arXiv subjects

Thomas Kirchartz

Publications and source records attributed to Thomas Kirchartz.

34 records · Page 2Linked to original sources

arXiv2022

Interpretation of Mott-Schottky Plots of Photoanodes for Water Splitting

A large body of literature reports that both bismuth vanadate and haematite photoanodes are semiconductors with an extremely high doping density between 10^18-10^21 cm^-3. Such values are obtained from Mott-Schottky plots by assuming that the measured capacitance is dominated by the capacitance of the depletion layer formed by the doping density within the photoanode. In this work, we show that such an assumption is erroneous in many cases because the injection of electrons from the collecting contact creates a ubiquitous capacitance step that is very difficult to distinguish from that of the depletion layer. Based on this reasoning, we derive an analytical resolution limit that is independent of the assumed active area and surface roughness of the photoanode, below which doping densities cannot be measured in a capacitance measurement. We find that the reported doping densities in literature lie very close to this value and therefore conclude that there is no credible evidence from capacitance measurements that confirms that bismuth vanadate and haematite photoanodes contain high doping densities.

cond-mat.mtrl-sci↗

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

Pathways towards 30% efficient single-junction perovskite solar cells and the role of mobile ions

Perovskite semiconductors have demonstrated outstanding external luminescence quantum yields, enabling high power conversion efficiencies (PCE). However, the precise conditions to advance to an efficiency regime above monocrystalline silicon cells are not well understood. Here, we establish a simulation model that well describes efficient p-i-n type perovskite solar cells and a range of different experiments. We then study important device and material parameters and we find that an efficiency regime of 30% can be unlocked by optimizing the built-in potential across the perovskite layer by using either highly doped (10^19 cm-3), thick transport layers (TLs) or ultrathin undoped TLs, e.g. self-assembled monolayers. Importantly, we only consider parameters that have been already demonstrated in recent literature, that is a bulk lifetime of 10 us, interfacial recombination velocities of 10 cm/s, a perovskite bandgap of 1.5 eV and an EQE of 95%. A maximum efficiency of 31% is predicted for a bandgap of 1.4 eV. Finally, we demonstrate that the relatively high mobile ion density does not represent a significant barrier to reach this efficiency regime. Thus, the results of this paper promise continuous PCE improvements until perovskites may become the most efficient single-junction solar cell technology in the near future.

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

Comment on "Resolving spatial and energetic distributions of trap states in metal halide perovskite solar cells"

Ni et al. report minimum bulk trap densities of 10^11 cm-3 and 1-4 orders change in interfacial trap densities derived from drive-level capacitance profiling of lead halide perovskites. From basic electrostatic arguments, we show that such bulk trap densities cannot be resolved for a p-i-n perovskite solar cell for the reported layer thicknesses, while the apparent interfacial charge densities are a consequence of the geometrical capacitance and of charge injection into the perovskite layer.

physics.app-ph↗

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

Pitfalls and prospects of optical spectroscopy to characterize perovskite-transport layer interfaces

Perovskite photovoltaics has witnessed an unprecedented increase in power conversion efficiency over the last decade. The choice of transport layers, through which photo-generated electrons and holes are transported to the electrodes, is a crucial factor for further improving both the device performance and stability. In this perspective, we critically examine the application of optical spectroscopy to characterize the quality of the transport layer-perovskite interface. We highlight the power of complementary studies that use both continuous wave (cw) and time-resolved photoluminescence (PL) to understand non-radiative losses, and additional transient spectroscopies for characterizing the potential for loss-less carrier extraction at the solar cell interfaces. Based on this discussion, we make recommendations on how to extrapolate results from optical measurements to assess the quality of a transport layer, and its impact on solar cell efficiency.

physics.app-ph↗

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

Requirements for functional pn-homojunctions in lead-halide perovskite solar cells

Cui et al. describe the fabrication and characterization of planar pn-junction solar cells based on lead-halide perovskites. The doping densities measured using Hall effect measurements vary from $N_D = 10^{12} cm^{-3}$ to $8\times 10^{12} cm^{-3}$ for the solution-processed n-type layer and $N_A = 8\times 10^9 cm^{-3}$ for the evaporated p-type layer. While these devices outperform their counterparts, that are supposedly un-doped, the results raise three important questions: (i) Are the reported doping densities high enough to change the electrostatic potential distribution in the device from that for the un-doped ones, (ii) are the doping densities high enough for the pn-junction to remain intact under typical photovoltaic operation conditions and (iii) is a pn-junction beneficial for photovoltaic performance given the typical properties of lead-halide perovskites.

physics.app-ph↗

arXiv2019

Type and Degree of Covalence: Empirical Derivation and Implications

The way atoms attach to each other defines the function(s), e.g., mechanical, optical, electronic, of a given material. The nature of the chemical bond is, therefore, one of the most fundamental issues in materials. Both ionic interactions, i.e., resulting from electrical charges associated with the atoms, and covalent ones, i.e., the sharing of electrons between nuclei of different atoms, are usually viewed as forces that attract between atoms to form a rigid structure. Although less common for solid materials, it was shown theoretically to be possible for covalent interactions at the chemically-active electronic shell (or valence-band maximum) of semiconductors to reverse their more common nature and become repulsive, i.e., act against bonding. Some semiconductors with such predicted anti-bonding valence-band maximum levels (such as halide perovskites) show experimentally some amazing (opto-) electronic properties. Predictions that anti-bonding character can allow tolerance for existing defects, at least in part, can explain the superior properties of such semiconductors. Although there are known experimental ways to estimate the degree of the covalent nature (e.g., electronegativity), this was not possible hitherto for the type, i.e., distinguishing whether a material exhibits bonding or anti-bonding covalent interactions. We have developed a simple way to reveal the complete nature (both type and degree) of chemical bonds, using experimental data. After confirming our development with classical models and theoretical predictions, with a set of ~40 different functional semi-conductors, we show how knowledge of the complete nature of covalent bonding is of critical importance for fundamental properties of semiconductors.

cond-mat.mtrl-sci↗

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↗

arXiv2019

High Open-Circuit Voltages in Lead-Halide Perovskite Solar Cells - Experiment, Theory and Open Questions

One of the most significant features of lead-halide perovskites are their ability to have comparably slow recombination despite the fact that these materials are mostly processed from solution at room temperature. The slow recombination allows achieving high open-circuit voltages when the lead-halide perovskite layers are used in solar cells. This perspective discusses the state of the art of our understanding and of experimental data with regard to recombination and open-circuit voltages in lead-halide perovskites. A special focus is put onto open questions that the community has to tackle to design future photovoltaic and optoelectronic devices based on lead-halide perovskites and other semiconductors with similar properties.

physics.app-ph↗

arXiv2018

The perovskite/transport layer interfaces dominate non-radiative recombination in efficient perovskite solar cells

Charge transport layers (CTLs) are key components of diffusion controlled perovskite solar cells, however, they can induce additional non-radiative recombination pathways which limit the open circuit voltage (V_OC) of the cell. In order to realize the full thermodynamic potential of the perovskite absorber, both the electron and hole transport layer (ETL/HTL) need to be as selective as possible. By measuring the quasi-Fermi level splitting (QFLS) of perovskite/CTL heterojunctions, we quantify the non-radiative interfacial recombination current for a wide range of commonly used CTLs, including various hole-transporting polymers, spiro-OMeTAD, metal oxides and fullerenes. We find that all studied CTLs limit the V_OC by inducing an additional non-radiative recombination current that is significantly larger than the loss in the neat perovskite and that the least-selective interface sets the upper limit for the V_OC of the device. The results also show that the V_OC equals the internal QFLS in the absorber layer of (pin, nip) cells with selective CTLs and power conversion efficiencies of up to 21.4%. However, in case of less selective CTLs, the V_OC is substantially lower than the QFLS which indicates additional losses at the contacts and/or interfaces. The findings are corroborated by rigorous device simulations which outline several important considerations to maximize the V_OC. This work shows that the real challenge to supress non-radiative recombination losses in perovskite cells on their way to the radiative limit lies in the suppression of carrier recombination at the perovskite/CTL interfaces.

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↗