Halide Perovskites Films for Ionizing Radiation Detection: An Overview of Novel Solid-State Devices.

Halide perovskites are a novel class of semiconductors that have attracted great interest in recent decades due to their peculiar properties of interest for optoelectronics. In fact, their use ranges from the field of sensors and light emitters to ionizing radiation detectors. Since 2015, ionizing radiation detectors exploiting perovskite films as active media have been developed. Recently, it has also been demonstrated that such devices can be suitable for medical and diagnostic applications. This review collects most of the recent and innovative publications regarding solid-state devices for the detection of X-rays, neutrons, and protons based on perovskite thin and thick films in order to show that this type of material can be used to design a new generation of devices and sensors. Thin and thick films of halide perovskites are indeed excellent candidates for low-cost and large-area device applications, where the film morphology allows the implementation on flexible devices, which is a cutting-edge topic in the sensor sector.

Characterization of the Response of Magnetron Sputtered In2O3-x Sensors to NO2.

The response of resistive In2O3-x sensing devices was investigated as a function of the NO2 concentration in different operative conditions. Sensing layers are 150 nm thick films manufactured by oxygen-free room temperature magnetron sputtering deposition. This technique allows for a facile and fast manufacturing process, at same time providing advantages in terms of gas sensing performances. The oxygen deficiency during growth provides high densities of oxygen vacancies, both on the surface, where they are favoring NO2 absorption reactions, and in the bulk, where they act as donors. This n-type doping allows for conveniently lowering the thin film resistivity, thus avoiding the sophisticated electronic readout required in the case of very high resistance sensing layers. The semiconductor layer was characterized in terms of morphology, composition and electronic properties. The sensor baseline resistance is in the order of kilohms and exhibits remarkable performances with respect to gas sensitivity. The sensor response to NO2 was studied experimentally both in oxygen-rich and oxygen-free atmospheres for different NO2 concentrations and working temperatures. Experimental tests revealed a response of 32%/ppm at 10 ppm NO2 and response times of approximately 2 min at an optimal working temperature of 200 °C. The obtained performance is in line with the requirements of a realistic application scenario, such as in plant condition monitoring.

Temperature-Dependent Amplified Spontaneous Emission in CsPbBr3 Thin Films Deposited by Single-Step RF-Magnetron Sputtering.

Due to their high optical efficiency, low-cost fabrication and wide variety in composition and bandgap, halide perovskites are recognized nowadays as real contenders for the development of the next generation of optoelectronic devices, which, among others, often require high quality over large areas which is readily attainable by vacuum deposition. Here, we report the amplified spontaneous emission (ASE) properties of two CsPbBr3 films obtained by single-step RF-magnetron sputtering from a target containing precursors with variable compositions. Both the samples show ASE over a broad range of temperatures from 10 K up to 270 K. The ASE threshold results strongly temperature dependent, with the best performance occurring at about 50 K (down to 100 µJ/cm2), whereas at higher temperatures, there is evidence of thermally induced optical quenching. The observed temperature dependence is consistent with exciton detrapping up to about 50 K. At higher temperatures, progressive free exciton dissociation favors higher carrier mobility and increases trapping at defect states with consequent emission reduction and increased thresholds. The reported results open the way for effective large-area, high quality, organic solution-free deposited perovskite thin films for optoelectronic applications, with a remarkable capability to finely tune their physical properties.

Magnetron Sputtered CsPbCl3 Perovskite Detectors as Real-Time Dosimeters for Clinical Radiotherapy.

The aim of this study is to investigate the feasibility of manufacturing thin real-time relative dosimeters for clinical radiotherapy (RT) with potential applications for transmission monitoring in vivo dosimetry and pre-treatment dose verifications. Thin (≈1µm) layers of a high sensitivity, wide bandgap semiconductor, the inorganic perovskite CsPbCl3, have been grown for the first time by magnetron sputtering on plastic substrates equipped with electrode arrays. Prototype devices have been tested in real-time configuration to evaluate the dose delivered by a 6MV photon beam from a linear accelerator. Linearity of the charge with the dose has been verified over three order of magnitudes, linearity of the current signal with the dose rate has been also successfully tested in the range 0.5-4.3Gy/min. The combination of high sensitivity per unit volume and wide bandgap provides high signal-to-noise ratios, up to 70, even at moderate applied voltages. The Schottky diode configuration allows the detector to operate without bias voltage (null bias).The blocking-barrier structure allows to confine the active volume within sub-millimetric sizes, a quite attractive feature in view to increase granularity and achieve the high spatial resolutions required in modern RT techniques. All the above-mentioned features indeed pave the way to a novel generation of flexible, transmission, real time dosimeters for clinical radiotherapy.

Electrical and Optical Characterization of CsPbCl3 Films around the High-Temperature Phase Transitions.

Large-area CsPbCl3 films in the range 0.1-1.5 µm have been grown by radio frequency (RF)-magnetron sputtering on glass substrates by means of a one-step procedure. Three structural phase transitions have been detected, which are associated with hysteresis behavior in the electrical current when measured as a function of temperature in the range 295-330 K. Similarly, photoluminescence (PL) experiments in the same temperature range bring evidence of a non-monotonic shift of the PL peak. Detailed electrical characterizations evidenced how phase transitions are not influencing detrimentally the electrical transport properties of the films. In particular, the activation energy (0.6-0.8 eV) extracted from the temperature-dependent film resistivity does not appear to be correlated with phase changes. A non-linear trend of the photoconductivity response as a function of a ultra violet (UV) 365 nm light emitting diode (LED) power has been interpreted considering the presence of an exponential tail of intragap defects. Thermally stimulated currents after exposure with the same LED measured from room temperature up to 370 K showed no evidence of trapping effects due to intragap states on the electrical transport properties at room temperature of the films. As a consequence, measured photocurrents at room temperature appear to be well reproducible and stable in time, which are attractive features for possible future applications in photodetection.

Large-Area Nanocrystalline Caesium Lead Chloride Thin Films: A Focus on the Exciton Recombination Dynamics.

Caesium lead halide perovskites were recently demonstrated to be a relevant class of semiconductors for photonics and optoelectronics. Unlike CsPbBr3 and CsPbI3, the realization of high-quality thin films of CsPbCl3, particularly interesting for highly efficient white LEDs when coupled to converting phosphors, is still a very demanding task. In this work we report the first successful deposition of nanocrystalline CsPbCl3 thin films (70-150 nm) by radio frequency magnetron sputtering on large-area substrates. We present a detailed investigation of the optical properties by high resolution photoluminescence (PL) spectroscopy, resolved in time and space in the range 10-300 K, providing quantitative information concerning carriers and excitons recombination dynamics. The PL is characterized by a limited inhomogeneous broadening (~15 meV at 10 K) and its origin is discussed from detailed analysis with investigations at the micro-scale. The samples, obtained without any post-growth treatment, show a homogeneous PL emission in spectrum and intensity on large sample areas (several cm2). Temperature dependent and time-resolved PL spectra elucidate the role of carrier trapping in determining the PL quenching up to room temperature. Our results open the route for the realization of large-area inorganic halide perovskite films for photonic and optoelectronic devices.

GaAs epilayers grown on patterned (001) silicon substrates via suspended Ge layers.

We demonstrate the growth of low density anti-phase boundaries, crack-free GaAs epilayers, by Molecular Beam Epitaxy on silicon (001) substrates. The method relies on the deposition of thick GaAs on a suspended Ge buffer realized on top of deeply patterned Si substrates by means of a three-temperature procedure for the growth. This approach allows to suppress, at the same time, both threading dislocations and thermal strain in the epilayer and to remove anti-phase boundaries even in absence of substrate tilt. Photoluminescence measurements show the good uniformity and the high optical quality of AlGaAs/GaAs quantum well structures realized on top of such GaAs layer.

Defective States in Micro-Crystalline CsPbBr3 and Their Role on Photoconductivity.

Intrinsic defects in CsPbBr3 microcrystalline films have been studied using thermally stimulated current (TSC) technique in a wide temperature range (100⁻400 K). Below room temperature, TSC emission is composed by a set of several energy levels, in the range 0.11⁻0.27 eV, suggesting a quasi-continuum distribution of states with almost constant density. Above room temperature, up to 400 K, the temperature range of interest for solar cells, both dark current and photocurrent, are mainly dominated by energy levels in the range 0.40⁻0.45 eV. Even if measured trap densities are high, in the range 1013⁻1016 cm-3, the very small capture cross-sections, about 10-26 m², agree with the high defect tolerance characterizing this material.

First Proof-of-Principle of Inorganic Lead Halide Perovskites Deposition by Magnetron-Sputtering.

The present work reports the application of RF-magnetron sputtering technique to realize CsPbBr 3 70 nm thick films on glass substrate by means of a one-step procedure. The obtained films show highly uniform surface morphology and homogeneous thickness as evidenced by AFM and SEM investigations. XRD measurements demonstrate the presence of two phases: a dominant orthorhombic CsPbBr 3 and a subordinate CsPb 2 Br 5 . Finally, XPS data reveals surface bromine depletion respect to the stoichiometrical CsPbBr 3 composition, nevertheless photoluminescence spectroscopy results confirm the formation of a highly luminescent film. These preliminary results demonstrate that our approach could be of great relevance for easy fabrication of large area perovskite thin films. Future developments, based on this approach, may include the realization of multijunction solar cells and multicolor light emitting devices.

Site-Controlled Single-Photon Emitters Fabricated by Near-Field Illumination.

Many of the most advanced applications of semiconductor quantum dots (QDs) in quantum information technology require a fine control of the QDs' position and confinement potential, which cannot be achieved with conventional growth techniques. Here, a novel and versatile approach for the fabrication of site-controlled QDs is presented. Hydrogen incorporation in GaAsN results in the formation of N-2H and N-2H-H complexes, which neutralize all the effects of N on GaAs, including the N-induced large reduction of the bandgap energy. Starting from a fully hydrogenated GaAs/GaAsN:H/GaAs quantum well, the NH bonds located within the light spot generated by a scanning near-field optical microscope tip are broken, thus obtaining site-controlled GaAsN QDs surrounded by a barrier of GaAsN:H (laterally) and GaAs (above and below). By adjusting the laser power density and exposure time, the optical properties of the QDs can be finely controlled and optimized, tuning the quantum confinement energy over more than 100 meV and resulting in the observation of single-photon emission from both the exciton and biexciton recombinations. This novel fabrication technique reaches a position accuracy <100 nm and it can easily be applied to the realization of more complex nanostructures.

Micro-photoluminescence of GaAs/AlGaAs triple concentric quantum rings.

A systematic optical study, including micro, ensemble and time resolved photoluminescence of GaAs/AlGaAs triple concentric quantum rings, self-assembled via droplet epitaxy, is presented. Clear emission from localized states belonging to the ring structures is reported. The triple rings show a fast decay dynamics, around 40 ps, which is expected to be useful for ultrafast optical switching applications.