Mixed-Halide Perovskite Film-Based Neuromorphic Phototransistors for Mimicking Experience-History-Dependent Sensory Adaptation.

Sensory adaptation is an essential function for humans to live on the earth. Herein, a hybrid synaptic phototransistor based on the mixed-halide perovskite/organic semiconductor film is reported. This hybrid phototransistor achieves photosensitive performance including a high photoresponsivity over 4 × 103 A/W and an excellent specific detectivity of 2.8 × 1016 Jones. Due to the photoinduced halide-ion segregation of the mixed-halide perovskites and their slow recovery properties, the experience-history-dependent sensory adaptation behavior can be mimicked. Moreover, the light pulse width, intensity, light wavelength, and gate bias can be used to regulate the adaptation processes to improve its adaptability and perceptibility in different environments. The CsPbBrxI3-x/organic semiconductor hybrid films produced by spin coating are beneficial to large-scale fabrication. This study fabricates a novel solution-processable light-stimulated synapse based on inorganic perovskites for mimicking the human sensory adaptation that makes it possible to approach artificial neural sensory systems.

Investigating the mapping of chromophore excitations onto the electron detachment spectrum: photodissociation spectroscopy of iodide ion-thiouracil clusters.

Laser photodissociation spectroscopy (3.1-5.7 eV) has been applied to iodide complexes of the non-native nucleobases, 2-thiouracil (2-TU), 4-thiouracil (4-TU) and 2,4-thiouracil (2,4-TU), to probe the excited states and intracluster electron transfer as a function of sulphur atom substitution. Photodepletion is strong for all clusters (I-·2-TU, I-·4-TU and I-·2,4-TU) and is dominated by electron detachment processes. For I-·4-TU and I-·2,4-TU, photodecay is accompanied by formation of the respective molecular anions, 4-TU- and 2,4-TU-, behaviour that is not found for other nucleobases. Notably, the I-·2TU complex does not fragment with formation of its molecular anion. We attribute the novel formation of 4-TU- and 2,4-TU- to the fact that these valence anions are significantly more stable than 2-TU-. We observe further similar behaviour for I-·4-TU and I-·2,4-TU relating to the general profile of their photodepletion spectra, since both strongly resemble the intrinsic absorption spectra of the respective uncomplexed thiouracil molecule. This indicates that the nucleobase chromophore excitations are determining the clusters' spectral profile. In contrast, the I-·2-TU photodepletion spectrum is dominated by the electron detachment profile, with the near-threshold dipole-bound excited state being the only distinct spectral feature. We discuss these observations in the context of differences in the dipole moments of the thionucleobases, and their impact on the coupling of nucleobase-centred transitions onto the electron detachment spectrum.

Facile fabrication of silver iodide/graphitic carbon nitride nanocomposites by notable photo-catalytic performance through sunlight and antimicrobial activity.

Silver iodide/graphitic carbon nitride nanocomposites have been successfully fabricated through sonication-assisted deposition-precipitation route at room temperature and hydrothermal method. Varied mass ratios and preparation processes can modify the structure, purity, shape, and scale of specimens. The purity of the product was confirmed by Energy Dispersive X-Ray Spectroscopy (EDS) and X-ray crystallography. The morphology and size of specimens could be observed with transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). The bandgap was evaluated around 2.82 eV for pure g-C3N4. The bandgap has reduced to 2.70 eV by increasing the quantity of silver iodide in the nanocomposites. The photocatalytic activity of AgI/C3N4 has been studied over the destruction of rhodamine B (RhB) and methyl orange (MO) through visible radiation due to their suitable bandgap. The as-prepared AgI/C3N4 nanocomposites photocatalyst revealed better photocatalytic behavior than the genuine AgI and C3N4 which ascribed to synergic impacts at the interconnection of C3N4 and AgI. Furthermore, these nanocomposites have great potential for being a great antibacterial agent.

Three-dimensional flower-like shaped Bi5O7I particles incorporation zwitterionic fluorinated polymers with synergistic hydration-photocatalytic for enhanced marine antifouling performance.

Herein, several novel composite films consisting of three-dimensional (3D) Bi5O7I flower-like shaped microsphere and zwitterionic fluorinated polymer (ZFP) were successfully fabricated with the aim of achieving high anti-fouling performance. The prepared Bi5O7I flower-like shaped microsphere particles with diameters in the range of 2∼3 µm were uniformly distributed on the surface and in the internal of ZFP. Benefiting from the hydration layer formed by the ZFP and the efficient photocatalytic performance of Bi5O7I flower-like microsphere, the resultant optimized Bi5O7I/ZFP composite film exhibited an excellent diatom anti-settling performance and a high antibacterial rate of 99.09% and 99.66% towards Escherichia coli and Staphylococcus aureus. In addition, the composite films possessed the strengthened visible light absorption, the effectively separation and transfer of the photo-induced electrons and holes, the large number of hydroxyl (OH) radicals and superoxide radicals (O2-) all in Bi5O7I/ZFP systems, all of which were beneficial for the photocatalytic antifouling activity. More importantly, the synergistic hydration-photocatalytic effect of the Bi5O7I/ZFP composite films are answerable for the improvement of the antifouling property compared to the control. Thus, the synergistic hydration-photocatalytic contribution of Bi5O7I/ZFP composite film will shows promise for potential application in marine antifouling.

Time-resolved dynamics in iodide-uracil-water clusters upon excitation of the nucleobase.

The dynamics of iodide-uracil-water (I-·U·H2O) clusters following π-π* excitation of the nucleobase are probed using time-resolved photoelectron spectroscopy. Photoexcitation of this cluster at 4.77 eV results in electron transfer from the iodide moiety to the uracil, creating a valence-bound anion within the cross correlation of the pump and probe laser pulses. This species can decay by a number of channels, including autodetachment and dissociation to I- or larger anion fragments. Comparison of the energetics of the photoexcited cluster and its decay dynamics with those of the bare iodide-uracil (I-·U) complex provides a sensitive probe of the effects of microhydration on these species.

Hot Biexciton Effect on Optical Gain in CsPbI3 Perovskite Nanocrystals.

Combining the superior optical properties of their bulk counterparts with quantum confinement effects, lead halide perovskite nanocrystals are unique laser materials with low-threshold optical gain. In such nonlinear optical regimes, multiple excitons are generated in the nanocrystals and strongly affect the optical gain through many-body interactions. Here, we investigate the exciton-exciton interactions in CsPbI3 nanocrystals by femtosecond transient absorption spectroscopy. From the analysis of the induced absorption signal observed immediately after the pump excitation, we estimated the binding energy for the hot biexcitons that are composed of an exciton at the band edge and a hot exciton generated by the pump pulse. We found that the exciton-exciton interaction becomes stronger for hot excitons with greater excess energies and that the optical gain can be controlled by changing the excess energy of the hot excitons.

Facile synthesis of magnetic Fe3O4@BiOI@AgI for water decontamination with visible light irradiation: Different mechanisms for different organic pollutants degradation and bacterial disinfection.

Magnetic Fe3O4@BiOI@AgI (FBA) spheres were synthesized through a multi-step process. The fabricated photocatalysts were characterized by different techniques. To testify the visible light driven photocatalytic activity of FBA, Rhodamine B and Bisphenol A were chosen as model common and emerging organic contaminants, respectively. While, gram-negative strain Escherichia coli was selected as model waterborne bacteria. The results showed that under visible light irradiation, FBA contained strong photocatalytic degradation capacity towards both RhB and BPA. Moreover, FBA was also found to exhibit excellent disinfection activity towards E. coli. The photocatalytic mechanisms for different pollutants by FBA were determined and found to vary for different pollutants. Specifically, scavenger experiments, degradation intermediates determination, as well as theoretical density functional theory (DFT) analysis showed that RhB and BPA were degraded via photosensitization (dominated by e- and ·O2-) and direct photocatalytic oxidation (contributed by h+, e- and ·O2-), respectively. Whereas, E. coli cells yet were found to be inactivated by the generation of e- and ·O2- rather than by the released Ag+. Since it contained superparamagnetic property, FBA could be easily separated from the reaction suspension after use. Due to the excellent photo stability, FBA exhibited strong photocatalytic activity in the fourth reused recycle. Therefore, FBA could serve as a promising alternative for water purification.

Study on highly enhanced photocatalytic tetracycline degradation of type â ¡ AgI/CuBi2O4 and Z-scheme AgBr/CuBi2O4 heterojunction photocatalysts.

Removal of antibiotics from aqueous solutions by photocatalysis is an advanced technology for environmental remediation. Herein, we have fabricated a series of AgX (X = I, Br)/CuBi2O4 composites through an in-situ precipitation method. The photocatalytic activity of the obtained photocatalysts was measured by the degradation of tetracycline (TC) under visible light irradiation (λ > 420 nm). All the AgX (X = I, Br)/CuBi2O4 composites exhibit much higher photocatalytic activity than that of pure CuBi2O4. The enhanced photocatalytic activity is mainly attributed to the efficient interfacial charge separation and migration in the AgX (X = I, Br)/CuBi2O4 heterojunctions. Meanwhile, AgX (X = I, Br)/CuBi2O4 heterojunctions display excellent photocatalytic stability, and the photocatalytic degradation rates were not obvious decreased even after five successive cycles. Based on the energy band structure, the radicals trapping and electronic spin resonance (ESR) experiments, the Z-scheme mechanism of AgBr/CuBi2O4 and type II mechanism of AgI/CuBi2O4 heterojunction photocatalysts were tentatively discussed, respectively.

Temporal Fluctuations in Indoor Background Gamma Radiation Using NaI(Tl).

An enhanced understanding of background gamma radiation is necessary for accurate radionuclide activity quantification. Background spectra are routinely subtracted from spectra of samples prepared in known geometries, with data collection time chosen to optimize statistics for counting uncertainties. The work presents measured background spectra collected inside and outside shields of varying geometry and composition, showing the effects of these on background. Gamma background measurements with and without blank samples are included along with spectra from different sizes and shapes of NaI(Tl) detectors. If the environment is being monitored for quick and confident detection of recently appearing radiation sources, a thorough knowledge of the background radiation and its temporal variation is essential. To study the requirements of such background measurements, sequential background gamma radiation collections were obtained on an hourly basis for a total of 316 h from an unshielded 5.5 × 11 × 40 cm NaI(Tl) detector located inside a laboratory setting where small sources are routinely stored and used. Finally, a strategy for optimizing data collection times and analyzing background gamma radiation spectra for long-term radionuclide monitoring is presented.

Photosensitization of CuI - the role of visible light induced CuI→ CuII transition in photocatalytic degradation of organic pollutants and inactivation of microorganisms.

Bare and photosensitized copper iodides were tested in photocatalysed degradation of an organic dye (Acid Red 1) and inactivation of fungi (Saccharomyces cerevisiae). CuI, with the band gap energy slightly lower than that of TiO2, appeared to be highly efficient in these processes. Sensitization of copper iodide was achieved by surface modification with [Cu(SCN)2(phen)2]. The photosensitization mechanism encompasses a metal to metal charge transfer, CuI→ CuII. The applied photosensitizer binds to CuI through thiocyanate ligands resulting in the formation of an active CuII/CuI hybrid photocatalyst ([CuII(SCN)2(phen)2]@CuII). Its absorption edge is red shifted towards a lower energy when compared with bare CuI, resulting in enhanced visible light induced photocatalytic activity. The studied materials appeared to be photoactive in current generation, degradation of organic compounds and inactivation of fungi.

Photo-induced halide redistribution in organic-inorganic perovskite films.

Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.

Effects of radiation and temperature on iodide sorption by surfactant-modified bentonite.

Bentonite, which is used as an engineered barrier in geological repositories, is ineffective for sorbing anionic radionuclides because of its negatively charged surface. This study modified raw bentonite using a cationic surfactant (i.e., hexadecyltrimethylammonium [HDTMA]-Br) to improve its sorption capability for radioactive iodide. The effects of temperature and radiation on the iodide sorption of surfactant-modified bentonite (SMB) were also evaluated under alkaline pH condition similar to that found in repository environments. Different amounts of surfactant, equivalent to the 50, 100, and 200% cation-exchange capacity of the bentonite, were used to produce the HDTMA-SMB for iodide sorption. The sorption reaction of the SMB with iodide reached equilibrium rapidly within 10 min regardless of temperature and radiation conditions. The rate of iodide sorption increased as the amount of the added surfactant was increased and nonlinear sorption behavior was exhibited. However, high temperature and γ-irradiation ((60)Co) resulted in significantly (∼2-10 times) lower iodide Kd values for the SMB. The results of FTIR, NMR, and XANES spectroscopy analysis suggested that the decrease in iodide sorption may be caused by weakened physical electrostatic force between the HDTMA and iodide, and by the surfactant becoming detached from the SMB during the heating and irradiation processes.

In situ preparation of novel p-n junction photocatalyst BiOI/(BiO)2CO3 with enhanced visible light photocatalytic activity.

Novel p-n junction photocatalysts BiOI/(BiO)2CO3 with different contents of BiOI were in situ synthesized by etching (BiO)2CO3 precursor with hydroiodic acid (HI) solution. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectrometry (FT-IR), energy-dispersive spectroscopy (EDS) and UV-vis diffuse reflectance spectroscopy (DRS) were employed to study the structures, morphologies and optical properties of the as-prepared samples. Under visible light (λ>420 nm), BiOI/(BiO)2CO3 hybrid displayed much higher photocatalytic activity than pure (BiO)2CO3 and BiOI for the degradation of methyl orange (MO). The increased photocatalytic activity of BiOI/(BiO)2CO3 could be attributed to the formation of the p-n junction between p-BiOI and n-(BiO)2CO3, which effectively suppresses the recombination of photoinduced electron-hole pairs. Moreover, the tests of radical scavengers confirmed that •O2- and h+ were the main reactive species for the degradation of MO.

One-pot solvothermal synthesis of three-dimensional (3D) BiOI/BiOCl composites with enhanced visible-light photocatalytic activities for the degradation of bisphenol-A.

Three-dimensional (3D) BiOI/BiOCl composite microspheres with enhanced visible-light photodegradation activity of bisphenol-A (BPA) are synthesized by a simple, one-pot, template-free, solvothermal method using BiI(3) and BiCl(3) as precursors. These 3D hierarchical microspheres with heterojunction structures are composed of 2D nanosheets and have composition-dependent absorption properties in the ultraviolet and visible light regions. The photocatalytic oxidation of BPA over BiOI/BiOCl composites followed pseudo first-order kinetics according to the Langmuir-Hinshelwood model. The highest photodegradation efficiency of BPA, i.e., nearly 100%, was observed with the BiOI/BiOCl composite (containing 90% BiOI) using a catalyst dosage of 1 g L(-1) in the BPA solution (C(0)=20 mg L(-1), pH=7.0) under visible light irradiation for 60 min. Under these conditions, the reaction rate constant was more than 4 and 20 times greater than that of pure BiOI and the commercially available Degussa P25, respectively. The superior photocatalytic activity of this composite catalyst is attributed to the suitable band gap energies and the low recombination rate of the photogenerated electron-hole pairs due to the presence of BiOI/BiOCl heterostructures. Only one intermediate at m/z 151 was observed in the photodegradation process of BPA by liquid chromatography combined with mass spectrometry (LC-MS) analysis, and a simple and hole-predominated photodegradation pathway of BPA was subsequently proposed. Furthermore, this photocatalyst exhibited a high mineralization ratio, high stability and easy separation for recycling use, suggesting that it is a promising photocatalyst for the removal of BPA pollutants.

Enhanced adsorption and photocatalytic activity of BiOI-MWCNT composites towards organic pollutants in aqueous solution.

BiOI-MWCNT composites, with high absorption and visible-light photocatalytic performance, were synthesized by a solvothermal process, in which ethylene glycol (EG) participated in the reaction. Synthesized BiOI-MWCNT composites were characterized by X-ray diffraction (XRD), diffuse reflectance spectra (DRS), scanning electronic microscopy (SEM), transmission electron microscopy (TEM), and electrochemical impedance spectroscopy (EIS). The results showed that the prepared BiOI-MWCNT composites exhibit strong adsorption ability with the increase of doped MWCNT amount. The efficiency of AOII degradation increased with the increase of MWCNT amount from 0.5 to 1.0% significantly. The photocatalytic degradation of AOII using BiOI-MWCNT composites under visible light (λ>400 nm) was almost completed within 180 min. BiOI-MWCNT composites maintained its degradation efficiency and durability after being reused for 5 batch runs. The high adsorption ability and degradation efficiency of BiOI-MWCNT for AOII was attributed to the sorption of doped MWCNT and the effective charge transfer from excited BiOI to MWCNTs, respectively. Moreover, organic compounds as intermediates of the degradation process were identified by LC/MS.

Application of the Monte Carlo method for the efficiency calibration of CsI and NaI detectors for gamma-ray measurements from terrestrial samples.

Gamma-ray measurements in terrestrial/environmental samples require the use of high efficient detectors because of the low level of the radionuclide activity concentrations in the samples; thus scintillators are suitable for this purpose. Two scintillation detectors were studied in this work; CsI(Tl) and NaI(Tl) with identical size for measurement of terrestrial samples for performance study. This work describes a Monte Carlo method for making the full-energy efficiency calibration curves for both detectors using gamma-ray energies associated with the decay of naturally occurring radionuclides (137)Cs (661keV), (40)K (1460keV), (238)U ((214)Bi, 1764keV) and (232)Th ((208)Tl, 2614keV), which are found in terrestrial samples. The magnitude of the coincidence summing effect occurring for the 2614keV emission of (208)Tl is assessed by simulation. The method provides an efficient tool to make the full-energy efficiency calibration curve for scintillation detectors for any samples geometry and volume in order to determine accurate activity concentrations in terrestrial samples.

A fast, angle-dependent, analytical model of CsI detector response for optimization of 3D x-ray breast imaging systems.

PURPOSE: Accurate models of detector blur are crucial for performing meaningful optimizations of three-dimensional (3D) x-ray breast imaging systems as well as for developing reconstruction algorithms that faithfully reproduce the imaged object anatomy. So far, x-ray detector blur has either been ignored or modeled as a shift-invariant symmetric function for these applications. The recent development of a Monte Carlo simulation package called MANTIS has allowed detailed modeling of these detector blur functions and demonstrated the magnitude of the anisotropy for both tomosynthesis and breast CT imaging systems. Despite the detailed results that MANTIS produces, the long simulation times required make inclusion of these results impractical in rigorous optimization and reconstruction algorithms. As a result, there is a need for detector blur models that can be rapidly generated. METHODS: In this study, the authors have derived an analytical model for deterministic detector blur functions, referred to here as point response functions (PRFs), of columnar CsI phosphor screens. The analytical model is x-ray energy and incidence angle dependent and draws on results from MANTIS to indirectly include complicated interactions that are not explicitly included in the mathematical model. Once the mathematical expression is derived, values of the coefficients are determined by a two-dimensional (2D) fit to MANTIS-generated results based on a figure-of-merit (FOM) that measures the normalized differences between the MANTIS and analytical model results averaged over a region of interest. A smaller FOM indicates a better fit. This analysis was performed for a monochromatic x-ray energy of 25 keV, a CsI scintillator thickness of 150 microm, and four incidence angles (0 degrees, 15 degrees, 30 degrees, and 45 degrees). RESULTS: The FOMs comparing the analytical model to MANTIS for these parameters were 0.1951 +/- 0.0011, 0.1915 +/- 0.0014, 0.2266 +/- 0.0021, and 0.2416 +/- 0.0074 for 0 degrees, 15 degrees, 30 degrees, and 45 degrees, respectively. As a comparison, the same FOMs comparing MANTIS to 2D symmetric Gaussian fits to the zero-angle PRF were 0.6234 +/- 0.0020, 0.9058 +/- 0.0029, 1.491 +/- 0.012, and 2.757 +/- 0.039 for the same set of incidence angles. Therefore, the analytical model matches MANTIS results much better than a 2D symmetric Gaussian function. A comparison was also made against experimental data for a 170 microm thick CsI screen and an x-ray energy of 25.6 keV. The corresponding FOMs were 0.3457 +/- 0.0036, 0.3281 +/- 0.0057, 0.3422 +/- 0.0023, and 0.3677 +/- 0.0041 for 0 degrees, 15 degrees, 30 degrees, and 45 degrees, respectively. In a previous study, FOMs comparing the same experimental data to MANTIS PRFs were found to be 0.2944 +/- 0.0027, 0.2387 +/- 0.0039, 0.2816 +/- 0.0025, and 0.2665 +/- 0.0032 for the same set of incidence angles. CONCLUSIONS: The two sets of derived FOMs, comparing MANTIS-generated PRFs and experimental data to the analytical model, demonstrate that the analytical model is able to reproduce experimental data with a FOM of less than two times that comparing MANTIs and experimental data. This performance is achieved in less than one millionth the computation time required to generate a comparable PRF with MANTIS. Such small computation times will allow for the inclusion of detailed detector physics in rigorous optimization and reconstruction algorithms for 3D x-ray breast imaging systems.

Sonochemical preparation of antimony subiodide.

The substantiated isolation of the antimony subiodide (Sb(3)I) is presented for the first time. It has been prepared using elemental Sb and I in ethanol under ultrasonic irradiation at 323 K. Its composition was characterized using X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDAX). The scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) investigations exhibit that the samples are made up of large quantity of nanoparticles with diameters smaller than 20 nm and single crystalline in nature. The interplanar spacings in Sb(3)I that have been determined using powder X-ray diffraction (XRD), selected area electron diffraction (SAED) and HRTEM are very similar. Surprisingly, the registered XRD patterns are identical to the one reported earlier for Sb(4)O(5)I(2).

Signal and noise transfer properties of CMOS based active pixel flat panel imager coupled to structured CsI:Tl.

Complementary metal-oxide-semiconductors (CMOS) active pixel sensors can be optically coupled to CsI:Tl phosphors forming a indirect active pixel flat panel imager (APFPI) for high performance medical imaging. The aim of this work is to determine the x-ray imaging capabilities of CMOS-based APFPI and study the signal and noise transfer properties of CsI:Tl phosphors. Three different CsI:Tl phosphors from two different vendors have been used to produce three system configurations. The performance of each system configuration has been studied in terms of the modulation transfer function (MTF), noise power spectra, and detective quantum efficiency (DQE) in the mammographic energy range. A simple method to determine quantum limited systems in this energy range is also presented. In addition, with aid of monochromatic synchrotron radiation, the effect of iodine characteristic x-rays of the CsI:Tl on the MTF has been determined. A Monte Carlo simulation of the signal transfer properties of the imager is also presented in order to study the stages that degrade the spatial resolution of our current system. The effect of using substrate patterning during the growth of CsI:Tl columnar structure was also studied, along with the effect of CsI:Tl fixed pattern noise due to local variations in the scintillation light. CsI:Tl fixed pattern noise appears to limit the performance of our current system configurations. All the system configurations are quantum limited at 0.23 microC/kg with two of them having DQE (0) equal to 0.57. Active pixel flat panel imagers are shown to be digital x-ray imagers with almost constant DQE throughout a significant part of their dynamic range and in particular at very low exposures.

Infrared studies of lead(II) halide-1,10-phenanthroline photosensitive materials.

Infrared spectroscopic studies of 1:1 and 1:2 complexes of lead(II) bromide and lead(II) iodide with 1,10-phenanthroline were reported. Vibrational assignments are made by comparison to reported spectra of the uncomplexed 1,10-phenanthroline molecule. Small shifts of the ligand vibrational bands are characteristic of the complexes.