Perovskite X-ray Detectors Research Articles

Straight Manipulation Annealing in a Solvent Atmosphere for Quality-Improved Cs2AgBiBr6 Perovskites.

As a new-generation photoelectric material, perovskites have attracted researchers' attention due to their excellent optoelectronic properties. However, the existence of defects inevitably causes structural degradation and restricts their performance, which need to be further improved by post-treatment. At present, post-treatments mostly focus on non-contact treatments, which may constrain the effect since the influence on the perovskites caused by the direct contact is much more straightly. Therefore, we proposed an annealing strategy of straight manipulation in a solvent atmosphere with the assistance of polyimide (PI) tape for the perovskite post-treatment, due to the high heat resistance and less glue residual of this tape. It casts an influence on the perovskite directly, proving the possibility of the straight manipulation by operators, promoting the recrystallization of the perovskite grains and removing the impurity substance. The optimized Pb-free perovskite film exhibits a better X-ray sensitivity of 7.5 × 104 μC Gyair-1 cm-2 and a great detection limit of 47 nGyair s-1, which is comparable to advanced Pb-based perovskite X-ray detectors and all commercial ones. The new annealing strategy provides a facile, effective, and simple method to improve the perovskite quality, exhibiting the potential and harmlessness of the direct contact post-treatment, which paves the way for a broader application of perovskites.

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.

High-performance metal halide perovskite X-ray detectors fabricated with antisolvent-assisted spray-coating

Metal halide perovskites have gained significant attention as promising materials for ionizing radiation detection due to their facile fabrication process, exceptional optoelectronic properties and high attenuation coefficients. To effectively absorb the incident X-ray photons, thick active layers have been reported and fabricated via spray-coating. However, the conventional spray-coating method is susceptible to various adverse effects, making it challenging to achieve high-quality thick perovskite films. In this work, we propose the use of antisolvent-assisted spray-coating to deposit perovskite films, which results in small surface roughness, thick films on various substrates. The slow growth of the thick film and the ability to regulate its crystallization through the modulation of processing atmosphere were also carefully studied. The optimized X-ray detector demonstrated a sensitivity of up to 3370.8 μC Gyair−1 cm−2, demonstrating its great potential for X-ray detection applications.

Lead-Free Halide Perovskites for Direct X-Ray Detectors.

Lead halide perovskites have made remarkable progress in the field of radiation detection owing to the excellent and unique optoelectronic properties. However, the instability and the toxicity of lead-based perovskites have greatly hindered its practical applications. Alternatively, lead-free perovskites with high stability and environmental friendliness thus have fascinated significant research attention for direct X-ray detection. In this review, the current research progress of X-ray detectors based on lead-free halide perovskites is focused. First, the synthesis methods of lead-free perovskites including single crystals and films are discussed. In addition, the properties of these materials and the detectors, which can provide a better understanding and designing satisfactory devices are also presented. Finally, the challenge and outlook for developing high-performance lead-free perovskite X-ray detectors are also provided.

Stable perovskite single-crystal X-ray imaging detectors with single-photon sensitivity

A major thrust of medical X-ray imaging is to minimize the X-ray dose acquired by the patient, down to single-photon sensitivity. Such characteristics have been demonstrated with only a few direct-detection semiconductor materials such as CdTe and Si; nonetheless, their industrial deployment in medical diagnostics is still impeded by elaborate and costly fabrication processes. Hybrid lead halide perovskites can be a viable alternative owing to their facile solution growth. However, hybrid perovskites are unstable under high-field biasing in X-ray detectors, owing to structural lability and mixed electronic–ionic conductivity. Here we show that both single-photon-counting and long-term stable performance of perovskite X-ray detectors are attained in the photovoltaic mode of operation at zero-voltage bias, employing thick and uniform methylammonium lead iodide single-crystal films (up to 300 µm) and solution directly grown on hole-transporting electrodes. The operational device stability exceeded one year. Detection efficiency of 88% and noise-equivalent dose of 90 pGyair are obtained with 18 keV X-rays, allowing single-photon-sensitive, low-dose and energy-resolved X-ray imaging. Array detectors demonstrate high spatial resolution up to 11 lp mm−1. These findings pave the path for the implementation of hybrid perovskites in low-cost, low-dose commercial detector arrays for X-ray imaging.

Additive-Induced Synergies of Ion Migration Inhibition and Defect Passivation toward Sensitive Perovskite X-ray Detectors

Two-dimensional (2D) Ruddlesden-Popper (RP) metal halide perovskites have emerged as a promising material for X-ray detection. However, defects and ion migration generated nonradiative recombination and high dark current could cause severe performance degradation, which hinders their application. Herein, rubrene was added to the precursor solution of BA2MA3Pb4I13 to modulate the performance of the 2D RP perovskite X-ray detectors. The cation-π interaction between rubrene and perovskite could passivate the defects and inhibit the ion migration, resulting in improved performance and stability. The detectors made with rubrene exhibited a sensitivity of 354.30 μC·Gyair-1 cm-2 and a detection limit of 112.85 nGyair s-1. This work highlights the synergistic effect of rubrene in defect passivation and ion migration inhibition, providing a facile approach toward sensitive perovskite X-ray detectors.

Sr-Doping All-Inorganic CsPbBr3 Perovskite Thick Film for Self-Powered X-ray Detectors.

The all-inorganic perovskite cesium lead bromine (CsPbBr3) has attracted much attention in the field of X-ray detectors because of its high X-ray absorption coefficient, high carrier collection efficiency, and easy solution preparation. The low-cost anti-solvent method is the main method to prepare CsPbBr3; during this process, solvent volatilization will bring a large number of holes to the film, leading to the increase of defects. Based on the heteroatomic doping strategy, we propose that Pb2+ should be partially replaced by Sr2+ to prepare leadless all-inorganic perovskite. The introduction of Sr2+ promoted the ordered growth of CsPbBr3 in the vertical direction, increased the density and uniformity of the thick film, and achieved the goal of CsPbBr3 thick film repairing. In addition, the prepared CsPbBr3 and CsPbBr3:Sr X-ray detectors were self-powered without external bias, maintaining a stable response during on and off states at different X-ray dose rates. Furthermore, the detector base on 160 µm CsPbBr3:Sr had a sensitivity of 517.02 µC Gyair-1 cm-3 at zero bias under the dose rate of 0.955 µGy ms-1 and it obtained a fast response speed of 0.053-0.148 s. Our work provides a new opportunity to produce cost-effective and highly efficient self-powered perovskite X-ray detectors in a sustainable way.

Realizing nearly-zero dark current and ultrahigh signal-to-noise ratio perovskite X-ray detector and image array by dark-current-shunting strategy

Although perovskite X-ray detectors have revealed promising properties, their dark currents are usually hundreds of times larger than the practical requirements. Here, we report a detector architecture with a unique shunting electrode working as a blanking unit to suppress dark current, and it theoretically can be reduced to zero. We experimentally fabricate the dark-current-shunting X-ray detector, which exhibits a record-low dark current of 51.1 fA at 5 V mm−1, a detection limit of 7.84 nGyair s−1, and a sensitivity of 1.3 × 104 μC Gyair−1 cm−2. The signal-to-noise ratio of our polycrystalline perovskite-based detector is even outperforming many previously reported state-of-the-art single crystal-based X-ray detectors by serval orders of magnitude. Finally, the proof-of-concept X-ray imaging of a 64 × 64 pixels dark-current-shunting detector array is successfully demonstrated. This work provides a device strategy to fundamentally reduce dark current and enhance the signal-to-noise ratio of X-ray detectors and photodetectors in general.

An interfacial toughening strategy for high stability 2D/3D perovskite X-ray detectors with a carbon nanotube thin film electrode.

Single-crystalline metal halide perovskite materials hold great promise for developing next-generation low-dose X-ray detection. To bring this new technology into reality, it is important to improve the durability of perovksite detectors by suppressing the well-known corrosion and ion diffusion problems at the perovskite/electrode interface. For imaging application, it is also imperative to develop new assembling approaches to realise non-planar interconnection between thick perovskite crystals and thin-film transistor (TFT) backplanes. Herein, a flexible and mechanically robust carbon nanotube (CNT) film was proposed to replace noble metal electrodes. The proposed CNT film, whose binder contains a carboxyl group, can form solid contact with a phenethylamine-based two-dimensional (2D) perovskite via amide coupling, thus toughening the perovskite-electrode interface. The resulting CNT/2D-3D perovskite detector shows an applaudable low dark current, high sensitivity, a low dose detection limit and excellent stability, retaining 98% of its initial sensitivity after storage for three months. Moreover, the flexible CNT films are also beneficial for making non-planar interconnection between thick perovskite crystals and TFT backplanes. The proposed flexible CNT thin film electrode thus provides a facile route towards realising a low-dose, high-resolution and highly stable perovskite X-ray detector.

Bulk Heterostructure BA2PbI4/MAPbI3 Perovskites for Suppressed Ion Migration To Achieve Sensitive X-ray Detection Performance.

Three-dimensional (3D) lead-halide perovskites with outstanding mobility-lifetime products and large attenuation coefficients for X-ray photons have demonstrated highly sensitive X-ray detection. However, there exists severe ion migration, especially under electrical bias, that results in dark-current drift and poorer device stability. Theoretical analyses suggest that 3D perovskites with two-dimensional (2D) perovskites may mitigate ion migration and reduce the dark current to achieve a drastically lower detection limit, which is badly needed for X-ray diagnostics. A bulk 2D/3D perovskite heterostructure is therefore designed and prepared by hot-pressing a mixture of BA2PbI4 and MAPbI3 particles. Compared with the pure MAPbI3 pellet, the bulk 2D/3D heterostructure pellet shows much higher resistivity, hence, significantly reduced ion migration and a much smaller dark-current drift of 4.84 × 10-5 nA cm-1 s-1 V-1, which is much lower than that of the pristine MAPbI3 pellet, thus demonstrating its effectiveness for the suppression of ion migration. The bulk 2D/3D heterostructure pellet attains an X-ray sensitivity of 2.0 × 103 μC Gyair-1 cm-2 as well as a lower detection limit of 111.76 nGy s-1 under 10 V bias. This work provides a successful strategy to prepare X-ray detectors with suppressed ion migration and negligible dark current drift, which will further benefit the development of lead-halide perovskite X-ray detectors.

An ultrafast x-ray photoelectric detector using CsPbI2Br perovskite film

Metal halide perovskites have attracted worldwide attention in the field of x-ray detection due to their effective light absorption, excellent optoelectronic yield, high charge carrier mobility, and facile solution-processed preparation. Most of the current metal halide perovskite x-ray detectors rely on photoconductive or photovoltaic effects. In this work, we use CsPbI2Br perovskite films to demonstrate an ultrafast x-ray detector based on the photoelectric effect. The photoelectric effect allows the detector to exhibit a temporal resolution of 170 ps and an ultra-low dark current (10−5–10−3 pA), and the temporal response is the fastest among the reported perovskite x-ray detectors. The detector also exhibits a detectivity of 1.28 × 1010 Jones and a noise equivalent power of 6.95 × 10−11 W Hz−1/2. This ultrafast x-ray photoelectric detector has been utilized to diagnose x-ray flux in inertial confinement fusion experiments.

Review: Perovskite X-ray Detectors (1997–Present)

Perovskite materials have attracted extensive attention because of their superior performance in the fields of photoelectric detection, photovoltaics, light-emitting diodes, metal–air batteries, etc. However, their development and application in the field of X-ray detectors have not been reviewed. In this paper, research on perovskite-based X-ray detectors is analyzed using the bibliometric method. This analysis sample includes the literature from 1997 to the present. In addition, the research status of perovskite-based scintillators and direct X-ray detectors under different crystallization conditions and different preparation methods is discussed. Finally, several problems that need to be overcome in the future of perovskite-based X-ray detectors are put forward.

Dark current modeling of thick perovskite X-ray detectors

Metal halide perovskites (MHPs) have demonstrated excellent performances in detection of X-rays and gamma-rays. Most studies focus on improving the sensitivity of single-pixel MHP detectors. However, little work pays attention to the dark current, which is crucial for the back-end circuit integration. Herein, the requirement of dark current is quantitatively evaluated as low as 10−9 A/cm2 for X-ray imagers integrated on pixel circuits. Moreover, through the semiconductor device analysis and simulation, we reveal that the main current compositions of thick perovskite X-ray detectors are the thermionic-emission current (JT) and the generation-recombination current (Jg-r). The typical observed failures of p–n junctions in thick detectors are caused by the high generation-recombination current due to the band mismatch and interface defects. This work provides a deep insight into the design of high sensitivity and low dark current perovskite X-ray detectors.Graphical

Hybrid perovskite X-ray detectors with enhanced radioluminescence via thermally activated delayed fluorescence

Recently, metal halide perovskites have received great attention for detecting ionizing radiation. Perovskite-based photodetectors and scintillators have been successfully implemented for X-ray and γ-ray detection due to their high attenuation coefficient and excellent optoelectronic properties. However, relatively thick absorbing layers are required for the complete absorption of X-ray photons, which are very challenging to fabricate with solution processes. In this work, we designed hybrid devices coupled with excellent perovskite photodiodes to utilize the incident X-rays fully. Considering the heavy reabsorption of the perovskite layers, we blended CsPbBr3 with a Cu(I)-containing thermally activated delayed fluorescent complex (MAC*)Cu(Cz) to achieve down-conversion luminescence effectively to maximize the radioluminescence quantum efficiency, and we also found a faster afterglow compared with the commercial scintillators. Furthermore, we systematically investigated the performance metrics of the CsPbIBr2 photodiodes and scintillator films. The hybrid devices demonstrated significantly improved X-rays sensitivity, indicating potential for X-ray detection and imaging.

Engineering stable perovskite X-ray detectors

Engineering stable perovskite X-ray detectors

Spray-coating of AgI incorporated metal halide perovskites for high-performance X-ray detection

Metal halide perovskites have emerged as a promising candidate for ionizing radiation detection, thanks to the facile fabrication, excellent optoelectronic properties and high attenuation coefficient. In order to fully absorb the incident X-ray photons, X-ray detectors require relatively thick active layers. However, it is challenging to obtain thick perovskite films based on conventional solution-based techniques, due to the limited solubility and viscosity of the perovskite precursors. In this work, we introduced spray-coating to deposit perovskite films on various substrates, and achieved tunable and thick films. On the other hand, the charge transport is another issue limiting the device performance of perovskite X-ray detectors. Compared with conventional inorganic semiconductors, hybrid perovskites possess relatively poor charge carrier mobility and lifetime. To address this issue, we incorporate AgI within the perovskite precursor, and systematically investigated their optoelectronic properties. It was found that the optimized AgI incorporated perovskite films exhibited the highest mobility-lifetime product, resulted X-ray sensitivity up to 3433 μGyair−1 cm−2 and ultra-low detection limit of 3.5 nGyair s−1, suggesting great potential for X-ray detection.

Synergistic strain engineering of perovskite single crystals for highly stable and sensitive X-ray detectors with low-bias imaging and monitoring

Although three-dimensional metal halide perovskite (ABX3) single crystals are promising next-generation materials for radiation detection, state-of-the-art perovskite X-ray detectors include methylammonium as A-site cations, limiting the operational stability. Previous efforts to improve the stability using formamidinium–caesium-alloyed A-site cations usually sacrifice the detection performance because of high trap densities. Here we successfully solve this trade-off between stability and detection performance by synergistic composition engineering, where we include A-site alloys to decrease the trap density and B-site dopants to release the microstrain induced by A-site alloying. As such, we develop high-performance perovskite X-ray detectors with excellent stability. Our X-ray detectors exhibit high sensitivity of (2.6 ± 0.1) × 104 μC Gyair−1 cm−2 under 1 V cm−1 and ultralow limit of detection of 7.09 nGyair s−1. In addition, they feature long-term operational stability over half a year and impressive thermal stability up to 125 °C. We further demonstrate the promise of our perovskite X-ray detectors for low-bias portable applications with high-quality X-ray imaging and monitoring prototypes.

Vertical matrix perovskite X-ray detector for effective multi-energy discrimination

Multi-energy X-ray detection is sought after for a wide range of applications including medical imaging, security checking and industrial flaw inspection. Perovskite X-ray detectors are superior in terms of high sensitivity and low detection limit, which lays a foundation for multi-energy discrimination. However, the extended capability of the perovskite detector for multi-energy X-ray detection is challenging and has never been reported. Herein we report the design of vertical matrix perovskite X-ray detectors for multi-energy detection, based on the attenuation behavior of X-ray within the detector and machine learning algorithm. This platform is independent of the complex X-ray source components that constrain the energy discrimination capability. We show that the incident X-ray spectra could be accurately reconstructed from the conversion matrix and measured photocurrent response. Moreover, the detector could produce a set of images containing the density-graded information under single exposure, and locate the concealed position for all low-, medium- and high-density substances. Our findings suggest a new generation of X-ray detectors with features of multi-energy discrimination, density differentiation, and contrast-enhanced imaging.

All-Vacuum-Deposited Perovskite X-ray Detector with a Record-High Self-Powered Sensitivity of 1.2 C Gy-1 cm-3.

Highly sensitive X-ray detection is crucial in, for example, medical imaging and secure inspection. Halide perovskite X-ray detectors are promising candidates for detecting highly energetic radiation. In this report, we describe vacuum-deposited Cs-based perovskite X-ray detectors possessing a p-i-n architecture. Because of the built-in potential of the p-i-n structure, these perovskite X-ray detectors were capable of efficient charge collection and displayed an exceptionally high X-ray sensitivity (1.2 C Gyair-1 cm-3) under self-powered, zero-bias conditions. We ascribe the outstanding X-ray sensitivity of the vacuum-deposited CsPbI2Br devices to their prominent charge carrier mobility. Moreover, these devices functioned with a lowest detection limit of 25.69 nGyair s-1 and possessed excellent stability after exposure to over 3000 times the total dose of a chest X-ray image. For comparison, we also prepared traditional spin-coated CH3NH3-based perovskite devices having a similar device architecture. Their volume sensitivity was only one-fifth of that of the vacuum-deposited CsPbI2Br devices. Thus, all-vacuum deposition appears to be a new strategy for developing perovskite X-ray detectors; with a high practical deposition rate, a balance can be reached between the thickness of the absorbing layer and the fabrication time.

Polycrystalline Formamidinium Lead Bromide X-ray Detectors

We have investigated the performance of formamidinium lead bromide (FAPbBr3) perovskite X-ray detectors fabricated from polycrystalline material that is pressed into a pellet at high pressures. FAPbBr3 has been shown to exhibit a remarkable combination of electrical and physical properties, such that mechanically-formed polycrystalline pellets exhibit good charge transport properties suitable for use as X-ray detectors. We characterise the morphology and structure of FAPbBr3 pellets using photoluminescence (PL), electron microscopy (SEM) and X-ray diffraction (XRD), and demonstrate an improvement in the microstructure, density, and charge transport performance of the material as the pressure is increased from 12 MPa to 124 MPa. The use of annealing of the pellets after pressing also improves the stability and charge transport performance of the devices. Using a 40 kV X-ray beam, a maximum X-ray sensitivity of 169 µC Gy−1 cm−2 was measured, and the fast time response of the devices was demonstrated using a chopped X-ray beam.