Suitable optoelectronic properties of lead halide perovskites make these materials interesting semiconductors for many applications. Toxic lead can be substituted by combining monovalent and trivalent cations, such as in Cs₂AgBiBr₆. However, efficiencies of Cs₂AgBiBr₆-based photovoltaics are still modest. To elucidate the loss mechanisms, in this report, we investigate charge dynamics in Cs₂AgBiBr₆ films by double-pulse excitation time-resolved microwave conductivity (DPE-TRMC). By exciting the sample with two laser pulses with identical wavelengths, we found a clear photoconductance enhancement induced by the second pulse even 30 μs after the first laser pulse. Modeling the DPE-TRMC results, complemented by photoluminescence and transient absorption, we reveal the presence of deep emissive electron traps, while shallow hole trapping is responsible for the long-lived transient absorption signals. These long-lived carriers offer interesting possibilities for X-ray detectors or photocatalysis. The DPE-TRMC methodology offers unique insight into the times involved in charge trapping and depopulation in Cs₂AgBiBr₆.

Cs₂AgBiBr₆ (CABB) has been proposed as a promising nontoxic alternative to lead halide perovskites. However, low charge carrier collection efficiencies remain an obstacle for the incorporation of this material in optoelectronic applications. In this work, we study the optoelectronic properties of CABB thin films using steady state and transient absorption and reflectance spectroscopy. We find that optical measurements on such thin films are distorted as a consequence of multiple reflections within the film. Moreover, we discuss the pathways behind conductivity loss in these thin films, using a combination of microsecond transient absorption spectroscopy and time-resolved microwave conductivity measurements. We demonstrate that a combined effect of carrier loss and localization results in the conductivity loss in CABB thin films. Moreover, we find that the charge carrier diffusion length and grain size are of the same order of magnitude. This suggests that the material's surface is an important contributor to charge-carrier loss.

Metal halide perovskite solar cells (PSCs) are of interest for high altitude and space applications due to their lightweight and versatile form factor. However, their resilience toward the particle spectrum encountered in space is still of concern. For space cells, the effect of these particles is condensed into an equivalent 1 MeV electron fluence. The effect of high doses of 1 MeV e-beam radiation up to an accumulated fluence to 10¹⁶ e⁻ cm⁻² on methylammonium lead iodide perovskite thin films and solar cells is probed. By using substrate and encapsulation materials that are stable under the high energy e-beam radiation, its net effect on the perovskite film and solar cells can be studied. The quartz substrate-based PSCs are stable under the high doses of 1 MeV e-beam irradiation. Time-resolved microwave conductivity analysis on pristine and irradiated films indicates that there is a small reduction in the charge carrier diffusion length upon irradiation. Nevertheless, this diffusion length remains larger than the perovskite film thickness used in the solar cells, even for the highest accumulated fluence of 10¹⁶ e⁻ cm⁻². This demonstrates that PSCs are promising candidates for space applications.

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.

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.

Tailoring the physical properties of hybrid lead metal halide APbX₃ perovskites by means of compositional engineering is one of the key factors contributing to the development of highly efficient and stable perovskite solar cells. While the beneficial effects of partial ionic replacement at the A- and X-sites are largely demonstrated, partial replacement of Pb²⁺ is less explored. Here, we developed a solution-based procedure to prepare thin films of mixed-metal MAPb_1-aMn_aI₃ perovskites. Although Mn²⁺ ions have a size that can potentially fit in the B-sites of MAPbI₃, using a combination of structural and chemical analysis, we show that only less than 10% of Pb²⁺ can be replaced by Mn²⁺. A 3% replacement of Pb²⁺ by Mn²⁺ leads to an elongation of the charge carrier lifetimes as concluded from time-resolved PL measurements. However, by analysis of the time-resolved microwave conductance data, we show that the charge carrier mobilities are largely unbalanced, which is in accordance with density functional theory (DFT) calculations indicating that the effective mass of the hole is much higher than that of the electron. Increasing the concentration of Mn²⁺ in the precursor solution above 10% results in formation of amorphous Mn-rich domains in the film, while the perovskite lattice becomes depleted of Mn²⁺. These domains negatively affect the charge carrier mobilities and shorten the lifetime of photogenerated carriers. The resulting reduction in charge carrier diffusion lengths will severely limit the photovoltaic properties of solar cells prepared from these mixed metal halide perovskites.

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.

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.

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.

Despite the unprecedented interest in organic-inorganic metal halide perovskite solar cells, quantitative information on the charge transfer dynamics into selective electrodes is still lacking. In this paper, we report the time scales and mechanisms of electron and hole injection and recombination dynamics at organic PCBM and Spiro-OMeTAD electrode interfaces. On the one hand, hole transfer is complete on the subpicosecond time scale in MAPbI₃/Spiro-OMeTAD, and its recombination rate is similar to that in neat MAPbI₃. This was found to be due to a high concentration of dark charges, i.e., holes brought about by unintentional p-type doping of MAPbI₃. Hence, the total concentration of holes in the perovskite is hardly affected by optical excitation, which manifested as similar decay kinetics. On the other hand, the decay of the photoinduced conductivity in MAPbI₃/PCBM is on the time scale of hundreds of picoseconds to several nanoseconds, due to electron injection into PCBM and electron-hole recombination at the interface occurring at similar rates. These results highlight the importance of understanding the role of dark carriers in deconvoluting the complex photophysical processes in these materials. Moreover, optimizing the preparation processes wherein undesired doping is minimized could prompt the use of organic molecules as a more viable electrode substitute for perovskite solar cell devices.