Halide perovskite solar cells have demonstrated a rapid increase in power conversion efficiencies. Understanding and mitigating remaining carrier losses in halide perovskites is now crucial to enable further increases to approach their practical efficiency limits. Recent observations in halide perovskites have revealed processes such as shallow carrier trapping, which give rise to an apparent non-radiative bimolecular channel that is difficult to distinguish from intrinsic radiative recombination. Here, we quantify this shallow-trap manifestation by jointly analyzing time-resolved photoluminescence and quantum efficiency to separate the total second-order term into radiative (η_esck_2r) and shallow-trap-mediated non-radiative contributions (k_2non), and evaluate their device impact. We show that k_2non is strongly modulated by temperature and surface chemistry and thus depends on extrinsic factors and its origin is independent from deep traps, whereas the intrinsic radiative coefficient and intrinsic second-order recombination follow detailed-balance expectations and align with theoretical evaluations through van Roosbroeck–Shockley relations. Based on density functional theory simulations and Quasi-Fermi level calculations, we propose that surface states are the primary origin of this shallow-trap-related second-order component, contributing up to ∼80 mV of the overall reduction in V_oc at room temperature. This work reveals that the origin of carrier losses from two non-radiative recombination types (first and second order) are not linked, emphasizing the need for distinctive mitigation strategies targeting each type to unlock the full efficiency potential of perovskite solar cells.

The presence of defects at the interface between the perovskite film and the carrier transport layer poses significant challenges to the performance and stability of perovskite solar cells (PSCs). Addressing this issue, we introduce a dual host-guest (DHG) complexation strategy to modulate both the bulk and interfacial properties of FAPbI₃-rich PSCs. Through NMR spectroscopy, a synergistic effect of the dual treatment is observed. Additionally, electro-optical characterizations demonstrate that the DHG strategy not only passivates defects but also enhances carrier extraction and transport. Remarkably, employing the DHG strategy yields PSCs with power conversion efficiencies (PCE) of 25.89% (certified at 25.53%). Furthermore, these DHG-modified PSCs exhibit enhanced operational stability, retaining over 96.6% of their initial PCE of 25.55% after 1050 hours of continuous operation under one-sun illumination, which was the highest initial value in the recently reported articles. This work establishes a promising pathway for stabilizing high-efficiency perovskite photovoltaics through supramolecular engineering, marking a significant advancement in the field.

To increase the open-circuit voltage in solar cells based on triple cation, mixed halide perovskites, reducing recombination processes at the interfaces with transport layers (TLs) is key. Here, we investigated the charge carrier dynamics in bilayers and trilayers of Cs_0.05MA_0.10FA_0.85Pb(I_0.97Br_0.03)₃ (CsMAFA) combined with TLs using time-resolved microwave conductance (TRMC) measurements without and with bias illumination (BI). In the bilayers, we find balanced mobilities for electrons and holes in CsMAFA and nearly quantitative carrier extraction. The small, rapidly decaying TRMC signals for n-i-p- and p-i-n triple layers indicate both carriers are extracted. Applying BI leads to the charging of the TLs and the corresponding electric field prevents additional charge extraction, which demonstrates long-lived charge separation over the CsMAFA/TLs. Most importantly, for all bilayer combinations showing long-lived charge separation, an increase of the quasi-Fermi level splitting with respect to that of the CsMAFA layer is found.

Multiple-source thermal evaporation is emerging as an excellent technique to obtain perovskite (PVK) materials for solar cell applications due to its solvent-free processing, accurate control of stoichiometric ratio, and potential for scalability. Nevertheless, the currently reported layer-by-layer deposition approach is afflicted by long processing times caused by the multiple repetitions of thin films, which hinder industrial uptake. On the other hand, the coevaporation entails higher complexity due to the challenges of controlling the sublimation of multiple sources simultaneously. In this work, we propose a simplified approach consisting of a single-cycle deposition (SCD) of three thick precursor layers to obtain high-quality Cs0.15FA0.85PbI2.85Br0.15 (CsFAPbIBr) films. After annealing, the optimized PVK film exhibits comparable properties to the one deposited by multicycle deposition in terms of crystal structure, in-depth uniformity, and optoelectrical properties. Also, the formation and evolution of SCD PVK during annealing are investigated. We found that, in the competitive processes of precursor diffusion and reaction, the presence of cesium bromide can assist precursor mixing driven by the annealing treatment, demonstrating a reaction-limited process in the PVK conversion. With this simplified SCD approach, a PVK film is obtained with expected optical and opto-electronic properties, providing an appealing way for future thermally evaporated PVK device preparation.

Perovskite-based solar cells have been rapidly developed, with record power conversion efficiencies now exceeding 25%. In order to rationally improve the efficiency of these devices, it is important to understand and quantify the dynamics of the excess charge carriers.

Metal-halide perovskites deposited by wet-chemical deposition have demonstrated great potential for various electronic applications, including solar cells. A remaining question is how light-induced excess charges become distributed over such polycrystalline material. Here, we examine the local conductive properties of MAPbI₃ and CsFAPbI₃ by using scanning microwave microscopy (sMIM) in the dark and light. sMIM is an atomic force microscopy (AFM)-based technique measuring variations of the in-phase and out-of-phase signals due to changes in the tip-sample interaction, yielding MIM-Re and MIM-Im images, respectively. Combining this information leads to a picture for CsFAPbI₃ in which excess charges are distributed evenly over the grains, but due to local defect-rich areas, possibly related to different crystal facets, local perturbations in carrier concentration exist. For solar cells, this distribution in carrier concentration under illumination leads to variation in the local Fermi level splitting, which should be suppressed to reduce the voltage deficit.

State-of-the-art triple cation, mixed halide perovskites are extensively studied in perovskite solar cells, showing very promising performance and stability. However, an in-depth fundamental understanding of how the phase behavior in Cs_0.05FA_0.85MA_0.10Pb(I_0.97Br_0.03)₃ (CsMAFA) affects the optoelectronic properties is still lacking. The refined unit cell parameters a and c in combination with the thermal expansion coefficients derived from X-ray diffraction patterns reveal that CsMAFA undergoes an α–β phase transition at ≈280 K and another transition to the γ-phase at ≈180 K. From the analyses of the electrodeless microwave photoconductivity measurements it is shown that shallow traps only in the γ-phase negatively affect the charge carrier dynamics. Most importantly, CsMAFA exhibits the lowest amount of microstrain in the β-phase at around 240 K, corresponding to the lowest amount of trap density, which translates into the longest charge carrier diffusion length for electrons and holes. Below 200 K a considerable increase in deep trap states is found most likely related to the temperature-induced compressive microstrain leading to a huge imbalance in charge carrier diffusion lengths between electrons and holes. This work provides valuable insight into how temperature-dependent changes in structure affect the charge carrier dynamics in FA-rich perovskites.

Mobilities and lifetimes of photogenerated charge carriers are core properties of photovoltaic materials and can both be characterized by contactless terahertz or microwave measurements. Here, the expertise from fifteen laboratories is combined to quantitatively model the current-voltage characteristics of a solar cell from such measurements. To this end, the impact of measurement conditions, alternate interpretations, and experimental inter-laboratory variations are discussed using a (Cs,FA,MA)Pb(I,Br)₃ halide perovskite thin-film as a case study. At 1 sun equivalent excitation, neither transport nor recombination is significantly affected by exciton formation or trapping. Terahertz, microwave, and photoluminescence transients for the neat material yield consistent effective lifetimes implying a resistance-free JV-curve with a potential power conversion efficiency of 24.6 %. For grainsizes above ≈20 nm, intra-grain charge transport is characterized by terahertz sum mobilities of ≈32 cm² V⁻¹ s⁻¹. Drift-diffusion simulations indicate that these intra-grain mobilities can slightly reduce the fill factor of perovskite solar cells to 0.82, in accordance with the best-realized devices in the literature. Beyond perovskites, this work can guide a highly predictive characterization of any emerging semiconductor for photovoltaic or photoelectrochemical energy conversion. A best practice for the interpretation of terahertz and microwave measurements on photovoltaic materials is presented.

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.

Co-evaporation of metal halide perovskites by thermal evaporation is an attractive method since it does not require harmful solvents and enables precise control of the film thickness. Furthermore, the ability to manipulate the Fermi level allows the formation of a graded homojunction, providing interesting opportunities to improve the charge carrier collection efficiency. However, little is known about how these properties affect the charge carrier dynamics. In this work, the structural and optoelectronic properties of co-evaporated MAPbI3 films varying in thickness (100, 400, and 750 nm) with a gradient in composition are analyzed. The X-ray diffraction patterns show that excess PbI2 is only present in the thick layers. From X-ray photoelectron spectroscopy depth analysis, the I/Pb atomic ratio indicates methylammonium iodide deficiencies that become more prominent with thicker films, resulting in differently n-doped regions across the thick MAPbI3 films. We suggest that due to these differently n-doped regimes, an internal electric field is formed. Side-selective time-resolved microwave photo conductivity measurements show an elongation of the charge carrier lifetimes on increasing thickness. These observations can be explained by the fact that excess carriers separate under the influence of the electric field, preventing rapid decay in the thick films.

Wide-band-gap perovskites such as methylammonium lead bromide (MAPB) are promising materials for tandem solar cells because of their potentially high open-circuit voltage, which is yet still far below the maximum limit. The relatively short charge-carrier lifetimes deduced from time-resolved photoluminescence (TRPL) measurements seem in strong contrast with the long lifetimes observed with time-resolved photoconductance measurements. This is explained by a large amount of hole defect states, NT > 1016 cm-3, in spin-coated layers of MAPB residing at or near the grain boundaries. The introduction of hypophosphorous acid (HPA) increases the average grain size by a factor of 3 and reduces the total concentration of the trap states by a factor of 10. The introduction of HPA also increases the fraction of initially generated holes that undergo charge transfer to the selective contact, Spiro-OMeTAD (SO), by an order of magnitude. In contrast to methylammonium lead iodide (MAPI)/SO bilayers, a reduction of the carrier lifetime is observed in MAPB/SO bilayers, which is attributed to the fact that injected holes undergo interfacial recombination via these trap states. Our findings provide valuable insight into the optoelectronic properties of bromide-containing lead halide perovskites essential for designing efficient tandem solar cells.

Recent progress of vapor-deposited perovskite solar cells (PSCs) has proved the feasibility of this deposition method in achieving promising photovoltaic devices. For the first time, it is probed the versatility of the co-evaporation process in creating perovskite layers customizable for different device architectures. A gradient of composition is created within the perovskite films by tuning the background chamber pressure during the growth process. This method leads to co-evaporated MAPbI₃ film with graded Fermi levels across the thickness. Here it is proved that this growth process is beneficial for p-i-n PSCs as it can guarantee a favorable energy alignment at the charge selective interfaces. Co-evaporated p-i-n PSCs, with different hole transporting layers, consistently achieve power conversion efficiency (PCE) over 20% with a champion value of 20.6%, one of the highest reported to date. The scaled-up p-i-n PSCs, with active areas of 1 and 1.96 cm², achieved the record PCEs of 19.1% and 17.2%, respectively, while the flexible PSCs reached a PCE of 19.3%. Unencapsulated PSCs demonstrate remarkable long-term stability, retaining ≈90% of their initial PCE when stored in ambient for 1000 h. These PSCs also preserve over 80% of their initial PCE after 500 h of thermal aging at 85 °C.