Enhanced Storage Capacity via Anion Substitution for Advanced Delayed X-ray Detection.

X-ray radiation information storage, characterized by its ability to detect radiation with delayed readings, shows great promise in enabling reliable and readily accessible X-ray imaging and dosimetry in situations where conventional detectors may not be feasible. However, the lack of specific strategies to enhance the memory capability dramatically hampers its further development. Here, we present an effective anion substitution strategy to enhance the storage capability of NaLuF4:Tb3+ nanocrystals attributed to the increased concentration of trapping centers under X-ray irradiation. The stored radiation information can be read out as optical brightness via thermal, 980 nm laser, or mechanical stimulation, avoiding real-time measurement under ionizing radiation. Moreover, the radiation information can be maintained for more than 13 days, and the imaging resolution reaches 14.3 lp mm-1. These results demonstrate that anion substitution methods can effectively achieve high storage capability and broaden the application scope of X-ray information storage.

Aligned Conjugated Polymer Nanofiber Networks in an Elastomer Matrix for High-Performance Printed Stretchable Electronics.

Conjugated polymer films are promising in wearable X-ray detection. However, achieving optimal film microstructure possessing good electrical and detection performance under large deformation via scalable printing remains challenging. Herein, we report bar-coated high-performance stretchable films based on a conjugated polymer P(TDPP-Se) and elastomer SEBS blend by optimizing the solution-processing conditions. The moderate preaggregation in solution and prolonged growth dynamics from a solvent mixture with limited dissolving capacity is critical to forming aligned P(TDPP-Se) chains/crystalline nanofibers in the SEBS phase with enhanced π-π stacking for charge transport and stress dissipation. The film shows a large elongation at break of >400% and high mobilities of 5.29 cm2 V-1 s-1 at 0% strain and 1.66 cm2 V-1 s-1 over 500 stretch-release cycles at 50% strain, enabling good X-ray imaging with a high sensitivity of 1501.52 µC Gyair-1 cm-2. Our work provides a morphology control strategy toward high-performance conjugated polymer film-based stretchable electronics.

Radiation Photovoltaics in a 2D Multilayered Chiral-Polar Halide Perovskite toward Efficient Self-Driven X-Ray Detection.

2D multilayered organic-inorganic hybrid perovskites (OIHPs) have exhibited bright prospects for high-performance self-driven X-ray detection due to their strong radiation absorption and long carrier transport. However, as an effective tool for self-driven X-ray detection, radiation photovoltaics remain rare, and underdeveloped in multilayered OIHPs. Herein, chirality to induce radiation photovoltaics in 2D multilayered chiral OIHPs is first utilized for efficient self-driven X-ray detection. Specifically, under X-ray irradiation, a multilayered chiral-polar (S-BPEA)2FAPb2I7 (1-S, S-BPEA = (S)-1-4-Bromophenylethylammonium, FA = formamidinium) shows remarkable radiation photovoltaics of 0.85 V, which endows 1-S excellent self-driven X-ray detection performance with a considerable sensitivity of 87.8 µC Gyair -1 cm-2 and a detection limit low to 161 nGyair s-1. Moreover, the sensitivity is high up to 1985.9 µC Gyair -1 cm-2 under 80 V bias, higher than most those of 2D OIHPs. These results demonstrate that chirality-induced radiation photovoltaics is an efficient strategy for self-driven X-ray detection.

Dion-Jacobson Type Lead-Free Double Perovskite with Ultra-Narrow Aromatic Interlayer Spacing for Highly Sensitive and Stable X-ray Detection.

The low-toxic and environmentally friendly 2D lead-free perovskite has made significant progress in the exploration of "green" X-ray detectors. However, the gap in detection performance between them and their lead-based analogues remains a matter of concern that cannot be ignored. To reduce this gap, shortening the interlayer spacing to accelerate the migration and collection of X-ray carriers is a promising strategy. Herein, a Dion-Jacobson (DJ) lead-free double perovskite (4-AP)2AgBiBr8 (1, 4-AP = 4-amidinopyridine) with an ultra-narrow interlayer spacing of 3.0 Å, is constructed by utilizing π-conjugated aromatic spacers. Strikingly, the subsequent enhanced carrier transport and increased crystal density lead to X-ray detectors based on bulk single crystals of 1 with a high sensitivity of 1117.3 µC Gy-1 cm-2, superior to the vast majority of similar double perovskites. In particular, the tight connection of the inorganic layers by the divalent cations enhances structural rigidity and stability, further endowing 1 detector with ultralow dark current drift (3.06 × 10-8 nA cm-1 s-1 V-1, 80 V), excellent multiple cycles switching X-ray irradiation stability, as well as long-term environmental stability (maintains over 94% photoresponse after 90 days). This work brings lead-free double perovskites one step closer to realizing efficient practical green applications.

Synergetic Electrostatic and Steric Effects in α-FAPbI3 Single Crystals For X-Ray Detection and Imaging.

It is still challenging to stabilize α-FAPbI3 perovskite for high performance optoelectrical devices. Herein, a novel strategy is proposed utilizing the synergetic electrostatic and steric effect to stabilize the α-FAPbI3 phase and suppress the ion migration. Dimethylamine (DMA+) cations are chosen as the dopant to fabricate FA0.96DMA0.04PbI3 single crystals (SCs). DFT calculations reveal that DMA+ cations can improve the stability of α-FAPbI3 phase in both thermodynamics (lower Gibbs free energy) and kinetics (higher defect formation and migration energy). The resulting SCs exhibit an environmental stability over 100 days and an extraordinary low dark current drift of 3.7 × 10-7 nA cm-1 s-1 V-1, comparable to 2D perovskite SCs. The X-ray detectors have also achieved the-state-of-the-art performance in X-ray detection and imaging. This work demonstrates the significance of electrostatic and steric effects in improving the phase and operational stability of perovskites.

Dimensionality Engineering of Organic-Inorganic Halide Perovskites for Next-Generation X-Ray Detector.

The next-generation X-ray detectors require novel semiconductors with low material/fabrication cost, excellent X-ray response characteristics, and robust operational stability. The family of organic-inorganic hybrid perovskites (OIHPs) materials comprises a range of crystal configuration (i.e., films, wafers, and single crystals) with tunable chemical composition, structures, and electronic properties, which can perfectly meet the multiple-stringent requirements of high-energy radiation detection, making them emerging as the cutting-edge candidate for next-generation X-ray detectors. From the perspective of molecular dimensionality, the physicochemical and optoelectronic characteristics of OIHPs exhibit dimensionality-dependent behavior, and thus the structural dimensionality is recognized as the key factor that determines the device performance of OIHPs-based X-ray detectors. Nevertheless, the correlation between dimensionality of OIHPs and performance of their X-ray detectors is still short of theoretical guidance, which become a bottleneck that impedes the development of efficient X-ray detectors. In the review, the advanced studies on the dimensionality engineering of OIHPs are critically assessed in X-ray detection application, discussing the current understanding on the "dimensionality-property" relationship of OIHPs and the state-of-the-art progresses on the dimensionality-engineered OIHPs-based X-ray detector, and highlight the open challenges and future outlook of this field.

A New Metal-Free Molecular Perovskite-Related Single Crystal with Quantum Wire Structure for High-Performance X-Ray Detection.

The family of metal-free molecular perovskites, an emerging novel class of eco-friendly semiconductor, welcomes a new member with a unique 1D hexagonal perovskite structure. Lowering dimensionality at molecular level is a facile strategy for crystal structure conversion, optoelectronic property regulation, and device performance optimization. Herein, the study reports the design, synthesis, packing structure, and photophysical properties of the 1D metal-free molecular perovskite-related single crystal, rac-3APD-NH4I3(rac-3APD= racemic-3-Aminopiperidinium), that features a quantum wire structure formed by infinite chains of face-sharing NH4I6 octahedra, enabling strong quantum confinement with strongly self-trapped excited (STE) states to give efficient warm orange emission with a photoluminescence quantum yield (PLQY) as high as ≈41.6%. The study accordingly unveils its photoexcited carrier dynamics: rac-3APD-NH4I3 relaxes to STE state with a short lifetime of 10 ps but decays to ground state by emitting photons with a relatively longer lifetime of 560 ps. Additionally, strong quantum confinement effect is conducive to charge transport along the octahedral channels that enables the co-planar single-crystal X-ray detectors to achieve a sensitivity as high as 1556 µC Gyair -1 cm-2. This work demonstrates the first case of photoluminescence mechanism and photophysical dynamics of 1D metal-free perovskite-related semiconductor, as well as the promise for high-performance X-ray detector.

Achieving High Operating-Temperature Self-powered X-Ray Detection in Multilayered Hybrid Perovskites through Arylamine Intercalation.

Polar metal halide hybrid perovskites (PHPs) that exhibit outstanding bulk photovoltaic effect (BPVE), excellent semiconductor features, and strong radiation absorption ability, have shown prominent advantages in highly sensitive direct X-ray detection. However, it is still a challenge to explore PHPs with high BPVE temperature ranges, answering the demand of developing thermally stable passive X-ray detection. Herein, by intercalating arylamine into lead tribromide and inducing order-disorder phase transition, a 2D multilayered PHPs (BZA)2(MA)Pb2Br7 (BZPB, BZA = benzylamine, MA = methylamine) is synthesized. BZPB crystallizes in a polar space group Aea2 at a low-temperature phase and demonstrates a significant open-circuit of 0.3 V deriving from BPVE under X-ray irradiation. Meanwhile, the strong X-ray absorption coefficient and outstanding carrier transport capability of the bilayered lead halide framework associated with the polar BPVE give BZPB excellent X-ray detection abilities. At 0 V bias, the impressive sensitivity of BZPB is 98 µC Gy-1 cm-2. Importantly, the introduction of the rigid BZA ring increases the energy barrier of phase transition and thus dramatically enhances the X-ray detection operating temperature of BZPB up to 409 K without significant performance degradation. This work strongly reveals the great potential of rational design of metal halide hybrid perovskites for X-ray detection applications.

Bulk Photovoltaic Effect Induced by Non-Covalent Interactions in Bilayered Hybrid Perovskite for Efficient Passive X-Ray Detection.

Hydrogen bonding as a multifunctional tool has always influenced the structure of hybrid perovskites. Compared with the research on hydrogen bonding, the study of halogen-halogen interactions on the structure and properties of hybrid perovskites is still in its early stages. Herein, a polar bilayered hybrid perovskite (IEA)2FAPb2I7 (IEA+ is 2-iodoethyl-1-ammonium, FA is formamidinium) with iodine-substituted spacer is successfully constructed by changing the configuration of interlayer cations and regulating non-covalent interactions at the organic-inorganic interface, which shows a shorter interlayer spacing and higher density (ρ = 3.862 g cm-3). The generation of structure polarity in (IEA)2FAPb2I7 is caused by the synergistic effect of hydrogen bonding and halogen-halogen interactions. Especially, as the length of the carbon chain in organic cations decreases, the I---I interaction in the system gradually strengthens, which may be the main reason for the symmetry-breaking. Polarity-induced bulk photovoltaics (Voc = 1.0 V) and higher density endow the device based on (I-EA)2FAPb2I7 exhibit a high sensitivity of 175.6 µC Gy-1 cm-2 and an ultralow detection limit of 60.4 nGy s-1 at 0 V bias under X-ray irradiation. The results present a facile approach for designing polar multifunctional hybrid perovskites, also providing useful assistance for future research on halogen-halogen interactions.

Photodarkening, Photobrightening, and the Role of Color Centers in Emerging Applications of Lanthanide-Based Upconverting Nanomaterials.

Upconverting nanoparticles (UCNPs) compose a class of luminescent materials that utilize the unique wavelength-converting properties of lanthanide (Ln) ions for light-harvesting applications, photonics technologies, and biological imaging and sensing experiments. Recent advances in UCNP design have shed light on the properties of local color centers, both intrinsic and controllably induced, within these materials and their potential influence on UCNP photophysics. In this review, we describe fundamental studies of color centers in Ln-based materials, including research into their origins and their roles in observed photodarkening and photobrightening mechanisms. We place particular focus on the new functionalities that are enabled by harnessing the properties of color centers within Ln-doped nanocrystals, illustrated through applications in afterglow-based bioimaging, X-ray detection, all-inorganic nanocrystal photoswitching, and fully rewritable optical patterning and memory.

Metal-Free Hydrazinium Halide Perovskitoid Single Crystals for X-ray Detection.

Metal-free perovskitoids (MFPs) with N2H5+ as B-site component possess higher crystal density and hydrogen bonding networks and have been recently expanded into X-ray detection. However, research on this material is in its infancy and lacks an understanding of the function of halide components on physical properties and device performance. Here, N2H5-based MFP single crystals (SCs) with different halides are fabricated, and the influence of halides on the crystal structure, band nature, charge transport characteristics, and final device performance is actively explored. Based on theory and experiments, the tolerance factor and octahedral factor jointly determine the octahedral composition. Further, halides with different electronegativities and ionic radii also affect octahedral distortion and energy band bending, further influencing carrier transport and device performance. Finally, a sensitivity of 1284 µC Gyair-1 cm-2 and low detection limits (LoD) of 5.62 µGyair s-1 were obtained by the Br-based device due to its superior physical properties.

Dimensional Regulation in Metal-Free Perovskites by Compositional Engineering to Achieve Record Low X-Ray Detection Limits.

Utilizing the manipulation of perovskite dimensions has been proven as an effective approach in regulating perovskite properties. Nevertheless, achieving precise control over the dimensions of perovskites within the same system poses a significant challenge. In this study, we introduce a sophisticated method to attain precise dimensional control in metal-free perovskites (MFPs), specifically through the process of octahedron tailoring by compositional engineering. Accordingly, we successfully instigated a transition from HPIP-NH4I3 ⋅ H2O (3D), HPIP2-NH4I5 (2D) and HPIP3-NH4I7 (1D) structures. Notably, HPIP2-NH4I5 is the first 2D MFP. As anticipated, these perovskites exhibited completely distinct fluorescence and X-ray detection capabilities due to their differing dimensions. Remarkably, the 2D HPIP2-NH4I5 device effectively hindered ion migration perpendicular to the 2D layers, achieving the lowest detection limit of 12.2 nGyair s-1 among metal-free single crystals-based detectors. This study expands the dimensionality control strategies for MFPs and introduces, for the first time, the potential of 2D MFPs as high-performance X-ray detectors, thereby enriching the diversity of the MFPs family.

Three-Dimensional Polar Perovskites for Highly Sensitive Self-Driven X-Ray Detection.

Three-dimensional (3D) organic-inorganic hybrid perovskites (OIHPs) have achieved tremendous success in direct X-ray detection due to their high absorption coefficient and excellent carrier transport. However, owing to the centrosymmetry of classic 3D structures, these reported X-ray detectors mostly require external electrical fields to run, resulting in bulky overall circuitry, high energy consumption, and operational instability. Herein, we first report the unprecedented radiation photovoltage in 3D OIHP for efficient self-driven X-ray detection. Specifically, the 3D polar OIHP MhyPbBr3 (1, Mhy=methylhydrazine) shows an intrinsic radiation photovoltage (0.47 V) and large mobility-lifetime product (1.1×10-3  cm2 V-1 ) under X-ray irradiation. Strikingly, these excellent physical characteristics endow 1 with sensitive self-driven X-ray detection performance, showing a considerable sensitivity of 220 µC Gy-1 cm-2 , which surpasses those of most self-driven X-ray detectors. This work first explores highly sensitive self-driven X-ray detection in 3D polar OIHPs, shedding light on future practical applications.

Multi-axial Self-driven X-ray Detection by a Two-dimensional Biaxial Hybrid Organic-Inorganic Perovskite Ferroelectric.

Metal halide perovskite ferroelectrics combining spontaneous polarization and excellent semiconducting properties is an ideal platform for enabling self-driven X-ray detection, however, achievements to date have been only based on uniaxiality, which increases the complexity of device fabrication. Multi-axial ferroelectric materials have multiple equivalent polarization directions, making them potentially amenable to multi-axial self-driven X-ray detection, but the report on these types of materials is still a huge blank. Herein, a high-quality (BA)2(EA)2Pb3I10 (1) biaxial ferroelectric single crystal was successfully grown, which exhibited significant spontaneous polarization along the c-axis and b-axis. Under X-ray irradiation, bulk photovoltaic effect (BPVE) was exhibited along both the c-axis and b-axis, with open circuit voltages (Voc) of 0.23 V and 0.22 V, respectively. Then, the BPVE revealed along the inversion of polarized direction with the polarized electric fields. Intriguingly, due to the BPVE of 1, 1 achieved multi-axial self-driven X-ray detection for the first time (c-axis and b-axis) with relatively high sensitivities and ultralow detection limits (17.2 nGyair s-1 and 19.4 nGyair s-1, respectively). This work provides a reference for the subsequent use of multi-axial ferroelectricity for multi-axial self-driven optoelectronic detection.

Highly Sensitive Direct X-Ray Detector Based on Copper(II) Coordination Polymer Single Crystal with Anisotropic Charge Transport.

Anisotropic charge transport plays a pivotal role in clarifying the conductivity mechanism in direct X-ray detection to improve the detection sensitivity. However, the anisotropic photoelectric effect of semiconductive single crystal responsive to X-ray is still lacking of theoretical and experimental proof. The semiconductive coordination polymers (CPs) with designable structures, adjustable functions, and high crystallinity provide a suitable platform for exploring the anisotropic conductive mechanism. Here,the study first reveals a 1D conductive transmission path for direct X-ray detection from the perspective of structural chemistry. The semiconductive copper(II)-based CP 1 single crystal detector exhibits unique anisotropic X-ray detection performance. Along the 1D π-π stacking direction, the single crystal device (1-SC-a) shows a superior sensitivity of 2697.15 µCGyair -1  cm-2 and a low detection limit of 1.02 µGyair  s-1 among CPs-based X-ray detectors. This study provides beneficial guidance and deep insight for designing high-performance CP-based X-ray detectors.

Centimeter-Sized Single Crystals of Dion-Jacobson Phase Lead-Free Double Perovskite for Efficient X-ray Detection.

2D Dion-Jacobson (DJ) phase hybrid perovskites have shown great promise in the photoelectronic field owing to their outstanding optoelectronic performance and superior structural rigidity. However, DJ phase lead-free double perovskites are still a virgin land with direct X-ray detection. Herein, we have designed and synthesized a new DJ phase lead-free layered double perovskite of (HIS)2 AgSbBr8 (1, HIS2+  = histammonium). Centimeter-sized (18 × 10 × 5 mm3 ) single crystals of 1 are successfully grown via the temperature cooling technique, exhibiting remarkable semiconductive characteristics such as a high resistivity (2.2 × 1011  Ω cm), a low trap state density (3.56 × 1010 cm-3 ), and a large mobility-lifetime product (1.72 × 10-3 cm2 V-1 ). Strikingly, its single-crystal-based X-ray detector shows a high sensitivity of 223 µC Gy-1 air cm-2 under 33.3 V mm-1 , a low detection limit (84.2 nGyair s-1 ) and superior anti-fatigue. As far as we know, we firstly demonstrates the potential of 2D DJ phase lead-free hybrid double perovskite in X-ray detection, showing excellent photoelectric response and operational stability. This work will pave a promising pathway to the innovative application of hybrid perovskites for eco-friendly and efficient X-ray detection.

Realization of Passive X-Ray Detection with a Low Detection Limit in Dion-Jacobson Halide Hybrid Perovskite.

Halide hybrid perovskites are a kind of intriguing contenders for X-ray detection, and their low detection limits (LoDs) have played a crucial part in X-ray safety inspection and medical examination. However, there is still a significant challenge in manufacturing perovskite X-ray detectors with low LoDs. Herein, attributed to the bulk photovoltaic effect (BPVE) of a Dion-Jacobson (DJ) type 2D halide hybrid perovskite polar structure (3-methylaminopropylamine)PbBr4 (1), self-powered X-ray detection with low detection limit is successfully realized. Specifically, the crystal-based detector of 1 exhibits a low dark current at zero bias, which reduces the noise current (0.34 pA), leading to a low detection limit (58.3 nGyair s-1 ) which is two orders of magnitude lower than that of under external voltage bias. The combination of BPVE and LoDs of halide hybrid perovskite provides an efficient strategy to achieve passive X-ray detection with low doses.

X-Site Substituted 2D Cs2 Pb(SCN)2 Br2 Perovskites for X-Ray Detection.

2D Ruddlesden-Popper (RP) perovskites have been intensively investigated due to their superior stability and outstanding optoelectrical properties. However, investigations on 2D RP perovskites are mainly focused on A-site substituted perovskites and few reports are on X-site substituted perovskites especially in X-ray detection field. Here, X-site substituted 2D RP perovskite Cs2 Pb(SCN)2 Br2 polycrystalline wafers are prepared and systematically studied for X-ray detection. The obtained wafers show a large resistivity of 2.0 × 1010 Ω cm, a high ion activation energy of 0.75 eV, a small current drift of 2.39 × 10-6 nA cm-1 s-1 V-1 , and charge carrier mobility-lifetime product under X-ray as high as 1.29 × 10-4 cm2 V-1 . These merits enable Cs2 Pb(SCN)2 Br2 wafer detectors with a sensitivity of 216.3 µC Gyair -1 cm-2 , a limit of detection of 42.4 nGyair s-1 , and good imaging ability with high spatial resolution of 1.08 lp mm-1 . In addition, Cs2 Pb(SCN)2 Br2 wafer detectors demonstrate excellent operational stability under high working field up to 2100 V cm-1 after continuous X-ray irradiation with a total dose of 45.2 Gyair . The promising features such as short octahedral spacing and weak ion migration will open up a new perspective and opportunity for SCN-based 2D perovskites in X-ray detection.

Metal-Free Perovskites for X-Ray Detection.

Metal-free perovskites are a promising class of materials for X-ray detection due to their unique structural, optical, and electrical properties. Here, we first delve into the stoichiometry and geometric argument of metal-free perovskites. Followed, the alternative A/B/X ions and hydrogen-bonding are clearly introduced to further optimize the materials' stability and properties. Finally, we provide a comprehensive overview of their potential applications for flexible X-ray images and prospects for metal-free perovskite development. In conclusion, metal-free perovskite is a promising material for X-ray detection. Its stoichiometric and geometric parameters, ion, and hydrogen bond selection, and application prospects are worthy of further study.

Hydrogen Bonds Strengthened Metal-Free Perovskite for Degradable X-ray Detector with Enhanced Stability, Flexibility and Sensitivity.

Metal-free perovskites (MFPs) with flexible and degradable properties have been adopted in flexible X-ray detection. For now, figuring out the key factors between structure and device performance are critical to guide the design of MFPs. Herein, MPAZE-NH4 I3 ⋅ H2 O was first designed and synthesized with improved structural stability and device performance. Through theoretical calculations, the introducing methyl group benefits modulating tolerance factor, increases dipole moment and strengthens hydrogen bonds. Meanwhile, H2 O increases the hydrogen bond formation sites and synergistically realizes the band nature modulation, ionic migration inhibition and structural stiffness optimization. Spectra analysis also proves that the improved electron-phonon coupling and carrier recombination lifetime contribute to enhanced performance. Finally, a flexible and degradable X-ray detector was fabricated with the highest sensitivity of 740.8 µC Gyair -1 cm-2 and low detection limit (0.14 nGyair s-1 ).