arXiv subjects

Uwe Rau

Publications and source records attributed to Uwe Rau.

16 recordsLinked to original sources

arXiv2026

Revealing the Role of Confined Molecular H$_2$ in the Passivation of Defective Silicon Using First-Principles Simulations

The passivation of silicon dangling bonds by hydrogen is a crucial requirement for silicon-based optoelectronic technology, especially for solar cells. Recent experiments on intense light soaking of silicon heterojunction solar cells unveiled interesting dynamical aspects of hydrogen passivation that are linked to Si-H bond breaking and repassivation. These processes take place predominantly in porous regions near the amorphous/crystalline interface, where hydrogen can exist in molecular form. This work addresses the question of whether molecular H$_2$ directly participates in Si-H depassivation and repassivation. Using density functional theory, we calculate and compare formation energies of point defects, multivacancy cavities and the Si(100) surface to identify relevant passivated and depassivated states. Furthermore, we employ nudged elastic band calculations to determine the activation barriers of the corresponding pathways. We find that sufficient local free volume enables a direct double-H pathway for depassivation through the formation of confined molecular H$_2$. Despite involving the breaking of two Si-H bonds, the double-H process can be energetically and kinetically competitive with the single-H process and can exhibit a reverse repassivation barrier as low as $0.15\,$eV under p-type conditions. These findings provide a plausible atomistic explanation for passivation recovery during light soaking and illuminated annealing in porous regions near amorphous/crystalline silicon interfaces.

cond-mat.mtrl-sci↗

arXiv2024

Deriving mobility-lifetime products in halide perovskite films from spectrally- and time-resolved photoluminescence

Lead-halide perovskites are semiconductor materials with attractive properties for photovoltaic and other optoelectronic applications. However, determining crucial electronic material parameters, such as charge-carrier mobility and lifetime, is plagued by a wide range of reported values and inconsistencies caused by interpreting and reporting data originating from different measurement techniques. In this paper, we propose a method for the simultaneous determination of mobility and lifetime using only one technique: transient photoluminescence spectroscopy. By measuring and simulating the decay of the photoluminescence intensity and the redshift of the photoluminescence peak as a function of time after the laser pulse, we extract the mobility, lifetime, and diffusion length of halide perovskite films. With a voltage-dependent steady-state photoluminescence measurement on a cell, we relate the diffusion length to the external voltage and quantify its value at the maximum power point.

cond-mat.mtrl-sci↗

arXiv2023

How Charge Carrier Exchange between Absorber and Contact influences Time Constants in the Frequency Domain Response of Perovskite Solar Cells

A model is derived for the frequency- and time-domain opto-electronic response of perovskite solar cells (PSCs) that emphasizes the role of charge carrier exchange, .i.e. extraction and injection, from (to) the perovskite through the transport layer to (from) the collecting electrode. This process is described by a charge carrier exchange velocity that depends on the mobility and electric field inside the transport layer. The losses implied by this process are modelled in an equivalent circuit model in the form of a voltage-dependent transport layer resistance. The analysis of the model predicts that the voltage dependence of the measured time constants allows discriminating situations where the transport layer properties dominate the experimental response. Application of this method to experimental impedance spectroscopy data identifies charge extraction velocities between 1-100 cm/s at 1 sun open-circuit conditions for p-i-n PSCs with PTAA as the hole transport layer, that corresponds to transport layer mobilities between 10^-4 - 3 x 10^-3 cm^2V^-1s^-1. The model paves the way for accurate estimation of photocurrent and fill factor losses in PSCs caused by the low mobilities in the transport layers, using small perturbation measurements in the time and frequency domain.

cond-mat.mtrl-sci↗

arXiv2023

Characterizing the Influence of Charge Extraction Layers on the Performance of Triple-Cation Perovskite Solar Cells

Selecting suitable charge transport layers and suppressing non-radiative recombination at interfaces to the absorber layer are vital to maximize the efficiency of halide perovskite solar cells. In this work, high-quality perovskite thin films and devices are fabricated with different fullerene-based electron transport layers and different self-assembled monolayers as hole transport layers. We then perform a comparative study of a significant variety of different electrical, optical and photoemission-based characterization techniques to quantify the properties of the solar cells, the individual layers and importantly the interfaces between them. In addition, we highlight the limitations and problems of the different measurements, the insights gained by combining different methods and the different strategies to extract information from the experimental raw data.

cond-mat.mtrl-sci↗

arXiv2023

Quantifying Charge Extraction and Recombination Using the Rise and Decay of the Transient Photovoltage of Perovskite Solar Cells

The extraction of photogenerated charge carriers and the generation of a photovoltage belong to the fundamental functionalities of any solar cell. These processes happen not instantaneously but rather come with finite time constants, e.g., a time constant related to the rise of the externally measured open circuit voltage following a short light pulse. The present paper provides a new method to analyze transient photovoltage measurements at different bias light intensities combining rise and decay times of the photovoltage. The approach uses a linearized version of a system of two coupled differential equations that is solved analytically be determining the eigenvalues of a 2 x 2 matrix. By comparison between the eigenvalues and the measured rise and decay times during a transient photovoltage measurement, we determine the rates of carrier recombination and extraction as a function of bias voltage and establish a simple link between their ratio and the efficiency losses in the perovskite solar cell.

cond-mat.mtrl-sci↗

arXiv2022

Fill Factor Losses and Deviations from the Superposition Principle in Lead-Halide Perovskite Solar Cells

The enhancement of the fill factor in the current generation of perovskite solar cells is the key for further efficiency improvement. Thus, methods to quantify the fill factor losses are urgently needed. A classical method to quantify Ohmic and non-Ohmic resistive losses in solar cells is based on the comparison between the voltage in the dark and under illumination analysed at equal recombination current density. Applied to perovskite solar cells, we observe a combination of an Ohmic series resistance with a voltage-dependent resistance that is most prominent at short circuit and low forward bias. The latter is most likely caused by the poor transport properties of the electron and/or hole transport layers. By measuring the photoluminescence of perovskite solar cells as a function of applied voltage, we provide direct evidence for a high quasi-Fermi level splitting at low and moderate forward bias that substantially exceeds the externally applied voltage. This quasi-Fermi level splitting causes recombination losses and, thus, reduces both the short-circuit current and the fill factor of the solar cell.

physics.app-ph↗

arXiv2021

Multilayer Capacitances: How Selective Contacts Affect Capacitance Measurements of Perovskite Solar Cells

Capacitance measurements as a function of voltage, frequency and temperature are useful tools to identify fundamental parameters that affect solar cell operation. Techniques such as capacitance-voltage (CV), Mott-Schottky analysis and thermal admittance spectroscopy (TAS) measurements are therefore frequently employed to obtain relevant parameters of the perovskite absorber layer in perovskite solar cells. However, state-of-the-art perovskite solar cells employ thin electron and hole transport layers that improve contact selectivity. These selective contacts are often quite resistive in nature, which implies that their capacitances will contribute to the total capacitance and thereby affect the extraction of the capacitance of the perovskite layer. Based on this premise, we develop a simple multilayer model that considers the perovskite solar cell as a series connection of the geometric capacitance of each layer in parallel with their voltage-dependent resistances. Analysis of this model yields fundamental limits to the resolution of spatial doping profiles and minimum values of doping/trap densities, built-in voltages and activation energies. We observe that most of the experimental capacitance-voltage-frequency-temperature data, calculated doping/trap densities and activation energies reported in literature are within these cut-off values derived, indicating that the capacitance response of the perovskite solar cell is indeed strongly affected by the capacitance of its selective contacts.

physics.app-ph↗

arXiv2021

Effect of doping, photodoping and bandgap variation on the performance of perovskite solar cells

Most traditional semiconductor materials are based on the control of doping densities to create junctions and thereby functional and efficient electronic and optoelectronic devices. The technology development for halide perovskites had initially only rarely made use of the concept of electronic doping of the perovskite layer and instead employed a variety of different contact materials to create functionality. Only recently, intentional, or unintentional doping of the perovskite layer is more frequently invoked as an important factor explaining differences in photovoltaic or optoelectronic performance in certain devices. Here we use numerical simulations to study the influence of doping and photodoping on photoluminescence quantum yield as well as other device relevant metrics. We find that doping can improve the photoluminescence quantum yield by making radiative recombination faster. This effect can benefit or harm photovoltaic performance given that the improvement of photoluminescence quantum efficiency and open-circuit voltage is accompanied by a reduction of the diffusion length. This reduction will eventually lead to inefficient carrier collection at high doping densities. The photovoltaic performance might improve at an optimum doping density which depends on a range of factors such as the mobilities of the different layers and the ratio of the capture cross sections for electrons and holes.

cond-mat.mtrl-sci↗

arXiv2021

Understanding Transient Photoluminescence in Halide Perovskite Layer Stacks and Solar Cells

While transient photoluminescence measurements are a very popular tool to monitor the charge-carrier dynamics in the field of halide perovskite photovoltaics, interpretation of data obtained on multilayer samples is highly challenging due to the superposition of various effects that modulate the charge-carrier concentration in the perovskite layer and thereby the measured PL. These effects include bulk and interfacial recombination, charge transfer to electron or hole transport layers and capacitive charging or discharging. Here, numerical simulations with Sentauraus TCAD, analytical solutions and experimental data with a dynamic range of ~7 orders of magnitude on a variety of different sample geometries from perovskite films on glass to full devices are combined to present an improved understanding of this method. A presentation of the decay time of the TPL decay that follows from taking the derivative of the photoluminescence at every time is proposed. Plotting this decay time as a function of the time-dependent quasi-Fermi level splitting enables distinguishing between the different contributions of radiative and non-radiative recombination as well as charge extraction and capacitive effects to the decay.

cond-mat.mtrl-sci↗

arXiv2021

Interface Optimization via Fullerene Blends Enables Open-Circuit Voltages of 1.35 V in CH3NH3Pb(I0.8Br0.2)3 Solar Cells

Non-radiative recombination processes are the biggest hindrance to approaching the radiative limit of the open-circuit voltage for wide-band gap perovskite solar cells. In addition, to high bulk quality, good interfaces and good energy level alignment for majority carriers at charge transport layer-absorber interfaces are crucial to minimize non-radiative recombination pathways. By tuning the lowest-unoccupied molecular-orbital of electron transport layers via the use of different fullerenes and fullerene blends, we demonstrate open-circuit voltages exceeding 1.35 V in CH3NH3Pb(I0.8Br0.2)3 device. Further optimization of mobility in binary fullerenes electron transport layer can boost the power conversion efficiency as high as 18.6%. We note in particular that the Voc-fill factor product is > 1.085 V, which is the highest value reported for halide perovskites with this band gap.

cond-mat.mtrl-sci↗

arXiv2020

Defect tolerant device geometries

The term defect tolerance is widely used in literature to describe materials such as lead-halides which exhibit long non-radiative lifetimes of carriers despite possessing a large concentration of point defects. Studies on defect tolerance of materials mostly look at the properties of the host material and/or the chemical nature of defects that affect the capture coefficients of defects. However, the recombination activity of a defect is not only a function of its capture coefficients alone but are also dependent on the electrostatics and the design of the layer stack of a photovoltaic device. Here we study the influence of device geometry on defect tolerance by combining calculations of capture coefficients with device simulations. We derive generic device design principles which can inhibit recombination inside a photovoltaic device for a given set of capture coefficients based on the idea of slowing down the slower of the two processes (electron and hole capture) even further by modifying electron and hole injection into the absorber layer. We use the material parameters and typical p-i-n device geometry representing methylammonium lead halide perovskites solar cells to illustrate the application of our generic design principles to improve specific devices .

cond-mat.mtrl-sci↗

arXiv2019

A highly integrated, stand-alone photoelectrochemical device for large-scale solar hydrogen production

Although photoelectrochemical water splitting is likely to be an important and powerful tool to provide environmentally friendly hydrogen, most developments in this field have been conducted on a laboratory scale so far. In order for the technology to make a sizeable impact on the energy transition, scaled up devices made of inexpensive and earth abundant materials must be developed. In this work, we demonstrate a scalable (64 cm2 aperture area) artificial photoelectrochemical device composed of triple-junction thin-film silicon solar cells in conjunction with an electrodeposited bifunctional nickel iron molybdenum water splitting catalyst. Our device shows a solar to hydrogen efficiency of up to 4.67% (5.33% active area) without bias assistance and wire connection. Furthermore, gas separation was enabled by incorporating a membrane in a 3D printed device frame.

physics.app-ph↗

arXiv2019

Solar Energy Conversion and the Shockley-Queisser Model, a Guide for the Perplexed

The Shockley-Queisser model is a landmark in photovoltaic device analysis by defining an ideal situation as reference for actual solar cells. However, the model and its implications are easily misunderstood. Thus, we present a guide to help understand and avoid misinterpreting it. Focusing on the five assumptions, underlying the model, we define figures of merit to quantify how close real solar cells approach each of these assumptions.

physics.app-ph↗

arXiv2018

Impact of Small Phonon Energies on the Charge-Carrier Lifetimes in Metal-Halide Perovskites

Solar cells based on metal-halide perovskite absorber layers have resulted in outstanding photovoltaic devices with long non-radiative lifetimes as a crucial feature enabling high efficiencies. Long non-radiative lifetimes occur if the transfer of the energy of the electron-hole pair into vibrational energy is slow, due to, e.g., a low density of defects, weak electron phonon coupling or the release of a large number of phonons needed for a single transition. Here, we discuss the implications of the known material properties of metal-halide perovskites (such as permittivities, phonon energies and effective masses) and combine those with basic models for electron-phonon coupling and multiphonon-transition rates in polar semiconductors. We find that the low phonon energies of MAPbI$_3$ lead to a strong dependence of recombination rates on trap position, which can be readily deduced from the underlying physical effects determining non-radiative transitions. Here, we show that this is important for the non-radiative recombination dynamics of metal-halide perovskites, as it implies that these systems are rather insensitive to defects that are not at midgap energy. This can lead to long lifetimes, which indicates that the low phonon energies are likely an important factor for the high performance of optoelectronic devices with metal halide perovskites.

cond-mat.mtrl-sci↗

arXiv2017

A Microscopic Perspective on Photovoltaic Reciprocity in Ultrathin Solar Cells

The photovoltaic reciprocity theory relates the electroluminescence spectrum of a solar cell under applied bias to the external photovoltaic quantum efficiency of the device as measured at short circuit conditions. Its derivation is based on detailed balance relations between local absorption and emission rates in optically isotropic media with non-degenerate quasi-equilibrium carrier distributions. In many cases, the dependence of density and spatial variation of electronic and optical device states on the point of operation is modest and the reciprocity relation holds. In nanostructure-based photovoltaic devices exploiting confined modes, however, the underlying assumptions are no longer justifiable. In the case of ultrathin absorber solar cells, the modification of the electronic structure with applied bias is significant due to the large variation of the built-in field. Straightforward use of the external quantum efficiency as measured at short circuit conditions in the photovoltaic reciprocity theory thus fails to reproduce the electroluminescence spectrum at large forward bias voltage. This failure is demonstrated here by numerical simulation of both spectral quantities at normal incidence and emission for an ultrathin GaAs p-i-n solar cell using an advanced quantum kinetic formalism based on non-equilibrium Green's functions of coupled photons and charge carriers. While coinciding with the semiclassical relations under the conditions of their validity, the theory provides a consistent microscopic relationship between absorption, emission and charge carrier transport in photovoltaic devices at arbitrary operating conditions and for any shape of optical and electronic density of states.

cond-mat.mes-hall↗

arXiv2016

From leaf to tree: upscaling of artificial photosynthesis

Energy storage becomes crucial for energy systems with an increasing share of renewable energy sources. Artificial photosynthesis, in particular photovoltaic water splitting, provides both sustainable energy generation and energy storage in the form of hydrogen. However, only a few concepts for scalable devices were reported in the literature. Here, we introduce a new concept which, by design, is scalable and compatible with every thin-film photovoltaic technology. The concept allows for independent geometrical optimization of the photovoltaic and the electrochemical part. The scalability is achieved by continuous mirroring of a base unit. We demonstrate a fully integrated, wireless device with a stable and bias-free operation for 40 hours. The concept was scaled to an area of 64 cm2 comprising 13 base units and exhibited a solar-to-hydrogen efficiency of 3.9%. The concept and its successful realization is an important contribution towards the large scale application of artificial photosynthesis.

cond-mat.mtrl-sci↗