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@PHDTHESIS{Krckemeier:1044223,
author = {Krückemeier, Lisa},
title = {{Q}uantifying {R}ecombination {L}osses and {C}harge
{E}xtraction in {H}alide {P}erovskite {S}olar {C}ells},
volume = {669},
school = {RWTH Aachen University},
type = {Dissertation},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {FZJ-2025-03112},
isbn = {978-3-95806-835-3},
series = {Schriften des Forschungszentrums Jülich Reihe Energie $\&$
Umwelt / Energy $\&$ Environment},
pages = {vi, 286},
year = {2025},
note = {Dissertation, RWTH Aachen University, 2025},
abstract = {Due to their exceptional properties, halide perovskite
materials have emerged as promising candidates for efficient
and cost-effective photovoltaics, with some devices
approaching the performance of silicon solar cells after a
decade of research. Despite their remarkable progress,
perovskite solar cells suffer from several loss mechanisms
that limit their efficiency. However, the rapid development
of perovskite research has outpaced advances in analyzing
characterization techniques tailored to the unique
properties of this material class. Thus, understanding and
quantifying the losses within these devices remains
difficult, especially in terms of recombination losses and
charge-extraction dynamics. This work aims to bridge this
gap by proposing innovative approaches and providing tools
for analyzing charge-carrier dynamics, which will help
correctly interpret and quantify experimental data for
perovskite solar cells. The overarching motivation is to
contribute to the advancement of perovskite solar cell
technology by gaining a deeper understanding of fundamental
processes. Transient photoluminescence (TPL) and transient
photovoltage (TPV) are popular techniques for monitoring
charge-carrier dynamics and investigating recombination
losses in perovskites. However, the low doping density of
lead-halide perovskites often places the device in
high-level injection during these measurements, leading to
non-linear relationships between the recombination rates and
carrier densities. This behavior leads to challenges in the
use of a scalar charge-carrier lifetime as a figure of merit
to quantify recombination. Furthermore, the interpretation
of data from complete solar cells or multilayer samples is
highly challenging due to the superposition of various
effects that modulate the charge-carrier concentration.
These effects include bulk and interfacial recombination,
charge transfer and extraction, and capacitive charging or
discharging. While theoretical work on TPL decays in full
solar-cell devices has been published for other photovoltaic
technologies, a comprehensive theory dealing with the
specific situation in halide-perovskite devices is currently
missing. In this work, improved spectroscopic techniques
with a high dynamic range of data acquisition are combined
with time-dependent, numerical simulations with Sentaurus
TCAD to break down the complex behavior of charge-carrier
dynamics in perovskite solar cells. The dissertation
contributes to the field by proposing new methods and
analytical models for data analysis of perovskite solar
cells. One major contribution involves a comprehensive
analysis of transient photoluminescence and transient
photovoltage decays, considering non-linear dependencies of
the recombination rate on charge-carrier density. This
multi-method quantitative data analysis of transient
photoluminescence and transient photovoltage decays goes
beyond traditional mono-exponential fitting methods,
introducing an approach to derive differential decay times
as a function of charge-carrier density and quasi-Fermi
level splitting. Time-dependent, numerical drift-diffusion
simulations of various sample structures, including
perovskite films, multilayer systems, and complete devices,
provide visualization and explanation of the injection
dependence of the decay time and allow distinguishing
between different carrier-density-dependent regimes.
Building upon these insights, analytical equations are
developed that serve as good approximations to the simulated
and experimental decay-time functions. These analytical
equations facilitate data analysis and the extraction of key
material parameters, like trapassisted Shockley-Read-Hall
recombination coefficients, by removing the need to do
extensive numerical simulations. The analytical approach is
further expanded to include the extraction of charge
carriers by the interlayers and contacts, in addition to
recombination. A twocomponent model for small-signal
measurements is developed that is based on the analytical
solution of coupled linear differential equations via the
determination of eigenvalues. The model describes the
transient behaviour of chemical and electrical potentials
and allows us to connect the rise and decay times in
small-signal transientphotovoltage experiments to
recombination, extraction, and capacitive charging and
discharging effects, providing quantitative values for
recombination and extractiontime constants as a function of
voltage. Another part of this work is the development of a
standardized framework for reporting voltage loss in
perovskite solar cells, addressing the impact of perovskite
composition changes on the limiting open-circuit voltage,
and proposing a consistent reference. This approach,
approximating the radiative limit, requires only a single
measurement of the external quantum efficiency for its
calculation, and is therefore fast and easy to apply. The
study compares different band gap definitions used in the
literature, revealing a substantial impact on the ranking of
the voltage losses. The proposal of referencing open-circuit
voltages to the radiative limit enables a meta-analysis of
previously published perovskite solar cells. In addition, I
present inverted, planar MAPI solar cells with open-circuit
voltages exceeding 1.26V. The combination of dry lead
acetate and lead chloride precursors, along with optimized
hole and electron transport layers, suppresses both bulk and
surface recombination, which is confirmed by an
exceptionally high photoluminescence external quantum
efficiency exceeding $5\%$ in complete cells. These solar
cells serve as the basis for subsequent investigations of
device physics and characterization techniques. These
scientific contributions significantly expand the
state-of-the-art by offering innovative methodologies for
characterizing halide perovskite solar cells. The proposed
frameworks and analytical approaches not only fill existing
gaps in understanding the implications of unconventional
material properties, but also pave the way for more accurate
and comprehensive analysis in future perovskite research.},
cin = {IMD-3},
cid = {I:(DE-Juel1)IMD-3-20101013},
pnm = {1215 - Simulations, Theory, Optics, and Analytics (STOA)
(POF4-121)},
pid = {G:(DE-HGF)POF4-1215},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)11},
urn = {urn:nbn:de:0001-2509261220158.637798969945},
doi = {10.34734/FZJ-2025-03112},
url = {https://juser.fz-juelich.de/record/1044223},
}