A better understanding of the materials' fundamental physical processes is necessary to push hybrid perovskite photovoltaic devices towards their theoretical limits. The role of the perovskite grain boundaries is essential to optimise the system thoroughly. The influence of the perovskite grain size and crystal orientation on physical properties and their resulting photovoltaic performance is examined. We develop a novel, straightforward synthesis approach that yields crystals of a similar size but allows the tuning of their orientation to either the (200) or (002) facet alignment parallel to the substrate by manipulating dimethyl sulfoxide (DMSO) and tetrahydrothiophene-1-oxide (THTO) ratios. This decouples crystal orientation from grain size, allowing the study of charge carrier mobility, found to be improved with larger grain sizes, highlighting the importance of minimising crystal disorder to achieve efficient devices. However, devices incorporating crystals with the (200) facet exhibit an s-shape in the current density-voltage curve when standard scan rates are used, which typically signals an energetic interfacial barrier. Using the drift-diffusion simulations, we attribute this to slower-moving ions (mobility of 0.37 × 10^-10 cm² V^-1 s^-1) in combination with a lower density of mobile ions. This counterintuitive result highlights that reducing ion migration does not necessarily minimise hysteresis.

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An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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The unprecedented rise in the power conversion efficiency of solar cells based on metal halide perovskites (MHPs) has led to enormous research effort to understand their photophysical properties. The progress made in understanding the mobility and recombination of photogenerated charge carriers from nanosecond to microsecond time scales, monitored using electrodeless transient photoconductivity techniques, is reviewed. In addition, a kinetic model to obtain rate constants from transient data recorded using a wide range of laser intensities is presented. For various MHPs the temperature dependence of the mobilities and recombination rates are evaluated. Furthermore, it is shown how these rate constants can be used to predict the upper limit for the open-circuit voltage V_oc of the corresponding device. Finally, the photophysical properties of MHPs that are not yet fully understood are explored, and recommendations for future research directions are made.

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To further understand the optoelectronic properties of metal halide perovskites, we investigate sub-bandgap absorption in methylammonium lead iodide (MAPbI3) films. Charge carrier dynamics are studied using time-resolved microwave conductivity measurements using sub-bandgap excitation. From changes in the decay dynamics as a function of excitation energy and intensity, we have identified three regimes: (i) Band-like charge transport at photon energies above 1.48 eV; (ii) a transitional regime between 1.48 and 1.40 eV; and (iii) below 1.40 eV localized optically active defects (8 × 1013 cm-3) dominate the absorption at low intensities, while two-photon absorption is observed at high intensities. We determined an Urbach energy of approximately 11.3 meV, indicative of a low structural and/or thermal disorder. Surprisingly, even excitation 120 meV below the bandgap leads to efficient charge transfer into electron (C60) or hole (spiro-OMeTAD) transport layers. Therefore, we conclude that for MAPbI3, the band tail states do not lead to nonradiative losses.

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While the power conversion efficiency of metal halide perovskite (MHP) solar cells has increased enormously, the open-circuit voltage, V _oc , is still below the conceivable limit. Here, we derive the Fermi level splitting, μ _F , for various types of noncontacted MHPs, which sets a limit for their achievable V _oc , using rate constants and mobilities obtained from time-resolved photoconductivity measurements. Interestingly, we find that for vacuum-evaporated MAPbI ₃ and K ⁺ -doped (MA,FA,Cs)Pb(I/Br) ₃ , the μ _F /e values are close to the reported V _oc values. This implies that for an improvement of the V _oc , charge carrier recombination within the bare perovskite has to be reduced. On the other hand, for MHPs with Cs ⁺ and/or Rb ⁺ addition, the experimental V _oc is still below μ _F /e, suggesting that higher voltages are feasible by optimizing the transport layers. The presented approach will help to select which techniques and transport layers are beneficial to improve the efficiency of MHP solar cells.

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Growing large, oriented grains of perovskite often leads to efficient devices, but it is unclear if properties of the grains are responsible for the efficiency. Domains observed in SEM are commonly misidentified with crystallographic grains, but SEM images do not provide diffraction information. We study methylammoinium lead iodide (MAPbI₃) films fabricated via flash infrared annealing (FIRA) and the conventional antisolvent (AS) method by measuring grain size and orientation using electron back-scattered diffraction (EBSD) and studying how these affect optoelectronic properties such as local photoluminescence (PL), charge carrier lifetimes, and mobilities. We observe a local enhancement and shift of the PL emission at different regions of the FIRA clusters, but we observe no effect of crystal orientation on the optoelectronic properties. Additionally, despite substantial differences in grain size between the two systems, we find similar optoelectronic properties. These findings show that optoelectronic quality is not necessarily related to the orientation and size of crystalline domains.

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Recently, several studies have investigated dielectric properties as a possible origin of the exceptional optoelectronic properties of metal halide perovskites (MHPs). In this study we investigated the temperature-dependent dielectric behavior of different MHP films at different frequencies. In the gigahertz regime, dielectric losses in methylammonium-based samples are dominated by the rotational dynamics of the organic cation. Upon increasing the temperature from 160 to 300 K, the rotational relaxation time, τ, decreases from 400 (200) to 6 (1) ps for MAPb-I₃ (-Br₃). By contrast, we found negligible temperature-dependent variations in τ for a mixed cation/mixed halide FA_0.85MA_0.15Pb(I_0.85Br_0.15)₃. From temperature-dependent time-resolved microwave conductance measurements we conclude that the dipolar reorientation of the MA cation does not affect charge carrier mobility and lifetime in MHPs. Therefore, charge carriers do not feel the relatively slow-moving MA cations, despite their great impact on the dielectric constants.

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Recently, halide double perovskites (HDPs), such as Cs₂AgBiBr₆, have been reported as promising nontoxic alternatives to lead halide perovskites. However, it remains unclear whether the charge-transport properties of these materials are as favorable as for lead-based perovskites. In this work, we study the mobilities of charges in Cs₂AgBiBr₆ and in mixed antimony-bismuth Cs₂AgBi_1-xSb_xBr₆, in which the band gap is tunable from 2.0 to 1.6 eV. Using temperature-dependent time-resolved microwave conductivity techniques, we find that the mobility is proportional to T^-p (with p ≈ 1.5). Importantly, this indicates that phonon scattering is the dominant scattering mechanism determining the charge carrier mobility in these HDPs similar to the state-of-the-art lead-based perovskites. Finally, we show that wet chemical processing of Cs₂AgBi_1-xSb_xBr₆ powders is a successful route to prepare thin films of these materials, which paves the way toward photovoltaic devices based on nontoxic HDPs with tunable band gaps.

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The relationship between the dipole moment of the methylammonium cation and the optoelectronic properties of lead halide perovskites remains under debate. We show that both the temperature-dependent charge carrier mobility and recombination kinetics are identical for methylammonium and cesium lead iodide, indicating that the role of the monovalent cation is subordinate to the lead iodide framework. From the observation that for both perovskites the electron-hole recombination is thermally activated, we speculate that the bandgap is slightly indirect.

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Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield - a quantity that must be maximized to obtain high efficiency - remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can approach the efficiency limits in tandem solar cells, coloured-light-emitting diodes and other optoelectronic applications.

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State-of-the-art perovskite-based solar cells employ expensive, organic hole transporting materials (HTMs) such as Spiro-OMeTAD that, in turn, limits the commercialization of this promising technology. Herein an HTM (EDOT-Amide-TPA) is reported in which a functional amide-based backbone is introduced, which allows this material to be synthesized in a simple condensation reaction with an estimated cost of <$5 g⁻¹. When employed in perovskite solar cells, EDOT-Amide-TPA demonstrates stabilized power conversion efficiencies up to 20.0% and reproducibly outperforms Spiro-OMeTAD in direct comparisons. Time resolved microwave conductivity measurements indicate that the observed improvement originates from a faster hole injection rate from the perovskite to EDOT-Amide-TPA. Additionally, the devices exhibit an improved lifetime, which is assigned to the coordination of the amide bond to the Li-additive, offering a novel strategy to hamper the migration of additives. It is shown that, despite the lack of a conjugated backbone, the amide-based HTM can outperform state-of-the-art HTMs at a fraction of the cost, thereby providing a novel set of design strategies to develop new, low-cost HTMs.

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Adding cesium (Cs) and rubidium (Rb) cations to FA_0.83MA_0.17Pb(I_0.83Br_0.17)₃ hybrid lead halide perovskites results in a remarkable improvement in solar cell performance, but the origin of the enhancement has not been fully understood yet. In this work, time-of-flight, time-resolved microwave conductivity, and thermally stimulated current measurements are performed to elucidate the impact of the inorganic cation additives on the trap landscape and charge transport properties within perovskite solar cells. These complementary techniques allow for the assessment of both local features within the perovskite crystals and macroscopic properties of films and full devices. Strikingly, Cs-incorporation is shown to reduce the trap density and charge recombination rates in the perovskite layer. This is consistent with the significant improvements in the open-circuit voltage and fill factor of Cs-containing devices. By comparison, Rb-addition results in an increased charge carrier mobility, which is accompanied by a minor increase in device efficiency and reduced current-voltage hysteresis. By mixing Cs and Rb in quadruple cation (Cs-Rb-FA-MA) perovskites, the advantages of both inorganic cations can be combined. This study provides valuable insights into the role of these additives in multiple-cation perovskite solar cells, which are essential for the design of high-performance devices.

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In this thesis, we have investigated the optoelectronic properties of metal halide perovskites with a special focus on their application in solar cells. In less than a decade of development, metal halide perovskites have yielded solar cells with efficiencies comparable to commercialized technologies. However, there has been limited knowledge about the fundamental properties of these materials. As mentioned in the introduction, the efficiency of perovskite-based solar cells is still not at its theoretical limit. In order to rationally design solar cells with maximized efficiencies, we need to understand which factors are currently limiting the performance of perovskite-based solar cells. In general, one of the first important processes in a solar cell is the absorption of light. For metal halide perovskites based on lead iodide, a thickness of 0.3 micrometer is already sufficient to absorb a substantial amount of visible (sun-)light, which makes these materials very suitable for solar cells. Furthermore, it is crucial that this absorbed light is converted into a current of moving charges, also known as electricity. Semiconductor materials such as silicon or metal halide perovskites have the ideal properties to generate a current of charges from light. In order to use this current however, the charges need to be collected. The efficiency with which charges are collected in a solar cell is closely related to its power conversion efficiency.@en

In view of its band gap of 2.2 eV and its stability, methylammonium lead bromide (MAPbBr₃) is a possible candidate to serve as a light absorber in a subcell of a multijunction solar cell. Using complementary temperature-dependent time-resolved microwave conductance (TRMC) and photoluminescence (TRPL) measurements, we demonstrate that the exciton yield increases with lower temperature at the expense of the charge carrier generation yield. The low-energy emission at around 580 nm in the cubic phase and the second broad emission peak at 622 nm in the orthorhombic phase originate from radiative recombination of charges trapped in defects with mobile countercharges. We present a kinetic model describing both the decay in conductance as well as the slow ingrowth of the TRPL. Knowledge of defect states at the surface of various crystal phases is of interest to reach higher open-circuit voltages in MAPbBr₃-based cells.

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Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum efficiencies of polycrystalline perovskite films from 1% to 89%, with carrier lifetimes of 32 μs and diffusion lengths of 77 μm, comparable with perovskite single crystals. Remarkably, the surface recombination velocity of holes in the treated films is 0.4 cm/s, approaching the values for fully passivated crystalline silicon, which has the lowest values for any semiconductor to date. The enhancements translate to solar cell power-conversion efficiencies of 19.2%, with a near-instant rise to stabilized power output, consistent with suppression of ion migration. We propose a mechanism in which light creates superoxide species from oxygen that remove shallow surface states. The work reveals an industrially scalable post-treatment capable of producing state-of-the-art semiconducting films. Metal halide perovskites are exciting materials for low-cost optoelectronic devices such as solar cells and LEDs. In order to reach the theoretical efficiency limits for both applications, any parasitic non-radiative charge-carrier recombination losses, such as those mediated by carrier trapping, must be eliminated. At present, perovskite materials still suffer from substantial non-radiative decay, particularly under solar illumination conditions, and are therefore yet to reach their full potential. Perovskite single crystals have very low trap concentrations but their controlled growth into devices does not lend themselves to the advantages offered by solution-processing thin films such as roll-to-roll depositions. Here, we demonstrate the use of light and atmospheric treatments on polycrystalline perovskite films, resulting in minimal non-radiative losses and properties approaching those of perovskite single crystals and even the best crystalline semiconductors reported to date. The authors demonstrate the use of light and atmospheric treatments on polycrystalline perovskite thin films, resulting in properties approaching those of the best crystalline semiconductors reported to date. The results translate to exceptional photovoltaic device performances with rapid rises to stabilized power output consistent with an inhibition of ionic migration.

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Perovskite-based photovoltaics have been rapidly developed, with record power conversion efficiencies now exceeding 22%. In order to rationally design efficient and stable perovskite solar cells, it is important to understand not only charge trapping and recombination events, but also processes occurring at the perovskite/transport material (TM) interface, such as charge transfer and interfacial recombination. In this work, time-resolved microwave conductivity measurements are performed to investigate these interfacial processes for methylammonium lead iodide and various state-of-the-art organic TMs. A global kinetic model is developed, which accurately describes both the dynamics of excess charges in the perovskite layer and transfer to charge-specific TMs. The authors conclude that for state-of-the-art materials, such as Spiro-OMeTAD and PCBM, the charge extraction efficiency is not significantly affected by intra-band gap traps for trap densities under 10¹⁵ cm^–3. Finally, the transfer rates to C60, PCBM, EDOT-OMeTPA, and Spiro-OMeTAD are sufficient to outcompete second order recombination under excitation densities representative for illumination by AM1.5.

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The optoelectronic properties of hybrid perovskites can be easily tailored by varying their components. Specifically, mixing the common short organic cation (methylammonium (MA)) with a larger one (e.g., butyl ammonium (BA)) results in 2-dimensional perovskites with varying thicknesses of inorganic layers separated by the large organic cation. In both of these applications, a detailed understanding of the dissociation and recombination of electron-hole pairs is of prime importance. In this work, we give a clear experimental demonstration of the interconversion between bound excitons and free charges as a function of temperature by combining microwave conductivity techniques with photoluminescence measurements. We demonstrate that the exciton binding energy varies strongly (between 80 and 370 meV) with the thickness of the inorganic layers. Additionally, we show that the mobility of charges increases with the layer thickness, in agreement with calculated effective masses from electronic structure calculations.

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Lastly, Chapter 7 elucidates the characterization of perovskite solar cells using time-resolved photoconductivity technique.

List of Abbreviations
Introduction
Methods
Light Absorption
Time-Resolved THz Spectroscopy
Time-Resolved Microwave Conductivity
Modeling of Kinetic Data
Transient Photoconductivity Measurements in the Picosecond to Few Nanosecond Time Scales
Properties of Intrinsic MAPbI3 Material
Properties of Intrinsic FAPbI3 Material
Charge Injection to Metal Oxide Electrodes
Charge Injection to Organic Electrodes
Transient Photoconductivity Measurements in the Hundreds of Nanoseconds to Microsecond Time Scales
Thin Film Perovskites
Single Crystal Perovskite
Conclusions and Perspectives
Acknowledgment
References
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Metal halide perovskites such as methylammonium lead iodide (MAPbI3) are highly promising materials for photovoltaics. However, the relationship between the organic nature of the cation and the optoelectronic quality remains debated. In this work, we investigate the optoelectronic properties of fully inorganic vapour-deposited and spin-coated black-phase CsPbI3 thin films. Using the time-resolved microwave conductivity technique, we measure charge carrier mobilities up to 25 cm2/(V s) and impressively long charge carrier lifetimes exceeding 10 μs for vapour-deposited CsPbI3, while the carrier lifetime reaches less than 0.2 μs in the spin-coated samples. Finally, we show that these improved lifetimes result in enhanced device performance with power conversion efficiencies close to 9%. Altogether, these results suggest that the charge carrier mobility and recombination lifetime are mainly dictated by the inorganic framework rather than the organic nature of the cation@en

Metal halide perovskites such as methylammonium lead iodide (CH₃ NH₃ PbI₃) are generating great excitement due to their outstanding optoelectronic properties, which lend them to application in high-efficiency solar cells and light-emission devices. However, there is currently debate over what drives the second-order electron-hole recombination in these materials. Here, we propose that the bandgap in CH₃ NH₃ PbI₃ has a direct-indirect character. Time-resolved photo-conductance measurements show that generation of free mobile charges is maximized for excitation energies just above the indirect bandgap. Furthermore, we find that second-order electron-hole recombination of photo-excited charges is retarded at lower temperature. These observations are consistent with a slow phonon-assisted recombination pathway via the indirect bandgap. Interestingly, in the low-temperature orthorhombic phase, fast quenching of mobile charges occurs independent of the temperature and photon excitation energy. Our work provides a new framework to understand the optoelectronic properties of metal halide perovskites and analyse spectroscopic data.

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