RESUMEN
Design of hypotoxic lead-free perovskites, e.g. Bismuth(Bi)-based perovskites, is much beneficial for commercialization of perovskite X-ray detectors due to their strong radiation absorption. Nevertheless, the design principles governing the selection of A-site cations for achieving high-performance X-ray detectors remain elusive. Here, seven molecules (methylamine MA, amine NH3, dimethylbiguanide DGA, phenylethylamine PEA, 4-fluorophenethylamine p-FPEA, 1,3-propanediamine PDA, and 1,4-butanediamine BDA) and calculated their dipole moments and interaction strength with metal halide (BiI3) are selected. The first-principles calculations and related spectroscopy measurements confirm that organic molecules (DGA) with large dipole moments can have strong interactions with perovskite octahedron and improve the carrier transport between the organic and inorganic clusters. Consequently, zero-dimensional single crystal (SC) (DGA)BiI5âH2O is synthesized. The (DGA)BiI5âH2O SCs demonstrate an exceptional carrier mobility-lifetime product of 6.55 × 10-3 cm2 V-1, resulting in the high sensitivity of 5879.4 µCGyair -1cm-2, featuring a low detection limit (4.7 nGyair s-1) and remarkable X-ray irradiation stability even after 100 days of aging at a high electric field (100 V mm-1). Furthermore, the (DGA)BiI5âH2O SCs for imaging, achieving a notable spatial resolution of 5.5 lp mm-1 are applied. This investigation establishes a pathway for systematically screening A-site cations to design low-dimensional SCs for high-performance X-ray detection.
RESUMEN
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.
RESUMEN
2D organic-inorganic hybrid perovskites (OIHPs) have shown great promise in direct X-ray detection. The development of high-performance passive X-ray detectors in 2D OIHPs calls for an increase in material density while maintaining structural polarity, which is becoming quite challenging. Here, a high-density, polar 2D alternating-cation-intercalated (ACI) perovskite, (4-AP)Cs2Pb2I8 (B, 4-AP = 4-amidinopyridinium), capable of addressing this problem is successfully constructed by introducing heavy Cs+ into the interlayer space of an aromatic Dion-Jacobson (DJ) perovskite (4-AP)PbI4 (A). Through such a DJ-to-ACI design, the newly developed 2D OIHP B not only significantly increases its density to 4.23 g cm-3 (even higher than that of 3D MAPbI3) but also crystallizes in a polar space group (Ama2), which further leads to enhanced X-ray attenuation and an obvious polar photovoltage (1.1 V) under X-ray irradiation. As a result, X-ray detectors fabricated by high-quality single crystals of B exhibit excellent and stable detection performance under self-powered mode with a high sensitivity of 107 µC Gy-1 cm-2 and a low detection limit of 289 nGy s-1. This work provides implications for the future exploration and regulation of novel ACI OIHPs for high-performance photoelectronic devices.
RESUMEN
Three-dimensional (3D) pseudohalide rare-earth double perovskites (PREDPs) have garnered significant attention for their versatile physical properties, including ferroelectricity, ferroelasticity, large piezoelectric responses, and circularly polarized luminescence. However, their potential for X-ray detection remains unexplored, and the low Curie temperature (TC) limits the performance window for PREDP ferroelectrics. Here, by applying the chemical regulation strategies involving halogen substitution on the organic cation and Rb/Cs substitution to the PREDP [(R)-M3HQ]2RbEu(NO3)6 [(R)-M3HQ = (R)-N-methyl-3-hydroxylquinuclidinium] with a low TC of 285 K, a novel 3D PREDP ferroelectric [(R)-CM3HQ]2CsEu(NO3)6 [(R)-CM3HQ = (R)-N-chloromethyl-3-hydroxylquinuclidinium] are successfully synthesized, for which the TC reaches 344 K. More importantly, such a strategy endowed [(R)-CM3HQ]2CsEu(NO3)6 with notable X-ray detection capabilities. Centimeter-sized [(R)-CM3HQ]2CsEu(NO3)6 single crystals fabricated from aqueous solutions demonstrated a sensitivity of 1307 µC Gyair-1 cm-2 and a low detectable dose rate of 152 nGyair s-1, the highest sensitivity reported for hybrid double perovskite ferroelectric detectors. This work positions PREDPs as promising candidates for the next generation of eco-friendly optoelectronic materials and also offers substantial insights into the interaction between structure, composition, and functionality in ferroelectric materials.
RESUMEN
Triplet exciton is both a luminescence quenching factor and an important luminescence sensitization technology solution, which is widely concerned in the field of optoelectronic materials. Since X-ray excited triplet excitons are dissipated through various pathways, there are still huge difficulties in achieving efficient triplet sensitized emission. Here, the antenna ligand is regulated through the carboxyl group, increasing the steric hindrance between the conjugated groups and improving triplet-enhanced radioluminescence (RL) efficiencies of Tb3+. The lanthanide metal-organic frameworks (Ln-MOFs) formed by the coordination of Tb3+ with mellitic acid (MA), pyromellitic acid (PMA) and trimesic acid (TMA) under low temperature preparation conditions. Among them, MA-Tb has a longer spacing between conjugated groups than PMA-Tb and TMA-Tb, and its triplet RL is relatively strongest, with a light yield of 28,000 photons MeV-1. Mechanistic studies revealed that the RL efficiency of Ln-MOFs is related to the π-π stacking effect in the benzene ring. In addition, the application of MA-Tb in the field of X-ray detection was demonstrated. The RL intensity of MA-Tb has a good linear relationship with the X-ray dose rate, and the detection limit for X-ray reaches 82 nGy/s, which is 66 times lower than the typical medical imaging dose. These results will provide a universal strategy for the design of Ln-MOFs scintillator.
RESUMEN
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.
RESUMEN
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 â 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 12.2â 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.
RESUMEN
Perovskite nanocrystals (PNCs) offer unique advantages in large-area and thick-film deposition for X-ray detection applications due to the decoupling of the crystallization of perovskite from film formation, as well as their low-temperature and scalable deposition methods. However, the partial detachment of long-chain ligands in PNCs during the purification process would lead to the exposure of surface defects, making it challenging to ensure efficient charge carrier extraction and stable X-ray detection. In this study, we propose a beneficial strategy that involves the in situ reparation of these exposed defects with sodium bromide (NaBr) during the purification process to construct CsPbBr3 PNC-organic bulk heterostructure X-ray detectors. The NaBr-passivated PNCs exhibit stronger photoluminescence intensity and lower trap density in films compared to those of the control samples, confirming the effective passivation of halide vacancy defects. Furthermore, the NiOx hole transport layer with remarkable electron blocking capability is introduced to further suppress the dark current of the devices. Consequently, the optimal devices exhibit a large sensitivity of 4237 µC Gyair-1 cm-2 and a low dark current density of 10 nA cm-2, as well as improved operational stability, which allows for high-contrast and low-dose X-ray imaging applications.
RESUMEN
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.
RESUMEN
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.
RESUMEN
Two-dimensional (2D) Dion-Jacobson (DJ) perovskites typically outperform Ruddlesden-Popper (RP) analogs in terms of photodetection (PD). However, the mechanism behind this enhanced performance remains elusive. Theoretical calculations for elucidating interlayer spacer conformation-induced multiple hydrogen bonds in 2D perovskite are presented, along with the synthesis of DPAPbBr4 (DPB) single crystals (SCs) and their PD properties under X-ray/ultraviolet (UV) excitation. The high-quality DPB SC enhances PD with exceptional photoresponse attributes, including a high on/off ratio (4.89 × 104), high responsivity (2.44 A Wâ»1), along with large dynamic linear range (154 dB) and low detection limit (7.1 nW cmâ»2), which are currently the best results among 2D perovskite SC detectors, respectively. Importantly, high-resolution images are obtained under UV illumination with weak light levels. The SC X-ray detector exhibits a high sensitivity of 663 µC Gyairâ»1 cm-2 at 10 V and a detection limit of 1.44 µGyair sâ»1. This study explores 2D DJ perovskites for efficient and innovative optoelectronic applications.
RESUMEN
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.
RESUMEN
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.
RESUMEN
Halide perovskites have emerged as highly promising materials for ionizing radiation detection due to their exceptional characteristics, including a large mobility-lifetime product, strong stopping power, tunable band gap, and cost-effective crystal growth via solution processes. Semiconductor-type X-ray detectors employing various micro/nano perovskite materials have shown impressive progress in achieving heightened sensitivity and lower detection limits. Here, we present a comprehensive review of the applications of micro/nano perovskite materials for direct type X-ray detection, with a focus on the requirements for micro/nano crystal assembly and device properties in advanced X-ray detectors. We explore diverse processing techniques and optoelectronic considerations applied to perovskite X-ray detectors. Additionally, this review highlights the challenges and promising opportunities for perovskite X-ray detector arrays in real-world applications, potentially necessitating further research efforts.
RESUMEN
Organic semiconducting materials are promising for the fabrication of flexible ionizing radiation detectors for imaging because of their tissue equivalence, simple large-scale processing, and mass production. However, it is challenging to achieve high-sensitivity detection for organic direct detectors prepared by low-cost solution processing because of the compromise between thickness and carrier transport. In this study, high-performance organic direct X-ray detectors were fabricated by building a micrometer-thick bulk heterojunction (BHJ) using poly(3-hexylthiophene-2,5-diyl) (P3HT):(6,6)-phenyl c71 butyric acid methyl ester. A 5 µm BHJ film was fabricated by drop-casting and enhanced crystallization of P3HT using binary solvents and high-boiling-point additives to improve the charge carrier mobility. Furthermore, this organic direct X-ray detector has a sensitivity of >654.26 µC Gyair s-1 and a self-powered response. Because of the architecture of the thick active layer and the energy cascade in this diode detector, it has a very low dark current of 46.26 pA at -2 V. A fast and efficient approach was developed for fabricating thick, highly mobile organic BHJ films for high-performance direct X-ray detectors. It has great potential for application in a new generation of flexible and portable large-area flat-panel detectors.
RESUMEN
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 (0.47â V) and large mobility-lifetime product (1.1×10-3 â 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 220â 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.
RESUMEN
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.
RESUMEN
Metal halide perovskite single crystals (MHP-SCs) are known for their facile fabrication into large sizes using inexpensive solution methods. Owing to their combination of large mobility-lifetime products and strong X-ray absorption, they are considered promising materials for efficient X-ray detection. However, they suffer from large dark currents and severe ion migration, which limit their sensitivity and stability in critical X-ray detection applications. Herein, a heterointerface design is proposed to reduce both the dark current and ion migration by forming a heterojunction. In addition, the carrier transport performance is significantly improved using heterointerface engineering by designing a gradient band structure in the SCs. The SC heterojunction detectors exhibit a high sensitivity of 3.98 × 105 µC Gyair -1 cm-2 with a low detection limit of 12.2 nGyair s-1 and a high spatial resolution of 10.2 lp mm-1 during imaging. These values are among the highest reported for state-of-the-art MHP X-ray detectors. Moreover, the detectors show excellent stability under continuous X-ray irradiation and maintainclear X-ray imaging after 240 d. This study provides novel insights into the design and fabrication of X-ray detectors with high detection efficiency and stability, which are beneficial for developing inexpensive, high-resolution X-ray imaging equipment.
RESUMEN
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.
RESUMEN
Nowadays, weak interlayer coupling and unclear mechanism in layered hybrid silver bismuth bromine (LH-AgBiBr) are the main reasons for limiting its further enhanced X-ray detection sensitivity and stability. Herein, the design rules for LH-AgBiBr and its influence on X-ray detection performance are reported for the first time. Although shortening amine size can enhance interlayer coupling, its detection performance is severely hampered by its easier defect formation caused by enlarged micro strain. In contrast, an appropriate divalent amine design endows the material with improved interlayer coupling and released micro strain, which benefits crystal stability and mechanical hardness. Another contribution is to increase material density and dielectric constant; thus, enhancing X-ray absorption and carrier transport. Consequently, the optimized parallel device based on BDA2 AgBiBr8 achieves a record sensitivity of 2638 µC Gyair -1 cm-2 and an ultra-low detection limit of 7.4 nGyair s-1 , outperforming other reported LH-AgBiBr X-ray detectors. Moreover, the unencapsulated device displays remarkable anti-moisture, anti-thermal (>150 °C), and anti-radiation (>1000 Gyair ) endurance. Eventually, high-resolution hard X-ray imaging is demonstrated by linear detector arrays under a benign dose rate (1.63 µGyair s-1 ) and low external bias (5 V). Hence, these findings provide guidelines for future materials design and device optimization.