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PFAT promotes the secondary growth of PbI2 clusters and the early formation of favorable perovskite phases via a two-step sequential deposition approach.

Lead halide perovskite single crystals have attracted wide interest in the field of X-ray detection due to their excellent photophysical properties. However, their inherent toxicity and high thickness restrict their applications in flexible devices. In this paper, designing a micronanometer-scale X-ray detector based on all-inorganic lead-free CsAg

Tin (Sn)-based perovskites are very promising for the fabrication of low-toxicity lead-free perovskite solar cells (PSCs), but they suffer from easy oxidation of Sn2+ to Sn4+ which leads to poor performance.

Halide perovskite semiconductors are poised to revitalize the field of ionizing radiation detection as they have done to solar photovoltaics. We show that all-inorganic perovskite CsPbBr3 devices resolve 137Cs 662-keV γ-rays with 1.4% energy resolution, as well as other X- and γ-rays with energies ranging from tens of keV to over 1 MeV in ambipolar sensing and unipolar hole-only sensing modes with crystal volumes of 6.65 mm3 and 297 mm3, respectively. We report the scale-up of CsPbBr3 ingots to up to 1.5 inches in diameter with an excellent hole mobility–lifetime product of 8 × 10−3 cm2 V−1 and a long hole lifetime of up to 296 μs. CsPbBr3 detectors demonstrate a wide temperature region from ~2 °C to ~70 °C for stable operation. Detectors protected with suitable encapsulants show a uniform response for over 18 months. Consequently, we identify perovskite CsPbBr3 semiconductor as an exceptional candidate for new-generation high-energy γ-ray detection. Energy resolution of high-energy photon detectors is desired for applications ranging from biomedical imaging to homeland security. In this work, perovskite-based γ-ray detection with 1.4% energy resolution is demonstrated.

The advent of the two-dimensional (2D) family of halide perovskites and their demonstration in 2D/three-dimensional (3D) hierarchical film structures broke new ground toward high device performance and good stability. The 2D Dion-Jacobson (DJ) phase halide perovskites are especially attractive in solar cells because of their superior charge transport properties. Here, we report on 2D DJ phase perovskites using a 3-(aminomethyl)piperidinium (3AMP) organic spacer for the fabrication of mixed Pb/Sn-based perovskites, exhibiting a narrow bandgap of 1.27 eV and a long carrier lifetime of 657.7 ns. Consequently, solar cells employing mixed 2D DJ 3AMP-based and 3D MA

International audience; The optical and light emission properties of tin and lead halide perovskites are remarkable because of the robust room-temperature (RT) performance, broad wavelength tunability, high efficiency, and good quenching resistance to defects. These highly desirable attributes promise to transform current light-emitting devices, phosphors, and lasers. One disadvantage in most of these materials is the sensitivity to moisture. Here, we report a new air-stable one-dimensional (1D) hybrid lead-free halide material (DAO)SnI (DAO, 1,8-octyldiammonium) that is resistant to water for more than 15 h. The material exhibits a sharp optical absorption edge at 2.70 eV and a strong broad orange light emission centered at 634 nm, with a full width at half-maximum (fwhm) of 142 nm (0.44 eV). The emission has a long photoluminescence (PL) lifetime of 582 ns, while the intensity is constant over a very broad temperature range (145-415 K) with a photoluminescence quantum yield (PLQY) of at least 20.3% at RT. Above 415 K the material undergoes a structural phase transition from monoclinic (2/) to orthorhombic ( accompanied by a red shift in the band gap and a quench in the photoluminescence emission. Density functional theory calculations support the trend in the optical properties and the 1D electronic nature of the structure, where the calculated carrier effective masses along the inorganic chain are significantly lower than those perpendicular to the chain. Thin films of the compound readily fabricated from solutions exhibit the same optical properties, but with improved PLQY of 36%, for a 60 nm thick film, among the highest reported for lead-free low-dimensional 2D and 1D perovskites and metal halides.

Mixed-dimensional 2D/3D hybrid halide perovskites retain the stability of 2D perovskites (formula (A′)2(A)₍ₙ₋₁₎PbₙI₍₃ₙ₊₁₎) and long diffusion lengths of the 3D materials (AMX₃), thereby affording devices with extended stability as well as state-of-the art efficiencies approaching those of the 3D materials. These films are made by spin-coating precursor solutions with an arbitrarily large average layer thickness n (⟨n⟩ > 7) to give films with both 2D and 3D phases. Although the 2D and 3D perovskite film formation mechanisms have been studied, little is understood about composite 2D/3D film formation. We used in-situ grazing-incidence wide-angle scattering with synchrotron radiation to characterize the films fabricated from precursor solutions with stoichiometries of (BA)₂(MA)₍ₙ₋₁₎PbₙI₍₃ₙ₊₁₎ (⟨n⟩ = 3, 4, 5, 7, 12, 50, and ∞ (MAPbI₃)). Four different mechanisms are seen depending on the stoichiometry in the precursor solution. Kinetic analysis shows faster and earlier growth of the solvate with increasing ⟨n⟩.

the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2017-A0010907682 made by GENCI; International audience; Two-dimensional hybrid halide perovskites offer high chemical versatility, strong potential in optoelectronics. Here, we report the highest layer thickness perovskites yet to be crystallographically characterized, for the Dion-Jacobson (DJ) family. The seven-layered DJ phase (4AMP)(MA) 6Pb 7I 22 (4AMP =4-aminomethylpyperidinium) shows less distortion in the crystal structure than the Ruddlesden-Popper (RP) phase (BA) 2(MA) 6Pb 7I 22 (BA = butylammonium). The comparison of the DJ and RP perovskites reveals that the fine structural details still influence the optical properties, with the DJ phase maintaining a lower energy absorption edge and photoluminescence emission (1.53 and 1.70 eV) than the RP phase (1.57 and 1.74 eV). Density functional theory (DFT) calculations show that the localized density of states of conduction band minimum and valence band maximum are situated at different parts of the layers, implying separate channels in the structure followed by electrons and holes. Unlocking high-layer-thickness layered perovskites provides accessibility to new perovskites for high-performance optoelectronics.

International audience; Two-dimensional (2D) halide perovskites have extraordinary optoelectronic properties and structural tunability. Among them, the Dion-Jacobson phases with the inorganic layers stacking exactly on top of each other are less explored. Herein, we present the new series of 2D Dion-Jacobson halide perovskites, which adopt the general formula of A′An-1PbnI3n+1 (A′ = 4-(aminomethyl)pyridinium (4AMPY), A = methylammonium (MA), n = 1−4). By modifying the position of the -CH2NH3+ group from 4AMPY to 3AMPY (3AMPY = 3-(aminomethyl)pyridinium), the stacking of the inorganic layers changes from exactly eclipsed to slightly offset. The perovskite octahedra tilts are also different between the two series, with the 3AMPY series exhibiting smaller bandgaps than the 4AMPY series. Compared to the aliphatic cation of the same size (AMP = (aminomethyl)piperidinium), the aromatic spacers increase the rigidity of the cation, reduce the interlayer spacing and decrease the dielectric mismatch between inorganic layer and the organic spacer, showing the indirect but powerful influence of the organic cations on the structure and consequently on the optical properties of the perovskite materials. All A′An-1PbnI3n+1 compounds exhibit strong photoluminescence (PL) at room temperature. Preliminary solar cell devices based on the n = 4 perovskites as absorbers of both series exhibit promising performances, with a champion power conversion efficiency (PCE) of 9.20 % for (3AMPY)(MA)3Pb4I13 based devices, which is higher than the (4AMPY)(MA)3Pb4I13 and the corresponding aliphatic analogue (3AMP)(MA)3Pb4I13 based ones.

There is strong interest in improving the environmental stability of hybrid perovskite solar cells while maintaining high efficiency. Here, we solve this problem by using epilayers of a wide-band-g...

Thorium as a potential nuclear fuel for the next-generation thorium-based molten salt reactors holds significant environmental and economic promise over the current uranium-based nuclear reactors. However, because thorium (Th4+) usually coexists with other rare earth elements, alkali or alkaline earth metals in minerals, or highly acidic radioactive waste, seeking acid-resistant sorbents with excellent selectivity, high capacity, and fast removal rate for Th4+ is still a challenging task. In this work, we investigated a robust layered metal sulfide (KInSn2S6, KMS-5) for Th4+ removal from strong acidic solutions. We report that KMS-5 could capture Th4+ from a 0.1 M HNO3 solution with extremely high efficiency (∼99.9%), fast sorption kinetics (equilibrium time < 10 min), and large distribution coefficient (up to 1.5 × 106 mL/g). Furthermore, KMS-5 exhibited excellent sorption selectivity towards Th4+ in the presence of large amounts of competitive metal ions like Eu3+, Na+, and Ca2+. This extraordinary capture property for Th4+ is attributed to the facile ion exchange of Th4+ with K+ in the interlayers and subsequent formation of a stable coordination complex via Th-S bonds. These results indicate that KMS-5 is a promising functional sorbent for the effective capture of Th4+ from highly acidic solutions.

Low-temperature solution–grown large high-quality perovskite single crystals enable integrated circuits for imaging., The triple-cation mixed-halide perovskite (FAxMAyCs1-x-y)Pb(IzBr1-z)3 (FAMACs) is the best composition for thin-film solar cells. Unfortunately, there is no effective method to prepare large single crystals (SCs) for more advanced applications. Here, we report an effective additive strategy to grow 2-inch-sized high-quality FAMACs SCs. It is found that the judiciously selected reductant [formic acid (FAH)] effectively minimizes iodide oxidation and cation deprotonation responsible for phase segregation. Consequently, the FAMACs SC shows more than fivefold enhancement in carrier lifetimes, high charge mobility, long carrier diffusion distance, as well as superior uniformity and long-term stability, making it possible for us to design high-performance self-powered integrated circuit photodetector. The device exhibits large responsivity, high photoconductive gain, excellent detectivity, and fast response speed; all values are among the highest reported to date for planar-type single-crystalline perovskite photodetectors. Furthermore, an integrated imaging system is fabricated on the basis of 12 × 12 pixelated matrixes of the single-crystal photodetectors.

This roadmap on Nanotechnology for Catalysis and Solar Energy Conversion focuses on the application of nanotechnology in addressing the current challenges of energy conversion: ‘high efficiency, stability, safety, and the potential for low-cost/scalable manufacturing’ to quote from the contributed article by Nathan Lewis. This roadmap focuses on solar-to-fuel conversion, solar water splitting, solar photovoltaics and bio-catalysis. It includes dye-sensitized solar cells (DSSCs), perovskite solar cells, and organic photovoltaics. Smart engineering of colloidal quantum materials and nanostructured electrodes will improve solar-to-fuel conversion efficiency, as described in the articles by Waiskopf and Banin and Meyer. Semiconductor nanoparticles will also improve solar energy conversion efficiency, as discussed by Boschloo et al in their article on DSSCs. Perovskite solar cells have advanced rapidly in recent years, including new ideas on 2D and 3D hybrid halide perovskites, as described by Spanopoulos et al ‘Next generation’ solar cells using multiple exciton generation (MEG) from hot carriers, described in the article by Nozik and Beard, could lead to remarkable improvement in photovoltaic efficiency by using quantization effects in semiconductor nanostructures (quantum dots, wires or wells). These challenges will not be met without simultaneous improvement in nanoscale characterization methods. Terahertz spectroscopy, discussed in the article by Milot et al is one example of a method that is overcoming the difficulties associated with nanoscale materials characterization by avoiding electrical contacts to nanoparticles, allowing characterization during device operation, and enabling characterization of a single nanoparticle. Besides experimental advances, computational science is also meeting the challenges of nanomaterials synthesis. The article by Kohlstedt and Schatz discusses the computational frameworks being used to predict structure–property relationships in materials and devices, including machine learning methods, with an emphasis on organic photovoltaics. The contribution by Megarity and Armstrong presents the ‘electrochemical leaf’ for improvements in electrochemistry and beyond. In addition, biohybrid approaches can take advantage of efficient and specific enzyme catalysts. These articles present the nanoscience and technology at the forefront of renewable energy development that will have significant benefits to society.

International audience; Large organic A cations cannot stabilize the 3D perovskite AMX3 structure because they cannot be accommodated in the cubo-octhedral cage (do not follow the Goldschmidt tolerance factor rule), and they generally template low-dimensional structures. Here we report that the large di-cation aminomethylpyridinium (AMPY), can template novel 3D structures which resemble conventional perovskites. They have the formula (xAMPY)M2I6 (x = 3 or 4, M = Sn2+ or Pb2+) which is doubled the AMX3 formula. However, because of the steric requirement of the Goldschmidt tolerance factor rule, it is impossible for (xAMPY)M2I6 to form proper perovskite structures. Instead, a combination of corner-sharing and edge-sharing connectivity is adopted in these compounds leading to the new 3D structures. DFT calculations reveal that the compounds are indirect-bandgap semiconductors with direct bandgaps presenting at slightly higher energies and dispersive electronic bands. The bandgaps of the Sn and Pb compounds are ~ 1.7 eV and 2.0 eV, respectively, which is slightly higher than the corresponding AMI3 3D perovskites. The Raman spectra for the compounds are diffuse, with a broad rising central peak at very low frequencies around 0 cm-1, a feature that is characteristic of dynamical lattices, highly anharmonic, and dissipative vibrations very similar to the 3D AMX3 perovskites. Devices of (3AMPY)Pb2I6 crystals exhibit clear photoresponse under ambient light without applied bias, reflecting a high carrier mobility (μ) and long carrier lifetime (τ). The devices also exhibit sizable X-ray generated photocurrent with a high μτ product of ~1.2×10-4 cm2 /V and an X-ray sensitivity of 207 μC Gy-1 cm-2.

All-inorganic Bi-based perovskites have attracted much attention due to their excellent stability, environmentally friendly, and low-cost solution processability. However, due to the large exciton binding energy and small light absorption coefficient, the performance of the Bi-based perovskite photodetector (PD) is far behind of the traditional Pb-based perovskite PDs. In this work, the lead-free all-inorganic Cs3Bi2I9 (CBI) perovskite single crystal was synthesized by a space-confined antisolvent-assisted crystallization method for high-performance, semi-transparent, and self-driven PDs with an ITO/SnO2/CBI/PTAA/Au/ITO structure. Electrical and optical properties of Au/ITO transparent electrode were studied considering its figure of merit and device quantum efficiency through optimizing the Au thickness. Finally, our optimized semi-transparent device showed excellent self-driven performance with a large on/off ratio of ∼5700, a high responsivity of 52.06 mA/W, a high detectivity of >1012 Jones, and a large linear dynamic range of up to 140.7 dB. In addition, our device demonstrated excellent characteristics to the weak light detection and the long-term stability. The Au/ITO electrode was adopted and tailored to balance the device performance and transparency, which provides a good route for developing high-performance and transparent devices in the future.

Halide perovskites exhibit remarkably high-performance as semiconductors compared to conventional materials because of an unusually favorable combination of optoelectronic properties. We demonstrate here that solution-grown single-crystals of organic–inorganic hybrid perovskite CH3NH3PbI3 (MAPbI3), implemented in a Schottky-type device design, can produce outstanding hard radiation detectors with high spectral response and low dark current for the first time. Schottky-type MAPbI3 detector achieves an excellent energy resolution of 6.8% for 57Co 122 keV gamma ray. The high detector performance is achieved due to the balanced charge collection efficiency for both electrons and holes, reflected in the high mobility-lifetime (μτ) products of both carriers (∼0.8 × 10–3 cm2/V). MAPbI3 also demonstrates remarkably long electron and hole lifetimes (τe = 10 μs and τh = 17 μs) and impressive operational stability over time. Furthermore, dual-source detection of α particle (5.5 MeV) and γ-ray (59.5 keV) from the 241...

Low-dimensional halide perovskites have recently attracted intense interest as alternatives to the three-dimensional (3D) perovskites because of their greater tunability and higher environmental stability. Herein, we present the new homologous 2D series (NH3CmH2mNH3)(CH3NH3)n−1PbnI3n+1 (m = 4–9; n = 1–4), where m represents the carbon-chain number and n equals layer-thickness number. Multilayer (n > 1) 2D perovskites incorporating diammonium cations were successfully synthesized by the solid-state grinding method for m = 4 and 6 and by the solution method for m = 7–9. Structural characterization by single-crystal X-ray diffraction for the m = 8 and m = 9 series (n = 1–4) reveals that these compounds adopt the Cc space group for even n members and Pc for odd n members. The optical bandgaps are 2.15 eV for two-layer (n = 2), 2.01 eV for three-layer (n = 3), and 1.90 eV for four-layer (n = 4). The materials exhibit excellent solution processability, and casting thin-films of the n = 3 members was successfull...

Hybrid halide perovskite solar cells with mixed cations demonstrate superior optical and electrical properties, especially for lead-based perovskite devices. Here, we report lead-free tin-based perovskite solar cells with diammonium cations, which can significantly improve the device performance. Formamidinium tin iodide (FASnI3) perovskite can incorporate propylenediammonium (PN) and trimethylenediammonium (TN) and retain its three-dimensional structure while at the same time providing better film morphology and optoelectronic properties. As a result, solar cell devices using FASnI3 absorbers mixed with 10% PN and 10% TN achieve higher power conversion efficiencies of 5.85% and 5.53%, respectively, compared to 2.53% of the pristine FASnI3 solar cell. This difference in device performance can be mainly attributed to the reduced leakage current, lower trap-state density, and reduced recombination, as evidenced by our dark current–voltage, space-charge-limited current, and impedance measurements. The result...

Fabricating highly efficient and stable inverted wide-bandgap (WBG) perovskite solar cells (PSCs) is the key factor for developing high-efficiency and stabilized tandem solar cells. Herein, we propose an interfacial engineering strategy to form a 2D/3D perovskite heterojunction using 2-thiopheneethylammonium chloride (TEACl). The thiophene-based 2D/3D perovskite heterojunction improves the optoelectronic properties of the perovskite absorber, passivates the electron and hole traps, increases the activation energy of the ion movement, and lowers the dark saturation current density of the device. As a result, the device with TEACl treatment delivers a champion power conversion efficiency of 20.31% with a 1.68-eV bandgap. In addition, the devices with TEACl treatment exhibit superior stability than the control devices under various testing conditions. Finally, an efficiency of 24.0% is achieved for a 4-terminal perovskite/CIGS tandem solar cell. Our results demonstrate that the thiophene-based 2D/3D perovskite heterojunction is a promising approach for achieving efficient and stable WBG PSCs.

Developing dopant-free hole transporting layers (HTLs) is critical in achieving high-performance and robust state-of-the-art perovskite photovoltaics, especially for the air-sensitive tin-based perovskite systems. The commonly used HTLs require hygroscopic dopants and additives for optimal performance, which adds extra cost to manufacturing and limits long-term device stability. Here we demonstrate the use of a novel tetrakis-triphenylamine (TPE) small molecule prepared by a facile synthetic route as a superior dopant-free HTL for lead-free tin-based perovskite solar cells. The best-performing tin iodide perovskite cells employing the novel mixed-cation ethylenediammonium/formamidinium with the dopant-free TPE HTL achieve a power conversion efficiency as high as 7.23%, ascribed to the HTL's suitable band alignment and excellent hole extraction/collection properties. This efficiency is one of the highest reported so far for tin halide perovskite systems, highlighting potential application of TPE HTL material in low-cost high-performance tin-based perovskite solar cells.

Electron-selective layers (ESLs) and hole-selective layers (HSLs) are critical in high-efficiency organic–inorganic lead halide perovskite (PS) solar cells for charge-carrier transport, separation, and collection. We developed a procedure to assess the quality of the ESL/PS junction by measuring potential distribution on the cross section of SnO2-based PS solar cells using Kelvin probe force microscopy. Using the potential profiling, we compared three types of cells made of different ESLs but otherwise having an identical device structure: (1) cells with PS deposited directly on bare fluorine-doped SnO2 (FTO)-coated glass; (2) cells with an intrinsic SnO2 thin layer on the top of FTO as an effective ESL; and (3) cells with the SnO2 ESL and adding a self-assembled monolayer (SAM) of fullerene. The results reveal two major potential drops or electric fields at the ESL/PS and PS/HSL interfaces. The electric-field ratio between the ESL/PS and PS/HSL interfaces increased in devices as follows: FTO < SnO2-ESL

Tin-based perovskites have very comparable electronic properties to lead-based perovskites and are regarded as possible lower toxicity alternates for solar cell applications. However, the efficiency of tin-based perovskite solar cells is still low and they exhibit poor air stability. Here, we report lead-free tin-based solar cells with greatly enhanced performance and stability using so-called “hollow” ethylenediammonium and methylammonium tin iodide ({en}MASnI3) perovskite as absorbers. Our results show that en can improve the film morphology and most importantly can serve as a new cation to be incorporated into the 3D MASnI3 lattice. When the cation of en becomes part of the 3D structure, a high density of SnI2 vacancies is created resulting in larger band gap, larger unit cell volume, lower trap-state density, and much longer carrier lifetime compared to classical MASnI3. The best-performing {en}MASnI3 solar cell has achieved a high efficiency of 6.63% with an open circuit voltage of 428.67 mV, a short...

Although the perovskite solar cells (PSCs) based on organic hole transport materials (HTMs) have demonstrated excellent photovoltaic performance, there are still some obstacles that limiting their future commercialization, one of which is the device stability. Herein, we first report that depositing a (200) orientated PbS thin film upon organic HTMs as buffer layer can significantly enhance the stability and improve the performance of PSCs. The superior hole extraction efficiency of spiro-OMeTAD/PbS bilayer can balance the charge transfer and the hydrophobic nature of PbS could avoid the permeation of moisture. As a result, the PSCs with PbS buffer layer exhibited a better photovoltaic performance (a champion power conversion efficiency of 19.58%) with respect to the reference cells (18.79%), and maintained almost 100% of its initial PCE after 1000 h stored in ambient air. Furthermore, when suffer from some more severe conditions, the device with PbS retained 56% of its initial PCE after 96 h annealing at 85 °C, while only 25% for the reference cells. Our results provide a simple method to avoid the weakness of organic HTMs, and suggest that PbS thin film could be an alternative buffer layer material in PSCs to simultaneously improve the device stability and photovoltaic performance.