of perovskite solar cells has been on an unparalleled improvement track com-
pared to previous work on solar cells in the past few decades. Efficiency has increased from
approximately 3.8% in 2009 to over 26% at the time of 2025 for laboratory single-junction solar
cells, as well as nearly 34% for laboratory perovskite-silicon tandem solar cells (10). Beyond

7
their rapid efficiency gains, several properties of perovskites position them as unrestrained al-
ternatives:

• Low Manufacturing Intensity: Compared to silicon’s energy-intensive process of grow-

ing and purifying its crystalline structure, perovskite solar cells can be manufactured using
low-energy methods of solution-based deposition at low temperatures (≤ 150◦ C) (11).

• Flexible Device Architecture: By changing the composition and the cation of the
halides in perovskite absorber layers, it is possible to tune the perovskite absorber layer
to absorb different wavelengths of light. Because of this tunability, perovskite cells can be
manufactured in tandem with other cells to form tandem arrays. Laboratory tandem arrays
of perovskite-silicon have achieved efficiencies exceeding 33%, exceeding the theoretical
efficiency of silicon alone (11).

• Thin-Film Technology: Because perovskite materials exhibit extremely high optical

absorption coefficients, the active layers of perovskite cells may be only 300-500 nm thick
compared to the 100+ micrometres of active layer material required for silicon, therefore
using much less cost and material to manufacture perovskite devices (12).

1.4 Lead Substitution Strategies in Perovskites

Perovskite crystals are made up of cations labelled A and B, and halide anions labelled X in
the (ABX3 ) stoichiometry (13). All perovskite crystalline materials will have similar and unique
physical characteristics which make them suitable for utilization in photovoltaic applications
through several ways. These include high optical absorption coefficients, tunable visible and near-
infrared spectrum bandgaps, long carrier diffusion lengths, and high intrinsic defect tolerance
compared to many traditional semiconductor structures (14) (15).

Figure 1.2: Structure of perovskite (16)

Although conventional lead-based perovskites are highly efficient at converting sunlight into
electricity, there are two major barriers to their widespread commercialization: lead’s (Pb)
toxicity presents significant environmental and health hazards, and conventional lead-based per-
ovskites are unstable when subjected to environmental stressors such as moisture, heat, and UV
radiation (17) (18). When exposed to moisture, water molecules can adsorb onto the perovskite’s
surface, thus altering interatomic distances and creating irreversible pathways for chemical degra-
dation (17). Furthermore, exposure to UV and O2 will result in increased rates of oxidative
degradation (19).
Lead toxicity has prompted researchers to employ a variety of substitution methods to mit-
igate the effects of lead. One of the simplest methods is to replace lead with other isovalent
elements from Group 14 on the periodic table. Tin (Sn) and Germanium (Ge) are particu-
larly attractive as direct lead substitutes from a Group 14 perspective because of their chemical
properties (20) (21). However, these elements also suffer from significant drawbacks related to
stability, as Sn2+ and Ge2+ ions are very unstable and readily oxidize to +4 oxidation states

8
in air (under ambient temperature and humidity conditions) (20)(22)(23). The oxidation of
Sn2+ and Ge2+ ions creates large numbers of p-type dopant defects, which contribute to a rapid
decline in device performance (20)(23).
The double perovskite architecture is a more robust strategy than either partial or total
replacement of a lead ion through an element of the same valence. With this type of heterovalent
substitution, two lead cations (P b2+ ) are replaced with two different types of metal cations, one
that is monovalent (B + ), and another that is trivalent (B 3+ ), or, alternatively, with divalent and
tetravalent (B 2+ and B 4+ ) metals (20)(24). As a result of maintaining charge neutrality during
the above-described cation substitutions, this approach to heterovalent substitution permits
the incorporation of elements that would otherwise be intrinsically non-toxic, as described in
references (20)(24)(25). Examples of successful double perovskites include Cs2 AgBiBr6 and
related Cs2 AgB ′ X6 compounds (where B ′ = Bi, Sb, In), all of which possess excellent chemical
stability, low toxicity, and long carrier lifetimes (24)(25).

Figure 1.3: (a) Elemental mapping images depicting the electronic charge distribution of the
LNMO compound along the (111) crystallographic plane in two-dimensional (2D) and three-
dimensional (3D) representations. (b) Variation in charge density between the (100) plane in
two-dimensional and three-dimensional contexts. (26)

The double perovskite crystal structure is defined by [A2 B ′ B ′′ X6 ], where the B ′ and B ′′ -site
cations coordinate with six (X) halide anions to form octahedral coordination surrounding the
cations as (B ′ X6 )5− and (B ′′ X6 )3− (24). The octahedra and the resulting three-dimensional
network are connected by corner and edge sharing of their (X) halide anions, while the A-site
cations occupy the voids of this octahedral framework (24). The preservation of the octahedral
three-dimensional coordination geometry enables double perovskites to exhibit some of the same
advantageous optoelectronic characteristics as traditional perovskites.

Chapter 2: SCAPS-1D Simulation Methodology

The SCAPS-1D (Solar Cell Capacitance Simulator), developed by the Department of Elec-

9
tronics and Information Systems (ELIS) at the University of Gent, Belgium, serves as the main
research tool in this study. This software provides a numerical simulation tool that has all of the
features needed for simulating thin film solar cells by providing the ability to define up to 7 layers
of semiconductors with properties such as bandgap, electron affinity, dielectric permittivity, and
defect density distribution.

Figure 2.1: SCAPS-1D Action Panel

The simulation solves three coupled differential equations self-consistently:

1. Poisson’s Equation: Relating electrostatic potential (ψ) to charge distribution.
 
d dψ
ϵ(x) +
= −q(p − n + ND − NA− + ρdef ) (2.1)
dx dx

2. Continuity Equation for Electrons:

dn 1 dJn
= + G(x) − R(x) (2.2)
dt q dx

3. Continuity Equation for Holes:

dp 1 dJp
=− + G(x) − R(x) (2.3)
dt q dx

Physical Interpretation of Variables

Based on the semiconductor properties defined in the simulation parameters:

• ψ(x): The electrostatic potential at position x.

• ϵ(x): The dielectric permittivity of the material layer.

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 • n, p: The concentrations of free electrons and holes, respectively.

• ND
+
, NA− : The ionized donor and acceptor dopant concentrations.

• ρdef : The charge density contribution from defects in the crystal lattice (related to Defect
Density).

• Jn , Jp : The electron and hole current densities.

• G(x): The generation rate of electron-hole pairs (Photogeneration) due to light absorption.

• R(x): The recombination rate of carriers (loss mechanisms).

Standard AM1.5G Illumination (1000 W/m2 ) and an initial temperature of 300K were used
for the simulations. The frequency of the AC analysis for the C-V measurements was set to 106
Hz. The configuration of the device was the standard n-i-p architecture: Glass /FTO/ETL/
Absorber(LNMO/ENMO/DNMO) /HTL/Metal Contact.

Figure 2.2: Workflow for SCAPS-1D simulation (27)

Chapter 3: Simulation Design

The numerical study was designed to systematically explore the combined influence of transport
layers and absorber composition on device performance within a SCAPS-1D framework. For
each of the three double perovskite absorbers, La2 N iM nO6 (LNMO), Eu2 N iM nO6 (ENMO),
and Dy2 N iM nO6 (DNMO), a full combinatorial sweep was defined over electron transport layers
(ETLs) and hole transport layers (HTLs):

• 7 candidate ETLs

• 10 candidate HTLs

• 3 absorbers (LNMO, ENMO, DNMO)

This yields a total of 7×10×3=210 distinct device configurations to be evaluated in the full
optimization space.

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 Table 3.1: Parameters of Double Perovskite Absorbers, FTO, and ITO used in the simulation.
Parameter ENMO DNMO LNMO FTO ITO
Thickness (nm) 350 350 350 500 500
Bandgap (eV) 1.06 1.03 1.05 3.5 3.5
Electron Affinity (eV) 3.52 3.52 3.52 4.0 4.0
Dielectric Permittivity 9 13 3.5 9 9
Nc (cm−3 ) 1018 1018 1018 2.2 × 1018 2.2 × 1018

12
Nv (cm−3 ) 1018 1018 1018 1.8 × 1019 1.8 × 1019
ve (cm/s) 107 107 107 107 107
vh (cm/s) 107 107 107 107 107
µe (cm2 /Vs) 22 22 22 20 20
µh (cm2 /Vs) 22 22 22 10 10
ND (cm−3 ) 7 × 1016 7 × 1016 7 × 1016 1019 1021
Defect Density (cm−3 ) 1014 1014 1014 1014 1015
References (28) (28) (28)(26)(29) (28)(29)(30)(31)(32) (26)(33)
 Table 3.2: Electronic and optical parameters of Electron Transport Layers (ETLs) used in the simulation.
Parameter C60 PCBM ZnO TiO2 SnO2 WS2 ZnS
Thickness (nm) 50 50 30 30 100 100 50
Bandgap (eV) 1.7 2.0 3.3 3.2 3.6 1.8 3.6
Electron Affinity (eV) 3.9 3.9 4.1 3.9 4.0 3.95 3.9
Dielectric Permittivity 4.2 3.9 9 32 9 13.6 9
Nc (cm−3 ) 8 × 1019 2.5 × 1021 1019 1019 2.2 × 1018 1018 2.2 × 1018
Nv (cm−3 ) 8 × 1019 2.5 × 1021 1019 1019 1.8 × 1019 2.4 × 1019 1.8 × 1019

13
ve (cm/s) 107 107 107 107 107 107 107
vh (cm/s) 107 107 107 107 107 107 107
µe (cm2 /Vs) 8 × 10−2 0.2 20 20 100 100 100
µh (cm2 /Vs) 3.5 × 10−2 0.2 10 10 25 100 12.5
ND (cm−3 ) 1017 2.93 × 1017 1017 1017 1017 1018 1.1 × 1018
NA (cm−3 ) 0 0 0 0 0 0 0
Defect Density (cm−3 ) 1015 1015 1014 1014 1015 1015 1015
References (26)(29)(27) (26)(29)(27) (26)(29)(33) (31)(30)(33)(29)(28) (33) (26)(33)(27) (32)
 Table 3.3: Electronic and optical parameters of Hole Transport Layers (HTLs) used in the simulation.
Parameter CuSCN P3HT PEDOT:PSS NiO CuI CFTS Cu2 O Spiro-MeOTAD CBTS CuO
Thickness (nm) 50 50 50 100 20 100 20 150 100 50
Bandgap (eV) 3.6 1.7 1.6 3.8 3.1 2.1 2.1 2.9 1.9 2.17
Electron Affinity (eV) 1.7 3.5 3.4 1.46 2.1 3.2 3.2 2.2 3.6 3.2
Dielectric Permittivity 10 3 3 10.7 6.5 9 7.1 3 5.4 7.11

14
Nc (cm−3 ) 2.2 × 1019 2 × 1021 2.2 × 1018 2.8 × 1019 2.2 × 1018 2.2 × 1018 2.0 × 1017 2.2 × 1018 2.2 × 1018 2.02 × 1017
Nv (cm−3 ) 1.8 × 1019 2 × 1021 1.8 × 1018 1019 1.8 × 1019 1.8 × 1019 1019 1.8 × 1019 1.8 × 1018 1.1 × 1019
µe (cm2 /Vs) 10−3 1.8 × 10−2 4.5 × 10−2 12 100 21.98 20 10−4 30 10
µh (cm2 /Vs) 25.6 × 10−2 1.8 × 10−2 4.5 × 10−2 2.8 43.9 21.98 80 10−4 10 0.1
NA (cm−3 ) 1018 1018 1018 1018 1018 1018 1018 1018 1018 1018
Defect Density (cm−3 ) 1015 1015 1015 1015 1014 1015 1015 1015 1015 1015
References (26)(31)(32) (26) (26) (26) (32)(31)(25)(29)(28) (26)(27) (32)(31) (31)(30)(34) (33) (32)
3.1 Baseline Reproduction and Model Validation
The initial step in validating the simulation environment was to duplicate the prototype de-
vice from Kumar et al. (28), which consists of the F T O/T iO2 /X/CuI/Au (where X =
LN M O, DN M O, EN M O) structure. The exact structure number, layer thicknesses and mate-
rial characteristics (band energy level gaps, electron affinities, density of defects, mobility, and
doping) were obtained from the reference study and associated supplementary data. The goal
of this step was to confirm the numerical implementation by demonstrating that the simulated
values of power conversion efficiency (PCE), short-circuit current density (JSC ), open circuit
voltage (VOC ), and fill factor (FF) were comparable to those reported by Kumar et al. (28).

Figure 3.1: (a) Device configuration of simulated PSCs of Kumar et al. (b) Energy-band
diagram of baseline reproduction simulation. (28)

Table 3.4: Comparison of photovoltaic parameters between reference literature (Manish et al.,
2021) and computed SCAPS-1D simulation results for LNMO, DNMO, and ENMO absorbers.
LNMO DNMO ENMO

Parameter Units Manish et al. Computed Manish et al. Computed Manish et al. Computed
2
JSC mA/cm 1.89 1.97 0.33 0.27 1.12 1.17
VOC V 0.208 0.188 0.174 0.205 0.185 0.207
FF % 49.27 48.35 49.70 50.71 49.04 49.77
PCE % 0.17 0.20 0.028 0.03 0.10 0.14

3.2 Optimization Strategy

To avoid an exhaustive 210-point sweep, a staged optimization protocol was adopted.

15
Phase 1: HTL Screening at Fixed ETL
During the first part of the experiment, we fixed one type of ETL material (T iO2 ) and kept the
LNMO as our photoactive layer or active region. Next, we tested different types of materials to
serve as our HTLs with all other variables being equal. For each type of our 10 HTL candidates:

• Fixed: Absorber = LNMO; ETL = T iO2

• Variable: HTL (10 candidates)

Steady-state J-V characteristics under AM1.5G illumination were computed and we selected the
configuration having the highest PCE as the champion HTL, with 10 total simulations performed
in this first phase.

Phase 2: ETL Screening at Fixed HTL

After identifying champion HTL, this material was fixed while the ETL set was systematically
screened. T iO2 was the reference material for the ETLs and has already been evaluated in Phase
1, leaving six ETLs to be simulated in combination with LNMO and champion HTL remaining:

• Fixed: Absorber = LNMO; HTL = Champion HTL

• Variable: ETL (6 candidates, excluding the T iO2 baseline)

Each configuration’s PCE, JSC , VOC , and FF were evaluated. The ETL that produced the high-
est PCE was identified in combination with champion HTL; therefore, the ETL/HTL/absorber
stack for the ETL that produced the highest PCE with champion HTL was established as the
optimal device configuration for LNMO and claimed as champion ETL/HTL. Therefore, this
phase required six simulations.

Phase 3: Transferability to Other Absorbers

In order to evaluate whether the optimal ETL/HTL pair for LNMO can also be utilized for
the other two double perovskites ENMO and DNMO, the champion ETL/HTL combinations
obtained from the previous study of LNMO were directly replicated on ENMO and DNMO. Two
simulations were performed:

• Champion ETL/HTL + ENMO

• Champion ETL/HTL + DNMO

This stage evaluates the robustness of the optimization approach against absorber replacements
and besides checking if there is still a performance increase on LNMO when changing the rare
earth cation. Overall, this hierarchical technique decreased the practical amount of optimizations
to complete; looking through and analyzing 210 theoretical configurations before arriving at just
1 (validation) + 10 (HTL tests) + 6 (ETL tests) + 2 (transferability tests) = 19 targeted
simulations; while still sampling the most relevant region of the design space.

3.2.1 Rationale for Sequential Optimization Across Absorbers

In general, changing the absorber layer in a heterojunction device can strongly perturb the
band alignment at both ETL/absorber and absorber/HTL interfaces, since the conduction band

16
minimum (CBM) and valence band maximum (VBM) positions depend on band gap and elec-
tron affinity (or ionization potential). Under such circumstances, an ETL that is optimal for
one absorber may introduce an energetic spike or cliff for another, degrading charge extraction
or enhancing interfacial recombination. For the present material set, however, the underlying
energy-level landscape justifies the use of a sequential, absorber-agnostic optimization strategy
(35)(36).
In the set of parameters used for the three absorbers, the electron affinity (which determines
the conduction band minimum (CBM) in reference to the vacuum) is the same for all three. The
values are ENMO: 3.52 eV, DNMO: 3.52 eV, and LNMO: 3.52 eV. Because the CBM determines
the energy levels of the junction at ETL/absorber, this means that all three absorbers have the
same conduction band offset when placed against a given ETL (35). Although the band gaps
of the absorbers are slightly different — ENMO has a gap of 1.06 eV, DNMO has a gap of 1.03
eV, and LNMO has a gap of 1.05 eV — these small differences in band gap will result in only
a small difference in the valence band maxima (VBM) of the absorbers, provided the CBM is
equal (as determined by the common electron affinity). As a result, the relative alignments of the
three absorbers when placed against a given hole transport layer (HTL) will also be very similar.
Thus, LNMO, ENMO, and DNMO are electronically ”near-degenerate twins” in the context of
the initial simulation phase, and a transport-layer stack optimized for LNMO is expected to
remain close to optimal for ENMO and DNMO as well (35).

3.2.2 Justification for Separating ETL and HTL Optimization

When performing sequential optimization, one of the possible issues is that there are likely to be
significant interactions between ETLs and HTLs so that optimizing them separately may lead
to missing significant interactions between them. The current strategy is still valid due to three
primary reasons:

(i) ”Sandwich” principle and physical separation

In the models of perovskite-based solar cells, it has been observed that for thicknesses of be-
tween 300 and 500 nm corresponding to experimentally observed thickness and models of oxide
double perovskites and hybrid perovskites, the ETLs and HTLs are physically spaced by a bulk
absorber layer at all times between them, therefore, the local electrostatics at each interface are
predominantly determined by the adjoining two layers:

• An ETL interacts with the conduction band of an absorber (via a conduction band coupling
during operation).

• An HTL interacts with the valence band of an absorber (via a valence band coupling during
operation).

As a result, the ETL interacts only with the ETL/absorber interface while the HTL interacts only
with the absorber/HTL interface. Hence, if any HTL provides a poor valence-band alignment
(e.g., excessive barrier for hole extraction or a deep recombination-active cliff) then all devices
with this fault will perform poorly irrespective of which type of ETL is placed on the HTL side
(36)(37).

(ii) Locality of band alignment

Band alignment is an intrinsically local interfacial property.

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 • At the ETL/absorber interface, the performance at this interface is primarily affected by
the conduction band offset, which is determined by the electron affinity difference of the
ETL and the absorber.

• At the absorber/HTL interface, the performance at this interface is primarily affected

by the valence band offset, which is related to the ionization potential difference of the
absorber and the HTL.

Because the two interfaces are physically separated by a comparatively thick absorber layer,
optimization of the ETL/absorber interface for favourable conduction-band alignment does not
alter the optimization of the absorber/HTL interface’s valence-band alignment, and vice versa.
This locality supports the validity of independently screening HTLs at fixed ETL and then
screening ETLs at fixed HTL (35).

(iii) Consistency with established SCAPS methodology

In SCAPS-1D modelling of perovskite, researchers typically fix a widely used transport layer
(such as T iO2 as ETL) while screening several HTLs and then revisit the ETL once an ideal
HTL is found. This sequential optimization protocol is in line with standard practice. Similar to
this work, the reference double perovskite study optimizes absorber parameters first and states
clearly that ETL, HTL, and defect properties can be tuned later to achieve further improvements
(28).

3.2.3 Limits of the Decoupling Approximation

Although ETL and HTL can be considered effectively decoupled in this study, their interaction
becomes non-negligible in certain well-defined regimes:

(i) Optical interference effects

The changes in ETL thickness (or) ETL refractive index that cause the internal optical interfer-
ence patterns to be modified change the spatial generation profile and the portion of incoming
light incident on the back side of the absorber and HTL. Although, for adjustments of nanometer
scale, these effects may be minimal; however, for ultra-thin or highly reflective stacks they may
have a considerable impact (38).

(ii) Ultra-thin absorber regime

When the thickness of an absorber is lowered to the fully depleted regime (¡ 100 nm for typical
perovskites), the space-charge region formed at the interface of ETL/absorber and absorber/HTL
interfaces can overlap, causing the internal electric field which is influenced simultaneously by
both contacts. This creates a situation where the ETL & HTL cannot be optimized indepen-
dently from one another, thus they must both be considered when optimizing a perovskite PV. In
the present work, however, the thickness of the absorber (≈ 350 nm in the reproduced structure)
is chosen large enough for it to not be impacted by either one of the contacts alone, allowing for
an independent optimization strategy (37)(39).
The sequential optimization of ETL and HTL is thus both physically justified and numerically
efficient under the thickness and parameter ranges taken into consideration, and it is completely
consistent with documented best practices in SCAPS-based device modelling.

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