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Methylammonium lead tribromide perovskite (MAPbBr 3 ) is an important material, for example, for light-emitting applications and tandem solar cells. The relevant photophysical properties are governed by a plethora of phenomena resulting from the complex and relatively poorly understood interplay of excitons and free charge carriers in the excited state. In this study, we combine transient spectroscopies in the visible and terahertz range to investigate the presence and evolution of excitons and free charge carriers at ultrafast times upon excitation at various photon energies and densities. For above- and resonant band-gap excitation, we find that free charges and excitons coexist and that both are mainly promptly generated within our 50-100 fs experimental time resolution. However, the exciton-to-free charge ratio increases upon decreasing the phonon energy toward resonant band gap excitation. The free charge signatures dominate the transient absorption response for above-band-gap excitation and low excitation densities, masking the excitonic features. With resonant band gap excitation and low excitation densities, we find that although the exciton density increases, free charges remain. We show evidence that the excitons localize into shallow trap and/or Urbach tail states to form localized excitons (within tens of picoseconds) that subsequently get detrapped. Using high excitation densities, we demonstrate that many-body interactions become pronounced and effects such as the Moss-Burstein shift, band gap renormalization, excitonic repulsion, and the formation of Mahan excitons are evident. The coexistence of excitons and free charges that we demonstrate here for photoexcited MAPbBr 3 at ultrafast time scales confirms the high potential of the material for both light-emitting diode and tandem solar cell applications., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Interfaces in perovskite solar cells play a crucial role in their overall performance, and therefore, detailed fundamental studies are needed for a better understanding. In the case of the classical n-i-p architecture, TiO 2 is one of the most used electron-selective layers and can induce chemical reactions that influence the performance of the overall device stack. The interfacial properties at the TiO 2 /perovskite interface are often neglected, owing to the difficulty in accessing this interface. Here, we use X-rays of variable energies to study the interface of (compact and mesoporous) TiO 2 /perovskite in such a n-i-p architecture. The X-ray photoelectron spectroscopy and X-ray absorption spectroscopy methods show that the defect states present in the TiO 2 layer are passivated by a chemical interaction of the perovskite precursor solution during the formation of the perovskite layer and form an organic layer at the interface. Such passivation of intrinsic defects in TiO 2 removes charge recombination centers and shifts the bands upward. Therefore, interface defect passivation by oxidation of Ti 3+ states, the organic cation layer, and an upward band bending at the TiO 2 /perovskite interface explain the origin of an improved electron extraction and hole-blocking nature of TiO 2 in the n-i-p perovskite solar cells.

Chemically processed methylammonium tin-triiodide (CH 3 NH 3 SnI 3 ) films include Sn in different oxidation states, leading to poor stability and low power conversion efficiency of the resulting solar cells (PSCs). The development of absorbers with Sn [2+] only has been identified as one of the critical steps to develop all Sn-based devices. Here, we report on coevaporation of CH 3 NH 3 I and SnI 2 to obtain absorbers with Sn being only in the preferred oxidation state [+2] as confirmed by X-ray photoelectron spectroscopy. The Sn [4+]-free absorbers exhibit smooth highly crystalline surfaces and photoluminescence measurements corroborating their excellent optoelectronic properties. The films show very good stability under heat and light. Photoluminescence quantum yields up to 4 × 10 -3 translate in a quasi Fermi-level splittings exceeding 850 meV under one sun equivalent conditions showing high promise in developing lead-free, high efficiency, and stable PSCs.

A key direction toward managing extrinsic instabilities in perovskite solar cells (PSCs) is encapsulation. Thus, a suitable sealing layer is required for an efficient device encapsulation, preventing moisture and oxygen ingression into the perovskite layer. In this work, a solution-based, low-cost, and commercially available bilayer structure of poly(methyl methacrylate)/styrene-butadiene (PMMA/SB) is investigated for PSCs encapsulation. Encapsulated devices retained 80% of the initial power conversion efficiency (PCE) at 85 °C temperature and 85% relative humidity after 100 h, while reference devices without SB (only PMMA) suffer from rapid and intense degradation after only 2 h, under the same condition. In addition, encapsulated devices retained 95% of the initial PCE under -15 °C freezing temperature after 6 h and retained ∼80% of the initial PCE after immersion in HCl (37%) for 90 min. Moreover, applying an additional aluminum metal sheet on the PMMA/SB protective bilayer leads to the improvement of device stability up to 500 h under outdoor illumination, retaining almost 90% of the initial PCE. Considering the urge to develop reliable, scalable, and simple encapsulation for future large-area PSCs, this work establishes solution-based bilayer encapsulation, which is applicable for flexible solar modules as well as other optoelectronic devices such as light-emitting devices and photodetectors.improvement of device stability up to 500 h under outdoor illumination, retaining almost 90% of the initial PCE. Considering the urge to develop reliable, scalable, and simple encapsulation for future large-area PSCs, this work establishes solution-based bilayer encapsulation, which is applicable for flexible solar modules as well as other optoelectronic devices such as light-emitting devices and photodetectors.

Understanding and controlling the crystallization of organic-inorganic perovskite materials is important for their function in optoelectronic applications. This control is particularly delicate in scalable single-step thermal annealing methods. In this work, the crystallization mechanisms of flash infrared-annealed perovskite films, grown on substrates with lithographically patterned Au nucleation seeds, are investigated. The patterning enables the in situ observation to study the crystallization kinetics and the precise control of the perovskite nucleation and domain growth, while retaining the characteristic polycrystalline micromorphology with larger crystallites at the boundaries of the crystal domains, as shown by electron backscattering diffraction. Time-resolved photoluminescence measurements reveal longer charge carrier lifetimes in regions with large crystallites on the domain boundaries, relative to the domain interior. By increasing the nucleation site density, the proportion of larger crystallites is increased. This study shows that the combination of rapid thermal annealing with nucleation control is a promising approach to improve perovskite crystallinity and thereby ultimately the performance of optoelectronic devices.

Negative capacitance in the low-frequency domain and inverted hysteresis are familiar features in perovskite solar cells, which origin is still under discussion. Here we use impedance spectroscopy to analyze these responses in methylammonium lead bromide cells treated with lithium cations at the electron-selective layer/perovskite interface and in iodide devices exposed to different relative humidity conditions. Employing the surface polarization model , we obtain a time constant associated with the kinetics of the interaction of ions/vacancies with the surface, τ kin , in the range of 10 0 -10 2 s for all the cases exhibiting both features. These interactions lead to a decrease in the overall recombination resistance, modifying the low-frequency perovskite response and yielding a flattening of the cyclic voltammetry. As a consequence of these results we find that negative capacitance and inverted hysteresis lead to a decrease in the fill factor and photovoltage values.

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 (MAPbI 3 ) 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.

PbS quantum dots (QDs) have been extensively studied for photovoltaic applications, thanks to their facile and low-cost fabrication processing and interesting physical properties such as size dependent and tunable band gap. However, the performance of PbS QD-based solar cells is highly sensitive to the humidity level in the ambient air, which is a serious obstacle toward its practical applications. Although it has been previously revealed that oxygen doping of the hole transporting layer can mitigate the cause of this issue, the suggested methods to recover the device performance are time-consuming and relatively costly. Here, we report a low-power oxygen plasma treatment as a rapid and low-cost method to effectively recover the device performance and stability. Our optimization results show that a 10 min treatment is the best condition, resulting in an enhanced power conversion efficiency from 6.9% for the as-prepared device to 9% for the plasma treated one. Moreover, our modified device shows long-term shelf-life stability.

Organo-lead halide perovskites have emerged as promising light harvesting materials for solar cells. The ability to prepare high quality films with a low concentration of defects is essential for obtaining high device performance. Here, we advance the procedure for the fabrication of efficient perovskite solar cells (PSCs) based on mechanochemically synthesized MAPbI 3 . The use of mechano-perovskite for the thin film formation provides a high degree of control of the stoichiometry and allows for the growth of relatively large crystalline grains. The best device achieved a maximum PCE of 17.5% from a current-voltage scan (J-V), which stabilized at 16.8% after 60 s of maximum power point tracking. Strikingly, PSCs based on MAPbI 3 mechanoperovskite exhibit lower "hysteretic" behavior in comparison to that comprising MAPbI 3 obtained from the conventional solvothermal reaction between PbI 2 and MAI. To gain a better understanding of the difference in J-V hysteresis, we analyze the charge/ion accumulation mechanism and identify the defect energy distribution in the resulting MAPbI 3 based devices. These results indicate that the use of mechanochemically synthesized perovskites provides a promising strategy for the formation of crystalline films demonstrating slow charge recombination and low trap density.

In this work we perform a computational study comparing the influence of monovalent cation substitution by methylammonium (MA + ), cesium (Cs + ), and rubidium (Rb + ) on the properties of formamidinium lead triiodide (FAPbI 3 )-based perovskites. The relative stability of the desired, photoactive perovskite α phase ("black phase") and the nonphotoactive, nonperovskite δ phase ("yellow phase") is studied as a function of dopant nature, concentration and temperature. Cs + and Rb + are shown to be more efficient in the stabilization of the perovskite α phase than MA + . Furthermore, varying the dopant concentration allows changing the relative stability at different temperatures, in particular stabilizing the α phase already at 200 K. Upon Cs + or Rb + doping, the corresponding onset of the optical spectrum is blue-shifted by 0.1-0.2 eV with respect to pure FAPbI 3 .

Perovskite solar cells (PSCs) have now achieved efficiencies in excess of 22%, but very little is known about their long-term stability under thermal stress. So far, stability reports have hinted at the importance of substituting the organic components, but little attention has been given to the metal contact. We investigated the stability of state-of-the-art PSCs with efficiencies exceeding 20%. Remarkably, we found that exposing PSCs to a temperature of 70 °C is enough to induce gold migration through the hole-transporting layer (HTL), spiro-MeOTAD, and into the perovskite material, which in turn severely affects the device performance metrics under working conditions. Importantly, we found that the main cause of irreversible degradation is not due to decomposition of the organic and hybrid perovskite layers. By introducing a Cr metal interlayer between the HTL and gold electrode, high-temperature-induced irreversible long-term losses are avoided. This key finding is essential in the quest for achieving high efficiency, long-term stable PSCs which, in order to be commercially viable, need to withstand hard thermal stress tests.

Organic-inorganic perovskites are highly promising solar cell materials with laboratory-based power conversion efficiencies already matching those of established thin film technologies. Their exceptional photovoltaic performance is in part attributed to the presence of efficient radiative recombination pathways, thereby opening up the possibility of efficient light-emitting devices. Here, we demonstrate optically pumped amplified spontaneous emission (ASE) at 780 nm from a 50 nm-thick film of CH3NH3PbI3 perovskite that is sandwiched within a cavity composed of a thin-film (∼7 μm) cholesteric liquid crystal (CLC) reflector and a metal back-reflector. The threshold fluence for ASE in the perovskite film is reduced by at least two orders of magnitude in the presence of the CLC reflector, which results in a factor of two reduction in threshold fluence compared to previous reports. We consider this to be due to improved coupling of the oblique and out-of-plane modes that are reflected into the bulk in addition to any contributions from cavity modes. Furthermore, we also demonstrate enhanced ASE on flexible reflectors and discuss how improvements in the quality factor and reflectivity of the CLC layers could lead to single-mode lasing using CLC reflectors. Our work opens up the possibility of fabricating widely wavelength-tunable "mirror-less" single-mode lasers on flexible substrates, which could find use in applications such as flexible displays and friend or foe identification.

Structure control in solution-processed hybrid perovskites is crucial to design and fabricate highly efficient solar cells. Here, we utilize in situ grazing incidence wide-angle X-ray scattering and scanning electron microscopy to investigate the structural evolution and film morphologies of methylammonium lead tri-iodide/chloride (CH3NH3PbI(3-x)Cl(x)) in mesoporous block copolymer derived alumina superstructures during thermal annealing. We show the CH3NH3PbI(3-x)Cl(x) material evolution to be characterized by three distinct structures: a crystalline precursor structure not described previously, a 3D perovskite structure, and a mixture of compounds resulting from degradation. Finally, we demonstrate how understanding the processing parameters provides the foundation needed for optimal perovskite film morphology and coverage, leading to enhanced block copolymer-directed perovskite solar cell performance.

The highest efficiencies in solution-processable perovskite-based solar cells have been achieved using an electron collection layer that requires sintering at 500 °C. This is unfavorable for low-cost production, applications on plastic substrates, and multijunction device architectures. Here we report a low-cost, solution-based deposition procedure utilizing nanocomposites of graphene and TiO2 nanoparticles as the electron collection layers in meso-superstructured perovskite solar cells. The graphene nanoflakes provide superior charge-collection in the nanocomposites, enabling the entire device to be fabricated at temperatures no higher than 150 °C. These solar cells show remarkable photovoltaic performance with a power conversion efficiency up to 15.6%. This work demonstrates that graphene/metal oxide nanocomposites have the potential to contribute significantly toward the development of low-cost solar cells.

Recently, inorganic and hybrid light absorbers such as quantum dots and organometal halide perovskites have been studied and applied in fabricating thin-film photovoltaic devices because of their low-cost and potential for high efficiency. Further boosting the performance of solution processed thin-film solar cells without detrimentally increasing the complexity of the device architecture is critically important for commercialization. Here, we demonstrate photocurrent and efficiency enhancement in meso-superstructured organometal halide perovskite solar cells incorporating core-shell Au@SiO2 nanoparticles (NPs) delivering a device efficiency of up to 11.4%. We attribute the origin of enhanced photocurrent to a previously unobserved and unexpected mechanism of reduced exciton binding energy with the incorporation of the metal nanoparticles, rather than enhanced light absorption. Our findings represent a new aspect and lever for the application of metal nanoparticles in photovoltaics and could lead to facile tuning of exciton binding energies in perovskite semiconductors.

We demonstrate the transition from isolated to collective optical modes in plasmonic oligomers. Specifically, we investigate the resonant behavior of planar plasmonic hexamers and heptamers with gradually decreasing the interparticle gap separation. A pronounced Fano resonance is observed in the plasmonic heptamer for separations smaller than 60 nm. The spectral characteristics change drastically upon removal of the central nanoparticle. Our work paves the road toward complex hierarchical plasmonic oligomers with tailored optical properties.

Highly efficient fabrication of well-ordered, embedded gold nanodot matrices using diffraction mask projection laser ablation is demonstrated. These gold nanodot arrays are ideally generated onto sapphire substrates but do also form onto AlO(x) thin films, enabling the application to arbitrary bulk substrates. Well-ordered gold dots become embedded into the Al(2)O(3) substrate during the process, thus improving their mechanical stability, chemical inertness, and technological compliance. Such substrates may be useful, for example, to enhance solar-cell efficiency by surface plasmons or as convenient, biocompatible focusing elements in nearfield optical tweezers.

The reaction of (PEt(3))(2)Ni(eta(2)-C(14)H(10)), a source of the reactive Ni(PEt(3))(2) moiety, with 1,2,4,5-F(4)C(6)H(2) yields a mixture of three C-F bond activation products that include the unexpected products (PEt(3))(2)NiF-2,3,5,6-F(4)C(6)H and (PEt(3))(2)NiF-2,3,5-F(3)C(6)H(2). Monitoring the reaction mixture via (19)F and (1)H NMR also reveals the presence of the C-H bond activation product, (PEt(3))(2)NiH-2,3,5,6-F(4)C(6)H which is produced in a rapid equilibrium reaction. This observation provides insight into the steps necessary to modify nickel complexes for selective C-F bond activation in a variety of polyfluorinated aromatic substrates, but also expands the potential of simple nickel compounds for C-H bond activation and functionalization reactions.