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The dynamic nature of the metal halide perovskite lattice upon photoexcitation plays a vital role in their properties. Here we report an observation of light-induced structure dynamics in quasi-2D Ruddlesden-Popper phase perovskite thin films and its impact on the carrier transport properties. By a time-resolved X-ray scattering technique, we observe a rapid lattice expansion upon photoexcitation, followed by a slow relaxation over the course of 100 ns in the dark. Theoretical modeling suggests that the expansion originates from the lattice's thermal fluctuations caused by photon energy deposition. Power dependent optical spectroscopy and photoconductivity indicate that high laser powers triggered a strong local structural disorder, which increased the charge dissociation activation energy that results in localized transport. Our study investigates the impact of laser energy deposition on the lattices and the subsequent carrier transport properties, that are relevant to device operations.

Compared with their three-dimensional (3D) counterparts, low-dimensional metal halide perovskites (2D and quasi-2D; B

SUMMARYRuddlesden-Popper (RP) perovskites are two-dimensional semiconductors for high performance devices. In this work, we report a long in-plane charge carrier diffusion length in 2D RP perovskite single crystals probed by scanning photocurrent microscopy. Carrier diffusion lengths of 7~14 µm are observed when the number of PbI6-2 octahedrons between organic spacers increases from 1 to 3. By detailed light intensity and electric field-dependent photocurrent measurements, we attribute the observed long diffusion length to the dominating dissociated free carrier transport. This is further validated by time-resolved photoluminescence measurements where the decay lifetime increases in the presence of an electric field. From our experiments, we conclude that the in-plane transport in RP perovskites is efficient because of the partial free carrier generation overcoming strong excitonic effects. Our results suggest that semiconducting devices fabricated from RP perovskite single crystals can be as efficient as their 3D counterparts.

Perovskite nanocrystals embedded in metal–organic frameworks (PeMOF) are a new nanoscale heterostructure for stable photonic sources. This perspective discusses the properties of PeMOF structures and their current progress in photonic devices.

Perovskite solar cell stability was investigated in moisture and gas mixtures. Moisture accelerates the degradation rate, but once light is removed, the performance is recoverable.

Perovskite nanocrystals are exceptional candidates for light-emitting diodes (LEDs). However, they are unstable in the solid film and tend to degrade back to the bulk phase, which undermines their potential for LEDs. Here we demonstrate that perovskite nanocrystals stabilized in metal–organic framework (MOF) thin films make bright and stable LEDs. The perovskite nanocrystals in MOF thin films can maintain the photoluminescence and electroluminescence against continuous ultraviolet irradiation, heat and electrical stress. As revealed by optical and X-ray spectroscopy, the strong emission originates from localized carrier recombination. Bright LEDs made from perovskite-MOF nanocrystals are demonstrated with a maximum external quantum efficiency of over 15% and a high brightness of over 105 cd m−2 after the device reaches stabilization. During LED operation, the nanocrystals can be well preserved, free of ion migration or crystal merging through protection by the MOF matrix, leading to a stable performance over 50 hours. The use of metal–organic frameworks helps protect perovskite nanocrystals, resulting in bright, stable light-emitting diodes.

Summary The one-step antisolvent approach is a widely employed method for fabricating perovskite devices at a low cost. However, the current antisolvent approach requires a strict set of processing conditions to obtain high-quality perovskite layers. Here, we introduce sulfolane as an additive in the perovskite precursor to convert the perovskite phase via a new reaction route, providing a large degree of flexibility to process crystalline perovskite layers with high uniformity on a large scale. As it is revealed by X-ray diffraction and Fourier-transform infrared spectroscopy findings, we find that the key concept lies in intermolecular hydrogen-bonding forces’ interaction between sulfolane and methylammonium iodide, which slows down the nucleation and subsequently the crystallization process. As a result, we demonstrate a mini module, 36.6 cm2 active area, and achieve a record PCE of 16.06%. More importantly, the encapsulated mini module retained about 90% of the initial performance after operating at the maximum power point under simulated AM1.5G irradiation for 250 h at 50°C.

Organic–inorganic hybrid perovskites have electronic and optoelectronic properties that make them appealing in many device applications1–4. Although many approaches focus on polycrystalline materials5–7, single-crystal hybrid perovskites show improved carrier transport and enhanced stability over their polycrystalline counterparts, due to their orientation-dependent transport behaviour8–10 and lower defect concentrations11,12. However, the fabrication of single-crystal hybrid perovskites, and controlling their morphology and composition, are challenging12. Here we report a solution-based lithography-assisted epitaxial-growth-and-transfer method for fabricating single-crystal hybrid perovskites on arbitrary substrates, with precise control of their thickness (from about 600 nanometres to about 100 micrometres), area (continuous thin films up to about 5.5 centimetres by 5.5 centimetres), and composition gradient in the thickness direction (for example, from methylammonium lead iodide, MAPbI3, to MAPb0.5Sn0.5I3). The transferred single-crystal hybrid perovskites are of comparable quality to those directly grown on epitaxial substrates, and are mechanically flexible depending on the thickness. Lead–tin gradient alloying allows the formation of a graded electronic bandgap, which increases the carrier mobility and impedes carrier recombination. Devices based on these single-crystal hybrid perovskites show not only high stability against various degradation factors but also good performance (for example, solar cells based on lead–tin-gradient structures with an average efficiency of 18.77 per cent). A solution-based lithography-assisted epitaxial-growth-and-transfer method is used to fabricate single-crystal hybrid perovskites on any surface, with precise control of the thickness, area and chemical composition gradient.

The intrinsic photophysical origin of lead halide perovskites (LHPs) that are used successfully in optolectronic applications remains hotly debated. Here, by using ultrafast X-ray transient absorption spectroscopy, we successfully tracked the fate of photogenerated charge carriers at room temperature within the thin films of two classic LHPs, namely, MAPbBr3 (MA = CH3NH3) and FAPbBr3 [FA = CH(NH2)2]. We clearly observed in both thin films that the hole polaron is formed by localizing the photogenerated hole at the Br 4p orbital and concurrently distorting the local structure surrounding the Br atom after the photoexcitation. Furthermore, the larger FA cation in the cavity of the [PbBr6]4- octahedral framework induces a stronger hole polaron effect due to the hybridization of its p orbital into valence and conduction bands, correlating with the slower charge carrier recombination dynamics. Our direct experimental observation of the localized hole polaron in perovskites should advance the fundamental comprehension of charge carrier behavior within LHPs and their related devices.

Gamma-ray spectroscopy that quantifies the gamma-ray energies is a critical technology widely needed in astrophysics, nuclear material detection and medical treatment. The key is to precisely count gamma-ray photons using sensitive detectors. In this paper, we investigate the operational principles of chlorine-doped methylammonium lead tribromide (MAPbBr3−xClx) perovskite single crystal detectors that can efficiently count gamma-ray photon events with electrical pulses. Specifically, we find the main dark current originates from the thermally activated electron injection from the impurities, and using high work function contacts can block out the dark noise thus allows for efficient pulse collection at higher electrical fields ∼500 V/cm. As a result, we observe strong electrical pulses when exposing the detector under radioactive sources emitting gamma-ray photons at various energies. Our results also reveal the fundamental issues that prevent the reliable observation of photo-electric peak. This work suggest pathway towards energy resolved gamma-ray spectroscopy using perovskite crystal detectors.

Metal-halide perovskites are emerging materials for radiation sensing featuring high absorption cross section, high charge mobility, and long carrier lifetime enabling superior detection efficiencies even at room temperature. Perovskite detector technologies are more complex involving different detecting modes and device architectures. To elucidate the working principles, we provide a Perspective on the device structures and the operational principles of halide perovskite direct conversion detectors for radiation sensing. We will first discuss different detection modes and introduce the commonly used device architectures and their working principles. Based on our work and pioneer developments in the field, we will next compare the performances of the reported detectors. Additionally, we will summarize the single crystal detectors and polycrystalline thin film devices and discuss their advantages and disadvantages for different applications. Finally, we provide a future Perspective on the critical problems that must be addressed to commercialize this technology.

Compared with their three-dimensional counterparts, low-dimensional metal halide perovskites with periodic inorganic/organic structures have shown promising stability and hysteresis-free electrical performance, which paves the way for next-generation optoelectronic devices. However, when integrated in devices, they have relatively limited efficiencies because devices usually require carrier transport through the film thickness direction. In conventionally grown single crystals, the carrier transport in the thickness direction is hindered by the insulating organic spacers. In addition, the strong quantum confinement from the organic spacers limits the generation and transport of free carriers. The carrier dynamics is further compromised by the presence of grain boundaries in polycrystals. Here, we report a low-dimensional metal halide perovskite superlattice with efficient carrier transport in three dimensions by epitaxial growth. Epitaxy on a slightly lattice-mismatched substrate compresses the organic spacers in the superlattice, which weakens the quantum confinement and further improves carrier dynamics. The performance of a low-dimensional perovskite superlattice solar cell has been certified under the quasi-steady state for the first time. Moreover, the device shows an unusually high open-circuit voltage, due to a unique intra-band exciton relaxation mechanism.

International audience; Despite the remarkable optoelectronic properties of halide perovskites, achieving reproducible field effect transistor (FET) action in polycrystalline films at room temperature has been challenging and represents a fundamental bottleneck for understanding electronic charge transport in these materials. In this work, we report halide perovskite-based FET operation at room temperature with negligible hysteresis. Extensive measurements and device modeling reveal that incorporating high-k dielectrics enables modulation of the channel conductance. Furthermore, continuous bias cycling or resting allows dynamical reconfiguration of the FETs between p-type behavior and ambipolar FET with balanced electron and hole transport and an ON/OFF ratio up to 104 and negligible degradation in transport characteristics over 100 cycles. These results elucidate the path for achieving gate modulation in perovskite thin-films and provide a platform to understand the interplay between the perovskite structure, and external stimuli such as photons, fields and functional substrates, which will lead to novel and emergent properties.

Electron sources are a critical component in a wide range of applications such as electron-beam accelerator facilities, photomultipliers, and image intensifiers for night vision. We report efficient, regenerative and low-cost electron sources based on solution-processed halide perovskites thin films when they are excited with light with energy equal to or above their bandgap. We measure a quantum efficiency up to 2.2% and a lifetime of more than 25 h. Importantly, even after degradation, the electron emission can be completely regenerated to its maximum efficiency by deposition of a monolayer of Cs. The electron emission from halide perovskites can be tuned over the visible and ultraviolet spectrum, and operates at vacuum levels with pressures at least two-orders higher than in state-of-the-art semiconductor electron sources., Electron sources play as important component in a wide range of applications. Here, the authors demonstrate efficient, regenerative, and low-cost electron sources based on solution-processed halide perovskite thin films with quantum efficiency up to 2.2% and a lifetime of more than 25 h.

The continuing improvement in quantum efficiency (above 90% for single visible photons), reduction in noise (below 1 electron per pixel), and shrink in pixel pitch (less than 1 micron) motivate billion-pixel X-ray cameras (BiPC-X) based on commercial CMOS imaging sensors. We describe BiPC-X designs and prototype construction based on flexible tiling of commercial CMOS imaging sensors with millions of pixels. Device models are given for direct detection of low energy X-rays ($, Comment: 6 pages, 8 figures

We in-situ observe the ultrafast dynamics of trapped carriers in organic methyl ammonium lead halide perovskite thin films by ultrafast photocurrent spectroscopy with a sub-25 picosecond time resolution. Upon ultrafast laser excitation, trapped carriers follow a phonon assisted tunneling mechanism and a hopping transport mechanism along ultra-shallow to shallow trap states ranging from 1.72–11.51 millielectronvolts and is demonstrated by time-dependent and independent activation energies. Using temperature as an energetic ruler, we map trap states with ultra-high energy resolution down to, Defect states in perovskites dictate the charge carriers behaviour, thus the ultimate optical and electrical properties. Here, the authors in-situ investigate trapped carrier dynamics in MAPbI3 thin films with ultra-fast temporal and high energetic resolution by means of ultrafast photocurrent spectroscopy.

Efficient photovoltaic cells based on thin films of solution-processed 2D Ruddlesden–Popper hybrid perovskites (RPPs) represent an exciting breakthrough due to their enhanced tunability and chemica...

Halide perovskites are promising optoelectronic semiconductors. For applications in solid-state detectors that operate in low photon flux counting mode, blocking interfaces are essential to minimize the dark current noise. Here, we investigate the interface between methylammonium lead tri-iodide (MAPbI3) single crystals and commonly used high and low work function metals to achieve photon counting capabilities in a solid-state detector. Using scanning photocurrent microscopy, we observe a large Schottky barrier at the MAPbI3/Pb interface, which efficiently blocks dark current. Moreover, the shape of the photocurrent profile indicates that the MAPbI3 single-crystal surface has a deep fermi level close to that of Au. Rationalized by first-principle calculations, we attribute this observation to the defects due to excess iodine on the surface underpinning emergence of deep band-edge states. The photocurrent decay profile yields a charge carrier diffusion length of 10-25 μm. Using this knowledge, we demonstrate a single-crystal MAPbI3 detector that can count single γ-ray photons by producing sharp electrical pulses with a fast rise time of

Rolston et al . suggest through a convective heating scheme that the mechanism of light-induced lattice expansion is from light-induced thermal heating. We bring out key differences in the physical observables that are not discussed and different from what is observed in the original paper by Tsai et al .

Solution-processed 2D perovskite diodes with fully depleted junction enable highly sensitive and robust thin-film x-ray detectors., Solid-state radiation detectors, using crystalline semiconductors to convert radiation photons to electrical charges, outperform other technologies with high detectivity and sensitivity. Here, we demonstrate a thin-film x-ray detector comprised with highly crystalline two-dimensional Ruddlesden-Popper phase layered perovskites fabricated in a fully depleted p-i-n architecture. It shows high diode resistivity of 1012 ohm·cm in reverse-bias regime leading to a high x-ray detecting sensitivity up to 0.276 C Gyair−1 cm−3. Such high signal is collected by the built-in potential underpinning operation of primary photocurrent device with robust operation. The detectors generate substantial x-ray photon–induced open-circuit voltages that offer an alternative detecting mechanism. Our findings suggest a new generation of x-ray detectors based on low-cost layered perovskite thin films for future x-ray imaging technologies.

Light‐emitting diodes (LEDs) made with quasi‐2D/3D and layered perovskites have undergone an unprecedented surge as their external quantum efficiency (EQE) is rapidly approaching other lighting technologies. Manipulating the charge recombination pathway in semiconductors is highly desirable for improving the device performance. This study reports high‐performance layered perovskites LEDs with benzyl ring as spacer where radiative recombination lifetime is longer, compared with much shorter alkyl chain spacer yields. Based on detailed optical and X‐ray absorption spectroscopy measurements, direct signature of charges localization is observed near the band edge in exchange with the shallow traps in benzyl organics containing layered perovskites. As a result, it boosts the photoluminescence intensity by 7.4 times compared to that made with the alkyl organics. As a demonstration, a bright LED made with the benzyl organics with current efficiency of 23.46 ± 1.52 cd A−1 is shown when the device emits at a high brightness of 6.6 ± 0.93 × 104 cd m−2. The average EQE is 9.2% ± 1.43%, two orders of magnitude higher than the device made with alkyl organics. The study suggests that the choices of organic spacers provide a path toward the manipulation of charge recombination, essential for efficient optoelectronic device fabrications., The charge recombination pathways in layered perovskites are closely related to the choice of the organic spacers. Using phenylethylamine as organic spacer greatly extends the charge recombination lifetime by localizing the hole near the band edge. Efficient Ruddlesden–Popper layered perovskites light emitting‐diodes are thus demonstrated.

Progress in flexible organic electronics necessitates a full understanding of how local inhomogeneities impact electronic and ionic conduction pathways and underlie macroscopic device characteristics. We used frequency- and time-resolved macro- and nanoprobe measurements to study spatiotemporal characteristics of multiscale charge transport dynamics in a series of ternary-blended hybrid organic inorganic perovskites (HOIPs) (MA0.95-xFAxCs0.05PbI3). We show that A-site cation composition defines charge transport mechanisms across broad temporal (102-10-6 s) and spatial (millimeters-picometers) scales. Ab initio molecular dynamic simulations suggest that insertion of FA results in a dynamic lattice, improved ion transport, and dipole screening. We demonstrate that correlations between macro- and nanoscale measurements provide a pathway for accessing distribution of relaxation in nanoscale polarization and charge transport dynamics of ionically conductive functional perovskites.

Polycrystalline perovskite film-based X-ray detector is an appealing technology for assembling large scale imager by printing methods. However, thick crystalline layer without trap and solvent residual is challenging to fabricate. Here, the authors report a solution method to produce high quality quasi-2D perovskite crystalline layers and detectors that are suitable for X-ray imaging. By introducing n-butylamine iodide into methylammonium lead iodide precursor and coating at elevated temperatures, compact and crystalline layers with exceptional uniformity are obtained on both rigid and flexible substrates. Photodiodes built with the quasi-2D layers exhibit a low dark current and stable operation under constant electrical field over 96 h in dark, and over 15 h under X-ray irradiation. The detector responds sensitively under X-ray, delivering a high sensitivity of 1214 µC Gy

In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)(2)(A)(n−1)M(n)X(3n+1) [where A = Cs(+), CH(3)NH(3)(+), HC(NH(2))(2)(+); A′ = ammonium cation acting as spacer; M = Ge(2+), Sn(2+), Pb(2+); and X = Cl(−), Br(−), I(−)] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members (n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n. To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure–function relationships. We report the effective synthesis of the highest iodide n-members yet, namely (CH(3)(CH(2))(2)NH(3))(2)(CH(3)NH(3))(5)Pb(6)I(19) (n = 6) and (CH(3)(CH(2))(2)NH(3))(2)(CH(3)NH(3))(6)Pb(7)I(22) (n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH(3)(CH(2))(2)NH(3))(2)(CH(3)NH(3))(8)Pb(9)I(28)” (“n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔH(f)), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n-dependent solar cell efficiency in the range of 9–12.6% in these higher n-members, highlighting the strong promise of these materials for high-performance devices.