Perovskite superlattices with efficient carrier dynamics.

Compared with their three-dimensional (3D) counterparts, low-dimensional metal halide perovskites (2D and quasi-2D; B2An-1MnX3n+1, such as B = R-NH3+, A = HC(NH2)2+, Cs+; M = Pb2+, Sn2+; X = Cl-, Br-, I-) with periodic inorganic-organic structures have shown promising stability and hysteresis-free electrical performance1-6. However, their unique multiple-quantum-well structure limits the device efficiencies because of the grain boundaries and randomly oriented quantum wells in polycrystals7. In single crystals, the carrier transport through the thickness direction is hindered by the layered insulating organic spacers8. Furthermore, the strong quantum confinement from the organic spacers limits the generation and transport of free carriers9,10. Also, lead-free metal halide perovskites have been developed but their device performance is limited by their low crystallinity and structural instability11. Here we report a low-dimensional metal halide perovskite BA2MAn-1SnnI3n+1 (BA, butylammonium; MA, methylammonium; n = 1, 3, 5) superlattice by chemical epitaxy. The inorganic slabs are aligned vertical to the substrate and interconnected in a criss-cross 2D network parallel to the substrate, leading to efficient carrier transport in three dimensions. A lattice-mismatched substrate compresses the organic spacers, which weakens the quantum confinement. The performance of a superlattice solar cell has been certified under the quasi-steady state, showing a stable 12.36% photoelectric conversion efficiency. Moreover, an intraband exciton relaxation process may have yielded an unusually high open-circuit voltage (VOC).

A fabrication process for flexible single-crystal perovskite devices.

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).

Light-Induced Structural Dynamics and Charge Transport in Layered Halide Perovskite Thin Films.

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.

Accessing One-Dimensional Chains of Halogenoindates(III) in Organic-Inorganic Hybrids.

Organic-inorganic hybrids of halogenoindates(III) are typically represented by one of the zero-dimensional units: InX4-, InX52-, InX63-, or In2X115-. Higher dimensional anionic forms, although not forbidden, have remained almost elusive. Here we report for the first time In3+-based organic-inorganic hybrids, (C4H5N2S)2InCl5 and (C4H5N2S)2InBr5, with 1D anionic chains of trans-halide-bridged InX6 octahedra whose formation is guided by 2-mercaptopyrimidinium cations (C4H5N2S+). The chains are characterized by the significant ease of deformation, which is reflected in the elongation of the bridging bonds or the displacement of In3+ ions. The materials show a robust band gap predominantly governed by C4H5N2S+ cations. Dielectric relaxation processes in (C4H5N2S)2InBr5 arise from the cations' dynamics and suggest the ability of the brominated system to accommodate even larger cations. Our work represents a successful attempt to expand the structural diversity of halogenoindates(III) and opens a pathway to reach multifunctional 1D In3+-based hybrids.

High-efficiency two-dimensional Ruddlesden-Popper perovskite solar cells.

Three-dimensional organic-inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley-Queisser limit for a single­junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden-Popper phases--layered two-dimensional perovskite films--have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

Structural and thermodynamic limits of layer thickness in 2D halide perovskites.

In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A')2(A) n-1M n X3n+1 [where A = Cs+, CH3NH3+, HC(NH2)2+; A' = ammonium cation acting as spacer; M = Ge2+, Sn2+, Pb2+; 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 (CH3(CH2)2NH3)2(CH3NH3)5Pb6I19 (n = 6) and (CH3(CH2)2NH3)2(CH3NH3)6Pb7I22 (n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for "(CH3(CH2)2NH3)2(CH3NH3)8Pb9I28" ("n = 9"). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔHf), 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.

Near-Room-Temperature Magnetoelectric Coupling via Spin Crossover in an Iron(II) Complex.

Magnetoelectric coupling is achieved near room temperature in a spin crossover FeII molecule-based compound, [Fe(1bpp)2 ](BF4 )2 . Large atomic displacements resulting from Jahn-Teller distortions induce a change in the molecule dipole moment when switching between high-spin and low-spin states leading to a step-wise change in the electric polarization and dielectric constant. For temperatures in the region of bistability, the changes in magnetic and electrical properties are induced with a remarkably low magnetic field of 3 T. This result represents a successful expansion of magnetoelectric spin crossovers towards ambient conditions. Moreover, the observed 0.3-0.4 mC m-2 changes in the H-induced electric polarization suggest that the high strength of the coupling obtained via this route is accessible not just at cryogenic temperatures but also near room temperature, a feature that is especially appealing in the light of practical applications.

Tuning Electronic Structure in Layered Hybrid Perovskites with Organic Spacer Substitution.

Two-dimensional layered halide organic perovskites (LHOPs) are promising candidates for many optoelectronic applications due to their interesting tunable properties. They provide a unique opportunity to control energy and charge dynamics via the independent tunability of the energy levels within the perovskite and the organic spacer for various optoelectronic applications. In the perovskite layer alone, one can replace the Pb (Sn), the halide (X = I, Br, Cl), the organic component, and the number of layers between the organic spacer layers. In addition, there are many possibilities for organic spacer layers between the perovskite layers, making it difficult for experimental methods to comprehensively explore such an extensive combinatorial space. Of particular technological interest is alignment of electronic levels between the perovskite layer and the organic spacer layer, leading to desired transfer of energy or charge carriers between perovskite and organic components. For example, as band edge absorption is almost entirely attributed to the perovskite layer, one way to demonstrate energy transfer is to observe triplet emission from organic spacers. State-of-the-art computational chemistry tools can be used to predict the properties of many stoichiometries in search for LHOPs that have the most promising electronic-structure features. In this first-principles study, we survey a group of π-conjugated organic spacer candidates for use in triplet light-emitting LHOPs. Utilizing density functional theory (DFT) and time-dependent DFT, we calculate the first singlet (S1) and triplet (T1) excitation energy in the ground-state geometry and the first triplet excitation energy in the excited-triplet-state relaxed geometry (T1*). By comparing these energies to the known lowest exciton energy level of PbnX3n+1 perovskite layers (X = I, Br, Cl), we can identify organic spacer and perovskite layer pairings for possible transfer of Wannier excitons from the inorganic perovskite lattice to spin-triplet Frenkel excitons located on the organic cation. We successfully identify ten organic spacer candidates for possible pairing with perovskite layers of specific halide composition to achieve triplet light emission across the visible energy range. Molecular dynamics simulations predict that finite temperatures and perovskite environment have little influence on the average excitation energies of the two common organic spacers naphthylethylammonium (NEA) and phenelethylammonium (PEA). We find significant thermal broadening up to 0.5 eV of the optical excitation energies appearing due to finite temperature effects. The findings herein provide insights into alignment of electronic levels of the conjugated organic spacer with the layer.

Concept of Lattice Mismatch and Emergence of Surface States in Two-dimensional Hybrid Perovskite Quantum Wells.

Surface states are ubiquitous to semiconductors and significantly impact the physical properties and, consequently, the performance of optoelectronic devices. Moreover, surface effects are strongly amplified in lower dimensional systems such as quantum wells and nanostructures. Layered halide perovskites (LHPs) are two-dimensional solution-processed natural quantum wells where optoelectronic properties can be tuned by varying the perovskite layer thickness n, i.e., the number of octahedra spanning the layer. They are efficient semiconductors with technologically relevant stability. Here, a generic elastic model and electronic structure modeling are applied to LHPs heterostructures with various layer thickness. We show that the relaxation of the interface strain is triggered by perovskite layers above a critical thickness. This leads to the release of the mechanical energy arising from the lattice mismatch, which nucleates the surface reorganization and may potentially induce the formation of previously observed lower energy edge states. These states, which are absent in three-dimensional perovskites are anticipated to play a crucial role in the design of LHPs for optoelectronic systems.

Two-Dimensional Halide Perovskites Incorporating Straight Chain Symmetric Diammonium Ions, (NH3C mH2 mNH3)(CH3NH3) n-1Pb nI3 n+1 ( m = 4-9; n = 1-4).

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 (NH3C mH2 mNH3)(CH3NH3) n-1Pb nI3 n+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 successfully accomplished. The films show a clear tendency for the higher- m members to have preferred orientation on the glass substrate, with m = 8 exhibiting almost perfect vertical layer orientation and m = 9 displaying both vertical and parallel layer orientation, as confirmed by grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The vertical layer orientation for the (NH3C8H16NH3)(CH3NH3)2Pb3I10 member results in the best thermal, light, and air stability within this series, thus showing excellent potential for solar cell applications.

New Type of 2D Perovskites with Alternating Cations in the Interlayer Space, (C(NH2)3)(CH3NH3)nPbnI3n+1: Structure, Properties, and Photovoltaic Performance.

We present the new homologous series (C(NH2)3)(CH3NH3)nPbnI3n+1 (n = 1, 2, 3) of layered 2D perovskites. Structural characterization by single-crystal X-ray diffraction reveals that these compounds adopt an unprecedented structure type, which is stabilized by the alternating ordering of the guanidinium and methylammonium cations in the interlayer space (ACI). Compared to the more common Ruddlesden-Popper (RP) 2D perovskites, the ACI perovskites have a different stacking motif and adopt a higher crystal symmetry. The higher symmetry of the ACI perovskites is expressed in their physical properties, which show a characteristic decrease of the bandgap with respect to their RP perovskite counterparts with the same perovskite layer thickness (n). The compounds show a monotonic decrease in the optical gap as n increases: Eg = 2.27 eV for n = 1 to Eg = 1.99 eV for n = 2 and Eg = 1.73 eV for n = 3, which show slightly narrower gaps compared to the corresponding RP perovskites. First-principles theoretical electronic structure calculations confirm the experimental optical gap trends suggesting that the ACI perovskites are direct bandgap semiconductors with wide valence and conduction bandwidths. To assess the potential of the ACI perovskites toward solar cell applications, we studied the (C(NH2)3)(CH3NH3)3Pb3I10 (n = 3) compound. Compact thin films from the (C(NH2)3)(CH3NH3)3Pb3I10 compound with excellent surface coverage can be obtained from the antisolvent dripping method. Planar photovoltaic devices from optimized ACI perovskite films yield a power-conversion-efficiency of 7.26% with a high open-circuit voltage of ∼1 V and a striking fill factor of ∼80%.

Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials.

Solution-processed organometallic perovskites have rapidly developed into a top candidate for the active layer of photovoltaic devices. Despite the remarkable progress associated with perovskite materials, many questions about the fundamental photophysical processes taking place in these devices, remain open. High on the list of unexplained phenomena are very modest mobilities despite low charge carrier effective masses. Moreover, experiments elucidate unique degradation of photocurrent affecting stable operation of perovskite solar cells. These puzzles suggest that, while ionic hybrid perovskite devices may have efficiencies on par with conventional Si and GaAs devices, they exhibit more complicated charge transport phenomena. Here we report the results from an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies using both periodic boundary conditions and isolated structures. Using the hybrid density functional theory, we found that volumetric strain in a CsPbI3 cluster creates a polaron with binding energy of around 300 and 900 meV for holes and electrons, respectively. In the MAPbI3 (MA = CH3NH3) cluster, both volumetric strain and MA reorientation effects lead to larger binding energies at around 600 and 1300 meV for holes and electrons, respectively. Such large reorganization energies suggest appearance of small polarons in organometallic perovskite materials. The fact that both volumetric lattice strain and MA molecular rotational degrees of freedom can cooperate to create and stabilize polarons indicates that in order to mitigate this problem, formamidinium (FA = HC(NH2)2) and cesium (Cs) based crystals and alloys, are potentially better materials for solar cell and other optoelectronic applications.

Halide Perovskites and Their Derivatives for Efficient, High-Resolution Direct Radiation Detection: Design Strategies and Applications.

The past decade has witnessed a rapid rise in the performance of optoelectronic devices based on lead-halide perovskites (LHPs). The large mobility-lifetime products and defect tolerance of these materials, essential for optoelectronics, also make them well-suited for radiation detectors, especially given the heavy elements present, which is essential for strong X-ray and γ-ray attenuation. Over the past decade, LHP thick films, wafers, and single crystals have given rise to direct radiation detectors that have outperformed incumbent technologies in terms of sensitivity (reported values up to 3.5 × 106 µC Gyair -1 cm-2 ), limit of detection (directly measured values down to 1.5 nGyair s-1 ), along with competitive energy and imaging resolution at room temperature. At the same time, lead-free perovskite-inspired materials (e.g., methylammonium bismuth iodide), which have underperformed in solar cells, have recently matched and, in some areas (e.g., in polarization stability), surpassed the performance of LHP detectors. These advances open up opportunities to achieve devices for safer medical imaging, as well as more effective non-invasive analysis for security, nuclear safety, or product inspection applications. Herein, the principles behind the rapid rises in performance of LHP and perovskite-inspired material detectors, and how their properties and performance link with critical applications in non-invasive diagnostics are discussed. The key strategies to engineer the performance of these materials, and the important challenges to overcome to commercialize these new technologies are also discussed.

Reconfigurable Resistive Switching in VO2/La0.7Sr0.3MnO3/Al2O3 (0001) Memristive Devices for Neuromorphic Computing.

The coexistence of nonvolatile and volatile switching modes in a single memristive device provides flexibility to emulate both neuronal and synaptic functions in the brain. Furthermore, such a device structure may eliminate the need for additional circuit elements such as transistor-based selectors, enabling low-power consumption and high-density device integration in fully memristive spiking neural networks. In this work, we report dual resistive switching (RS) modes in VO2/La0.7Sr0.3MnO3 (LSMO) bilayer memristive devices. Specifically, the nonvolatile RS is driven by the movement of oxygen vacancies (Vo) at the VO2/LSMO interface and requires a higher biasing voltage, whereas the volatile RS is controlled by the metal-insulator transition (MIT) of VO2 under a lower biasing voltage. The simple device structure is electrically driven between the two RS modes and thus can operate as a one selector-one resistor (1S1R) cell, which is a desirable feature in memristive crossbar arrays to avoid the sneak-path current issue. The RS modes are found to be stable and repeatable and can be reconfigured by exploiting the interfacial and phase transition properties, and thus, they hold great promise for applications in memristive neural networks and neuromorphic computing.

Intersubband Transitions in Lead Halide Perovskite-Based Quantum Wells for Mid-Infrared Detectors.

Due to their excellent optical and electrical properties as well as versatile growth and fabrication processes, lead halide perovskites have been widely considered as promising candidates for green energy and applications related to optoelectronics. Here, we investigate their potential applications at infrared wavelengths by modeling the intersubband transitions in perovskite-based quantum well systems. Both single-well and double-well structures are studied, and their energy levels as well as the corresponding wave functions and intersubband transition energies are calculated by solving the one-dimensional Schrödinger equations. Via adjustment of the quantum well and barrier thicknesses, the intersubband transition energies can be tuned to cover a broad infrared wavelength range. We also find that the lead halide perovskite-based quantum wells possess high absorption coefficients. The widely tunable transition energies and high absorption coefficients of the perovskite-based quantum well systems, combined with their unique material and electrical properties, may enable an alternative material system for infrared photodetector applications.

Environmental and health risks of perovskite solar modules: Case for better test standards and risk mitigation solutions.

Perovskite solar cells (PSCs) promise high efficiencies and low manufacturing costs. Most formulations, however, contain lead, which raises health and environmental concerns. In this review, we use a risk assessment approach to identify and evaluate the technology risks to the environment and human health. We analyze the risks by following the technology from production to transportation to installation to disposal and examine existing environmental and safety regulations in each context. We review published data from leaching and air emissions testing and highlight gaps in current knowledge and a need for more standardization. Methods to avoid lead release through introduction of absorbing materials or use of alternative PSC formulations are reviewed. We conclude with the recommendation to develop recycling programs for PSCs and further standardized testing to understand risks related to leaching and fires.

Heterocyclic Functionalized Donor-Acceptor Hole-Transporting Materials for Inverted Perovskite Solar Cells.

Hole transport materials (HTMs) with appropriate energy levels and comprehensive passivation effects help to obtain highly efficient and stable perovskite solar cells (PSCs). Electron-deficient character-induced HTMs can generate varying energy level alignments near the HTM/perovskite interface. Herein, we report the synthesis and investigation of two new dipolar HTMs, WWC103 and WWC105, based on 2-(1,1-dicyanomethylene)rhodamine and 4-cynophenylacetonitrile acceptors, enabling high-efficiency mixed-cation mixed-halide perovskite solar cells. Apart from having different acceptors, these HTMs are built on a heterocyclic frame, which can provide passivation effects and improve the morphology of the perovskite layer. As a result, these dopant-free HTM-based solar cells show a high open-circuit voltage and good power conversion efficiency. Among both, the solar cell based on the HTM with 2-(1,1-dicyanomethylene)rhodamine exhibits a high open-circuit voltage of 1.09 V with a champion power conversion efficiency of over 20.51%. The improved performance of WWC103 over WWC105 (19.74%) is attributed to the new acceptor, which, in addition to providing good energy-level alignments and hole mobility, also holds the ability to passivate the defects. The findings suggest a new acceptor unit for constructing dopant-free HTMs for efficient PSCs.

Strain Engineering: A Pathway for Tunable Functionalities of Perovskite Metal Oxide Films.

Perovskite offers a framework that boasts various functionalities and physical properties of interest such as ferroelectricity, magnetic orderings, multiferroicity, superconductivity, semiconductor, and optoelectronic properties owing to their rich compositional diversity. These properties are also uniquely tied to their crystal distortion which is directly affected by lattice strain. Therefore, many important properties of perovskite can be further tuned through strain engineering which can be accomplished by chemical doping or simply element substitution, interface engineering in epitaxial thin films, and special architectures such as nanocomposites. In this review, we focus on and highlight the structure-property relationships of perovskite metal oxide films and elucidate the principles to manipulate the functionalities through different modalities of strain engineering approaches.

Point Defects in Two-Dimensional Ruddlesden-Popper Perovskites Explored with Ab Initio Calculations.

Two-dimensional Ruddlesden-Popper (RP) halide perovskites stand out as excellent layered materials with favorable optoelectronic properties for efficient light-emitting, spintronic, and other spin-related applications. However, properties often determined by defects are not well understood in these perovskite systems. This work investigates the ground state electronic structure of commonly formed defects in a typical RP perovskite structure by density functional theory. Our study reveals that these 2D perovskites generally retain their defect tolerance with limited perturbation of the electronic structure in the case of neutral-type point defects. In contrast, donor/acceptor defects induce deep midgap states, potentially causing harm to the material's electronic performance. To retain positive intrinsic properties, the halide vacancies and interstitial defects should be avoided. The observed strong electron localization results in trap states and consequently leads to reduced device performance. This understanding can guide experimental efforts that aim for improved 2D halide perovskite-based device performance.

Quasi-2D Perovskite Crystalline Layers for Printable Direct Conversion X-Ray Imaging.

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 Gyair -1  cm-2 and a sensitivity gain is observed when operated under higher fields. Finally, high resolution images are demonstrated using a single pixel device that can resolve 80-200 µm features. This work paves the path for printable direct conversion X-ray imager development.