Lead halide perovskites have attracted significant attention for their wide-ranging applications in optoelectronic devices. A ubiquitous element in these applications is that charging of the perovskite is involved, which can trigger electrochemical degradation reactions. Understanding the underlying factors governing these degradation processes is crucial for improving the stability of perovskite-based devices. For bulk semiconductors, the electrochemical decomposition potentials depend on the stabilization of atoms in the lattice-a parameter linked to the material’s solubility. For perovskite nanocrystals (NCs), electrochemical surface reactions are strongly influenced by the binding equilibrium of passivating ligands. Here, we report a spectro-electrochemical study on CsPbBr₃ NCs and bulk thin films in contact with various electrolytes, aimed at understanding the factors that control cathodic degradation. These measurements reveal that the cathodic decomposition of NCs is primarily determined by the solubility of surface ligands, with diminished cathodic degradation for NCs in high-polarity electrolyte solvents where ligand solubilities are lower. However, the solubility of the surface ligands and bulk lattice of NCs are orthogonal, such that no electrolyte could be identified where both the surface and bulk are stabilized against cathodic decomposition. This poses inherent challenges for electrochemical applications: (i) The electrochemical stability window of CsPbBr₃ NCs is constrained by the reduction potential of dissolved Pb²⁺ complexes, and (ii) cathodic decomposition occurs well before the conduction band can be populated with electrons. Our findings provide insights to enhance the electrochemical stability of perovskite thin films and NCs, emphasizing the importance of a combined selection of surface passivation and electrolyte.

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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.

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To increase the open-circuit voltage in perovskite-based solar cells, recombination processes at the interface with transport layers (TLs) should be identified and reduced. We investigated the charge carrier dynamics in bilayers of methylammonium lead iodide (MAPbI3) with C60 or Spiro-OMeTAD using time-resolved microwave conductance (TRMC) measurements with and without bias illumination (BI). By modeling the results, we quantified recombination losses in bare MAPbI3 and extraction into the TLs. Only under BI did we find that the density of deep traps increases in bare MAPbI3, substantially enhancing trap-mediated losses. This reversible process is prevented in a bilayer with C60 but not with Spiro-OMeTAD. While under BI extraction rates reduce significantly in both bilayers, only in MAPbI3/Spiro-OMeTAD does interfacial recombination also increases, substantially reducing the quasi Fermi level splitting. This work demonstrates the impact of BI on charge dynamics and shows that adjusting the Fermi level of TLs is imperative to reduce interfacial recombination losses.

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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.

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For centuries we have relied on fossil fuels to produce energy for our needs, causing significant damage to the environment and our own health. To make an energy transition possible, technology has to step up, providing solutions for cleaner and cheaper energy production. In the field of solar energy, perovskite-based devices can offer a feasible alternative to conventional technologies, involving less energy intensive and cheaper manufacturing processes. Despite the great technological advancements of the past years, open circuit voltage losses and especially poor long-term stability are two of the main bottlenecks that still have to be overcome in order to bring the technology to market. In this thesis we have addressed such issues by investigating the origin and impact of electronic trap states on charge carrier dynamics in perovskite thin films of different composition...@en

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.

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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.

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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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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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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.

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Combining halide perovskites with tailored dimensionality into two/three-dimensional (2D/3D) systems has revealed a powerful strategy to boost the performances of perovskite photovoltaics (PVs). Despite recent advances, a clear understanding of the intimate link between interface structure and physics is still missing, leading so far to a blind optimization of the 2D/3D PVs. Here, we reveal the impact of 2D/3D crystal alignment in driving interface charge-recombination dynamics. The 2D crystal growth and orientation are manipulated by specific fluorination of phenethylammonium (PEA), used here as the organic cation backbone of the 2D component. By means of time-resolved optoelectronic analysis from the femto- to microsecond regions, we demonstrate a static function of the 2D layer as an electron barrier and homogeneous surface passivant, together with a dynamic role in retarding back charge recombination. Our results reveal a crucial dependence of such beneficial effects with the 2D layer, leading to an enhanced open-circuit voltage (Voc), mostly attributed to the 2D phase which orients parallel on the 3D layer. Such findings provide a deep understanding and delineate precise guidelines for the smart design of multidimensional perovskite interfaces for advanced PVs and beyond.@en

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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Two of the key parameters that characterize the usefulness of organic semiconductors for organic or hybrid organic/inorganic solar cells are the mobility of charges and the diffusion length of excitons. Both parameters are strongly related to the supramolecular organization in the material. In this work we have investigated the relation between the solid-state molecular packing and the exciton diffusion length, charge carrier mobility, and charge carrier separation yield using two perylene diimide (PDI) derivatives which differ in their substitution. We have used the time-resolved microwave photoconductivity technique and measured charge carrier mobilities of 0.32 and 0.02 cm2/(Vs) and determined exciton diffusion lengths of 60 and 18 nm for octyl- and bulky hexylheptyl-imide substituted PDIs, respectively. This diffusion length is independent of substrate type and aggregate domain size. The differences in charge carrier mobility and exciton diffusion length clearly reflect the effect of solid-state packing of PDIs on their optoelectronic properties and show that significant improvements can be obtained by effectively controlling the solid-state packing.@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.

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