Centimeter-Sized Single Crystals of Two-Dimensional Hybrid Iodide Double Perovskite (4,4-Difluoropiperidinium)4AgBiI8 for High-Temperature Ferroelectricity and Efficient X-Ray Detection

Ferroelectricity and X-ray detection property have been recently implemented for the first time in hybrid bromide double perovskites. It sheds a light on achieving photosensitive and ferroelectric multifunctional materials based on 2D lead-free hybrid halide double perovskites. However, the low T_c, small P_s, and relatively low X-ray sensitivity in the reported bromide double perovskites hinder practical applications. Herein, the authors demonstrate a novel 2D lead-free iodide double perovskite (4,4-difluoropiperidinium)₄AgBiI₈ (1) for high-performance X-ray sensitive ferroelectric devices. Centimeter-sized single crystal of 1 is obtained and exhibits an excellent ferroelectricity including a high T_c up to 422 K and a large P_s of 10.5 μC cm⁻². Moreover, due to a large X-ray attenuation and efficient charge carrier mobility (μ)–charge carrier lifetime (τ) product, the crystal 1 also exhibits promising X-ray response with a high sensitivity up to 188 μC·Gy_air⁻¹ cm⁻² and a detection limit below 3.13 μGy_air·s⁻¹. Therefore, this finding is a step further toward practical applications of lead-free halide perovskite in high-performance photoelectronic devices. It will afford a promising platform for exploring novel photosensitive ferroelectric multifunctional materials based on lead-free double perovskites.     

Discovering New Type of Lead-Free Cluster-Based Hybrid Double Perovskite Derivatives with Chiral Optical Activities and Low X-Ray Detection Limit

2D chiral hybrid perovskites have recently emerged as outstanding semiconductor materials. However, most of the reported 2D chiral perovskites have limited structural types and contain high levels of toxic lead, which severely hinders their further applications. Herein, by using a mixed-cation strategy, an unprecedented type of lead-free cluster-based 2D chiral hybrid double perovskite derivatives are successfully obtained, [(R/S-PPA)₄(IPA)₆Ag₂Bi₄I₂₄]·2H₂O ( 1-R and 1-S ), and [(R/S-PPA)₄(n-BA)₆Ag₂Bi₄I₂₄]·2H₂O ( 2-R and 2-S ) (R/S-PPA=R/S–1-phenylpropylamine; IPA=isopentylamine; n-BA=n-butylamine). Their inorganic skeletons are linked by binuclear {Bi₂I₁₀} and infinite chain {Ag₂Bi₂I₁₄}_∞, in which bismuth clusters and multiple coordination modes (e.g., tetrahedral AgI₄ and octahedral AgI₆) are introduced into the double perovskite system for the first time. This introduction induces distortion of the inorganic layer, which may facilitate the transfer of chirality from the chiral cations into achiral double perovskite skeletons. Further, circular dichroism measurements and circularly polarized light detection confirm their inherent chiral optical activities. In addition, 1-S exhibits an ultralow X-ray detection limit of 129.5 nGy s⁻¹, which is 42-fold lower than that of demands in regular medical diagnosis (5.5 µGy s⁻¹). This study provides a pathway to construct novel type of lead-free cluster-based double perovskite derivatives.     

Self-Healing Cs3Bi2Br3I6 Perovskite Wafers for X-Ray Detection

Self-healing of defects imposed by external stimuli such as high energy radiation is a possibility to sustain the operational lifetime of electronic devices such as radiation detectors. Cs₃Bi₂Br₃I₆ polycrystalline wafers are introduced here as novel X-ray detector material, which not only guarantees a high X-ray stopping power due to its composition with elements with high atomic numbers, but also outperforms other Bi-based semiconductors in respect to detector parameters such as detection limit, transient behavior, or dark current. The polycrystalline wafers represent a size scalable technology suitable for future integration in imager devices for medical applications. Most astonishingly, aging of these wafer-based devices results in an overall improvement of the detector performance—dark currents are reduced, photocurrents are increased, and one of the most problematic properties of X-ray detectors, the base line drift is reduced by orders of magnitude. These aging induced improvements indicate self-healing effects which are shown to result from recrystallization. Optimized synthetic conditions also improve the as prepared X-ray detectors; however, the aged device outperforms all others. Thus, self-healing acts in Cs₃Bi₂Br₃I₆ as an optimization tool, which is certainly not restricted to this single compound, it is expected to be beneficial also for many further polycrystalline ionic semiconductors.     

3D/2D Perovskite Single Crystals Heterojunction for Suppressed Ions Migration in Hard X-Ray Detection

Halide perovskites exhibit diverse properties depending on their compositions. However, integrating desired properties into one material is still challenging. Here, a facile solution-processed epitaxial growth method to grow 2D perovskite single crystal on top of 3D perovskite single crystal, which can passivate the surface defects for improved device performance is reported. Short formamidine (FA⁺) ions are replaced by long organic cations, which can fully align and cover the single crystal surface to prevent the ions migration or short FA⁺ ions volatilization. The thickness of epitaxial layer can be finely adjusted by controlling the growth time. The defect density of single crystals heterojunction is only 3.18 × 10⁹ cm⁻³, and the carrier mobility is 80.43 cm² V⁻¹ s⁻¹, which is greater than that of the control 3D perovskite single crystal. This study for the first time realized large area 3D/2D perovskite single crystals heterojunction, which suppressed ions migration and exhibited advanced performance in hard X-rays detection applications. This strategy also provides a way to grow large area 2D perovskite single crystal from solution processes.     

Sintered Polycrystalline BiVO4 Pellet for Stable X-Ray Detector with Low Detection Limit

Semiconductors based on Bi element show large attenuation coefficients to X-ray photons and have been recognized as candidates for X-ray detectors. However, the application of stable Bi-based oxide materials to X-ray detectors has been rarely investigated. In this research, the X-ray response of a BiVO₄ pellet has been studied. It has been found that the BiVO₄ pellet has a large resistivity of 1.3 × 10¹² Ω cm, negligible current drift of 6.18 × 10⁻⁸ nA cm⁻¹ s⁻¹ V⁻¹ under electrical bias and mobility lifetime product, µτ, of 1.75 × 10⁻⁴ cm² V⁻¹, which renders the pellet with an X-ray sensitivity of 241.3 µC Gy_air⁻¹ cm⁻² and a detection limit of 62 nGy_air s⁻¹ under 40 KVp X-ray illumination and 40 V bias voltage. The BiVO₄ pellet also shows operational stability under steady X-ray illumination with total dose of 2.01 Gy_air, equal to the dose of 20 000 medical chest X-ray inspections. This research reveals the potential application of BiVO₄ in X-ray detection devices and inspires further research in this area.     

Interfacial Pyro-Phototronic Effect: A Universal Approach for Enhancement of Self-Powered Photodetection Based on Perovskites with Centrosymmetry

Utilizing the pyro-phototronic effect presents a potent approach to augment the efficacy of self-powered photodetectors (PDs) that rely on metal halide perovskites (MHPs). Nevertheless, the pyro-phototronic effect has thus far been restricted to perovskites possessing a non-centrosymmetric crystal structure, limiting their scope of application. This study introduces a universal interfacial pyro-phototronic effect (IPPE) strategy to MHP single crystals with centrosymmetry. The utilization of heterojunctions or Schottky junctions has resulted in the observation of typical four-stage photoresponses with rapid speed, thereby significantly enhancing the performance of self-powered PDs and expanding the spectral response range. The contact conditions, such as the choice of metals and surface smoothness, have an important impact on IPPE. The IPPE approach is a versatile technique that can be employed to fabricate self-powered PDs based on diverse 3D and 2D perovskites. This study broadens the utilization of the pyro-phototronic phenomenon in centrosymmetric perovskites, which offer advantages in producing optoelectronic devices with superior performance.