The dual-source vacuum deposition of 2D perovskite films of the type PEA2PbX4, (PEA = phenethylammonium and X = I-, Br-, or a combination of both) is presented. Low-temperature deposited 2D perovskite films showed high crystallinity with the expected trend of bandgap as a function of halide type and concentration. Importantly, we observed an unavoidable halide cross-contamination among different deposition runs, as well as a strong dependence of the material quality on the type of halide precursors used. These findings should be taken into account in the development of vacuum processing for low-dimensional mixed halide perovskites.@en

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.@en

Mixed-halide lead perovskites have attracted significant attention in the field of photovoltaics and other optoelectronic applications due to their promising bandgap tunability and device performance. Here, the changes in photoluminescence and photoconductance of solution-processed triple-cation mixed-halide (Cs0.06MA0.15FA0.79)Pb(Br0.4I0.6)3 perovskite films (MA: methylammonium, FA: formamidinium) are studied under solar-equivalent illumination. It is found that the illumination leads to localized surface sites of iodide-rich perovskite intermixed with passivating PbI2 material. Time- and spectrally resolved photoluminescence measurements reveal that photoexcited charges efficiently transfer to the passivated iodide-rich perovskite surface layer, leading to high local carrier densities on these sites. The carriers on this surface layer therefore recombine with a high radiative efficiency, with the photoluminescence quantum efficiency of the film under solar excitation densities increasing from 3% to over 45%. At higher excitation densities, nonradiative Auger recombination starts to dominate due to the extremely high concentration of charges on the surface layer. This work reveals new insight into phase segregation of mixed-halide mixed-cation perovskites, as well as routes to highly luminescent films by controlling charge density and transfer in novel device structures.@en

A long photoluminescence decay lifetime has been regarded as a generic indication of long charge carrier recombination lifetime in semiconductors such as metal halide perovskites (MHPs), which have shown tremendous success in solar cells. Here, we report that MHP polycrystalline films with extrinsic metal ions have a very long charge recombination lifetime, but a much shorter photoluminescence decay lifetime, and this huge difference can be explained by a model of lateral homojunction within each individual grain. The lateral homojunction is formed due to the doping along grain boundaries by metal ions, and then verified by nanoscale potential mapping and transient photo-response mapping. The built-in electric field within each grain reduces the recombination of free charge carriers within the perovskite grain and along grain boundaries, while the free electrons and holes are collected to cathode and anode through the grain boundaries and grain interiors, respectively. Then, the efficiencies of MHP polycrystalline solar cells are increased.@en

Despite intense research into the optoelectronic properties of metal halide perovskites (MHPs), sub-bandgap absorption in MHPs remains largely unexplored. Here we recorded two-photon absorption spectra of MHPs using the time-resolved microwave conductivity technique. A two-step upward trend is observed in the two-photon absorption spectrum for methylammonium lead iodide, and some analogues, which implies that the commonly used scaling law is not applicable to MHPs. This aspect is further confirmed by temperature-dependent conductivity measurements. Using an empirical multiband tight binding model, spectra for methylammonium lead iodide were calculated by integration over the entire Brillouin zone, showing compelling similarity with experimental results. We conclude that the second upward trend in the two-photon absorption spectrum originates from additional optical transitions to the heavy and light electron bands formed by the strong spin-orbit coupling. Hence, valuable insight can be obtained in the opto-electronic properties of MHPs by sub-bandgap spectroscopy, complemented by modelling.@en

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 Voc 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.@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.@en

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. @en

The highest reported efficiencies of metal halide perovskite (MHP) solar cells are all based on mixed perovskites, such as (FA,MA,Cs)Pb(I1-xBrx)3. Despite demonstrated structural changes induced by light soaking, it is unclear how the charge carrier dynamics are affected across this entire material family. Here, various (FA,MA,Cs)Pb(I1-xBrx)3 perovskite films are light-soaked in nitrogen, and changes in optoelectronic properties are investigated through time-resolved microwave conductivity (TRMC) and optical and structural techniques. To fit the TRMC decay kinetics obtained for pristine (FA,MA,Cs)Pb(I1-xBrx)3 for various excitation densities, additional shallow states have to be included, which are not required for describing TRMC traces of single-cation MHPs. These shallow states can, independently of x, be removed by light soaking, which leads to a reduction in the imbalance between the diffusional motion of electrons and holes. We interpret the shallow states as a result of initially well-intermixed halide distributions, which upon light soaking segregate into domains with distinct band gaps.@en

Metal halide perovskites (MHPs) are interesting candidates for application in photovoltaic devices. During the past decade the efficiency of perovskite solar cells has improved enormously exceeding now values over 24%. In an MHP absorber layer, charge carriers are generated on optical excitation, and decay by band-to-band recombination or by other undesired loss mechanisms. In this thesis, the relationship between material properties, including constituents and morphology of the MHP layer and these processes is studied. The charge carrier dynamics describing these light-induced processes are studied by the time resolved microwave photoconductivity (TRMC) technique, in combination with standard optical techniques such as time-resolved photoluminescence (TRPL)… @en

Low-dimensional (quasi-) 2D perovskites are being extensively studied in order to enhance the stability and the open-circuit voltage of perovskite solar cells. Up to now, thin 2D perovskite layers on the surface and/or at the grain boundaries of 3D perovskites have been deposited solely by solution processing, leading to unavoidable intermixing between the two phases. In this work, we report the fabrication of 2D/3D/2D perovskite heterostructures by dual-source vacuum deposition, with the aim of studying the interaction between the 3D and 2D phases as well as the charge transport properties of 2D perovskites in neat 2D/3D interfaces. Unlike what is normally observed in solution-processed 3D/2D systems, we found a reduced charge transport with no direct evidence of surface passivation, in spite of larger open-circuit voltage. This is likely due to a nonfavorable orientation of the 2D perovskite with respect to methylammonium lead iodide and to the formation of 2D phases with very low dimensionality (pure 2D).@en

Organic-inorganic halide perovskites (OIHPs) bring an unprecedented opportunity for radiation detection with their defecttolerance nature, large mobility-lifetime product, and simple crystal growth from solution. Here we report a dopant compensation in alloyed OIHP single crystals to overcome limitations of device noise and charge collection, enabling -ray spectrum collection at room temperature. CH3NH3PbBr3 and CH3NH3PbCl3 are found to be p-type and n-type doped, respectively, whereas dopant-compensated CH3NH3PbBr2.94Cl0.06 alloy has over tenfold improved bulk resistivity of 3.6×109 φcm. Alloying also increases the hole mobility to 560 cm2 V-1 s-1, yielding a high mobility-lifetime product of 1.8×10-2 cm2 V-1. The use of a guard ring electrode in the detector reduces the crystal surface leakage current and device dark current. A distinguishable 137Cs energy spectrum with comparable or better resolution than standard scintillator detectors is collected under a small electric field of 1.8Vmm-1 at room temperature.@en

Time-resolved, pulsed excitation methods are widely used to deduce optoelectronic properties of semiconductors, including now also Halide Perovskites (HaPs), especially transport properties. However, as yet, no evaluation of their amenability and justification for the use of the results for the above-noted purposes has been reported. To check if we can learn from pulsed measurement results about steady-state phototransport properties, we show here that, although pulsed measurements can be useful to extract information on the recombination kinetics of HaPs, great care should be taken. One issue is that no changes in the material are induced during or as a result of the excitation, and another one concerns in how far pulsed excitation-derived data can be used to find relevant steady-state parameters. To answer the latter question, we revisited pulsed excitation and propose a novel way to compare between pulsed and steady state measurements at different excitation intensities. We performed steady-state photoconductivity and ambipolar diffusion length measurements, as well as pulsed time-resolved microwave conductivity and time-resolved photoluminescence measurements as a function of excitation intensity on the same samples of different MAPbI3 thin films, and found good quasi-quantitative agreement between the results, explaining them with a generalized single level recombination model that describes the basic physics of phototransport of HaP absorbers. Moreover, we find the first experimental manifestation of the boundaries between several effective recombination regimes that exist in HaPs, by analyzing their phototransport behavior as a function of excitation intensity.@en