Searching for better X-ray and γ-ray photodetectors: structure-composition properties of the TlPb2Br5-x I x quaternary system.

Developing X-ray and γ-ray detectors with stable operation at ambient temperature and high energy resolution is an open challenge. Here, we present an approach to search for new detector materials, combining binary photodetector compounds. More specifically, we explore quaternary TlPb2Br5-x I x compositions, relying on materials synergy between TlBr, TlI, and PbI2 photodetectors. We discover a broad solid solution in the TlPb2Br5-'TlPb2I5' section, which can be derived from a new quaternary compound, TlPb2BrI4, by partial substitution of Br by I atoms on the 4c site or by replacement of I by Br atoms on the 16l site. We carry out a thorough crystallographic analysis of the new TlPb2BrI4 compound and prepare a high-quality standardized structure file. We also complete the phase diagram of the TlPb2Br5-'TlPb2I5' section, based on 21 alloys. Furthermore, we synthesize a series of high quality centimeter-sized TlPb2Br5-x I x single crystals (x = 2, 2.5, 3, 3.5, 4, 4.5) by the Bridgman-Stockbarger method and study their structure and properties using a combination of experimental techniques (X-ray diffraction, X-ray photoelectron spectroscopy, and absorption spectroscopy) and theoretical calculations.

Defect engineering, microstructural examination and improvement of ultrafast third harmonic generation in GaZnO nanostructures: a study of e-beam irradiation.

Electron beam induced effects on defect engineering and structural, morphological and optical properties of Ga doped ZnO (GaZnO) nanostructures for improved ultrafast nonlinear optical properties are presented. A microstructural analysis was carried out based on the Scherrer, Williamson-Hall, and size-strain models. All three models reveal a peak broadening effect upon electron beam irradiation (EBI) and the crystallite size of the films shows a decrease of 30% compared to unirradiated nanostructures. The decrease in intensity, variation in the peak position and broadening of the Raman E2H mode confirm that the EBI treatment introduces disorder into the nanostructures. The interband gap emissions observed in photoluminescence spectra are primarily due to defect-related emissions originating from intrinsic defects such as Zni, Oi, VZn, VO, VZn+, VO+ and OZn. The O1s core-level spectra show that the peak related to oxygen vacancy defects is suppressed upon EBI. Surface morphology studies reveal that the nucleation barriers of GaZnO nanostructures are reduced upon irradiation treatment resulting in a coalescence mechanism. Third harmonic generation studies show that higher electron-beam doses lead to the occurrence of enhanced THG signals due to a drastic change in the occupation of localized defect levels. Thermally induced nonlinear optical studies depict an improved χ(3) of 1.71 × 10-3 esu upon irradiation due to enhanced FCA induced TPA mechanism and non-radiative transitions which indicates the credibility of the grown films in photonic devices.

DFT modeling of thermoelectric and optical features of novel MgxSn1-xSe (x = 6%, 12% & 18%).

We explore influence of Mg alloying effect on electronic band structure dispersion and thermoelectric properties of tin chalcogenide materials. Based on density functional theory (DFT) within a framework of full potential linearized augmented plane wave method (FP-LAPW), we evaluate the energy band structure and optical properties of MgxSn1-xSe (x = 6%, 12% and 18%) materials. Moreover, we extend our calculations to simulate the electrical transport properties using Boltzmann transport theory. Within the approximations employed in our calculations the theoretically predicted band energy gap values and the temperature dependence of electrical transport properties of MgxSn1-xSe compounds revealed that the Mg-alloying have enhanced thermoelectric features. To verify the quality of calculations the comparison with the experimental absorption spectra are presented. The better thermoelectric performance in MgxSn1-xSe is expected to occur for all doping concentrations, however 18% Mg-doped material exhibits higher value of Seebeck coefficient and lower thermal conductivity which is suggestive that at higher Mg concentration the holes become dominant over electrons and hence make these materials to be more promising candidates for their use in thermoelectric power generation and in cooling devices.

N→Sn-Coordinated Stannaoxidoborates Containing a SnB4O6 Unit.

We report here the synthesis of new N→Sn-coordinated stannaoxidoborates H[LSnB4O6R4] {L = [2,6-(Me2NCH2)C6H3](-) and R = Ph (6), 4-Br-Ph (7), 3,5-(CF3)2-Ph (8), and 4-CHO-Ph (9)} containing a nonsymmetric SnB4O6 unit. Compounds 6-9 represent new derivatives of the pentaborates [B5O6R4](-) in which the central boron is substituted by a tin atom. Compounds 6-9 were characterized by means of elemental analysis, electrospray ionization mass spectrometry, and NMR spectroscopy and in the case of 6-8 also by single-crystal X-ray diffraction analysis. The structures of N→Sn-coordinated stannaoxidoborates 6-8 consist of a spirobicyclic arrangement, with two six-membered SnB2O3 rings at the tin atom providing the new stannaoxidoborate [LSnB4O6R4](-) motif, which is compensated for by the proton atom coordinated to the Me2N group of the ligand L. The linear and thermal properties of 6-9 were studied with the help of electronic absorption spectra and differential scanning calorimetry. In addition, the presence of the nonsymmetric stannaoxidoborate SnB4O6 unit in 6, 7, and 9 prompted us to investigate their second-order nonlinear-optical properties.

Second-order susceptibility spectra for δ-BiB3O6 polymer nanocomposites deposited on the chalcogenide crystals.

The optimized conditions for the enhancement of the second harmonic generation in the composites of the orthorhombic δ-BiB3O6:Pr(3+) nanoparticles embedded in polyvinyl alcohol films and deposited on the AgGaGe2Se6, AgGaGe2.7Si0.3Se8 (90 mol.% AgGaGe3Se8 - 10 mol.% AgGaSi3Se8), and AgGaGe3Se8:Cu substrates were established. The highest second-order susceptibility was achieved during the Ag-Ga-Ge-Se crystalline substrates photo-illumination by nanosecond laser pulses of about 2900 nm wavelength. The effect was found to be completely reversible after the interruption of the photo-inducing stimulation. Complementary studies of Atomic Force Microscopy, AFM, X-ray Diffraction, XRD, and Fourier-Transform Infrared Spectroscopy, and DFT simulations of spectral dependences of the corresponding second-order nonlinear optical susceptibilities, were performed.

Synthesis of amorphous platinum nanofibers directly on an ITO substrate and its heterogeneous catalytic hydrogenation characterization.

This paper reports a facile, solution-phase approach to synthesizing a one-dimensional amorphous face-centered-cubic (fcc) platinum (a-Pt) nanostructure (nanofibers) directly on an indium-tin oxide (ITO) substrate. The electron microscopy analysis result shows that the a-Pt nanofiber has a diameter and length of approximately 50 nm and 1 µm, respectively, and is grown in high density on the entire surface of the ITO substrate. The X-ray photoelectron spectroscopy analysis result further reveals that the a-Pt nanofibers feature metallic properties with highly reactive surface chemistry, promising novel performance in electrochemistry, catalysis, and sensors. A synergetic interplay between the formic acid reducing agent and the hexamethylenetetramine surfactant in the reduction of Pt ions is assumed as the driving force for the formation of the amorphous phase in the Pt nanostructure. The catalytic properties of a-Pt were examined in the acetone hydrogenation reaction under microwave irradiation. a-Pt shows excellent heterogeneous catalytic properties for converting acetone to isopropyl alcohol with turnover number and frequency as high as 400 and 140 min(-1), respectively. The preparation and formation mechanism of the a-Pt nanofibers will be discussed in detail in this paper.

Absorption, fluorescence and second harmonic generation in Cr³âº-doped BiB3O6 glasses.

Synthesis, spectral properties and photoinduced nonlinear optical effects of chromium-doped BiB3O6 glass are studied in the present paper. Absorption, excitation and time resolved luminescence spectra are presented and luminescence decay behavior is discussed. Detailed analysis of the obtained spectra (assignment of the most prominent spectral features in terms of the corresponding Cr(3+) energy levels, crystal field strength Dq, Racah parameters B and C) was performed. A weak photostimulated second harmonic generation signal was found to increase drastically due to poling by proton implantation in the investigated sample.

Laser induced infrared spectral shift of the MgB2:Cr superconductor films.

During illumination of the MgB2:Cr2O3 films it was established substantial spectral shift of the infrared spectra in the vicinity of 20-50cm(-1). The excitations were performed by nanosecond Er:glass laser operating at 1.54µm and by microsecond 10.6µm CO2 laser. The spectral shifts of the IR maxima were in opposite spectral directions for the two types of lasers. This one observed difference correlates well with spectral shift of their critical temperatures. The possible explanation is given by performance of DFT calculations of the charge density redistribution and the time kinetics of the photovoltaic response. To understand the kinetics of the photoinduced processes the time kinetics of photoresponse was done for the particular laser wavelengths.

Ag-ZnO nanoreactor grown on FTO substrate exhibiting high heterogeneous photocatalytic efficiency.

This Research Article reports an unusually high efficiency heterogeneous photodegradation of methyl orange (MO) in the presence of Ag nanoparticle-loaded ZnO quasi-nanotube or nanoreactor (A-ZNRs) nanocatalyst grown on FTO substrate. In typical process, photodegradation efficiency of as high as 21.6% per µg per Watts of used catalyst and UV power can be normally obtained within only a 60-min reaction time from this system, which is 10(3) order higher than the reported results. This is equivalent to the turnover frequency of 360 mol mol(-1) h(-1). High-density hexagonal A-ZNRs catalysts were grown directly on FTO substrate via a seed-mediated microwave-assisted hydrolysis growth process utilizing Ag nanoparticle of approximately 3 nm in size as nanoseed and mixture aqueous solution of Zn(NO3)·6H2O, hexamethylenetetramine (HMT), and AgNO3 as the growth solution. A-ZNRs adopts hexagonal cross-section morphology with the inner surface of the reactor characterized by a rough and rugged structure. Transmission electron microscopy imaging shows the Ag nanoparticle grows interstitially in the ZnO nanoreactor structure. The high photocatalytic property of the A-ZNRs is associated with the highly active of inner side's surface of A-ZNRs and the oxidizing effect of Ag nanoparticle. The growth mechanism as well as the mechanism of the enhanced-photocatalytic performance of the A-ZNRs will be discussed.

Dicyanobenzene and dicyanopyrazine derived X-shaped charge-transfer chromophores: comparative and structure-property relationship study.

A series of novel X-shaped push-pull compounds based on benzene-1,2-dicarbonitrile has been designed, synthesized and further investigated by X-ray analysis, electrochemistry, absorption and emission spectra, SHG experiment and quantum-chemical calculations. The obtained data were compared with those for isolobal 5,6-disubstituted pyrazine-2,3-dicarbonitriles. Structure-property relationships were elucidated. The extension, composition and planarization of the π-linker used as well as the electron-withdrawing ability of both dicyano-substituted acceptor units affect the linear and nonlinear properties of the target charge-transfer chromophores most significantly.

Specific features of the electronic structure of a novel ternary Tl3PbI5 optoelectronic material.

A novel Tl3PbI5 crystal has been studied both experimentally and theoretically. Complex measurements of the X-ray photoelectron core-level and valence-band spectra for the pristine and Ar(+)-ion irradiated surfaces of a Tl3PbI5 single crystal grown by the Bridgman-Stockbarger method were performed in order to clarify their principal properties (charge carriers mobility, effective inter-band distances, effective absorption etc.) relevant for optoelectronic applications. The principal role of two heavy cations - Tl and Pb - is explored. The X-ray photoelectron spectroscopy results reveal a high chemical stability of the Tl3PbI5 single crystal surface which makes it very promising for technological applications. Theoretical band-structure calculations for the Tl3PbI5 compound reveal that the I 5p states dominate in the top of the valence band and play a crucial role in the formation of the optical features and charge carrier mobility. The bottom of the Tl3PbI5 valence band is formed mainly by the admixture of Tl 6s and Pb 6s states, while the unoccupied Pb 6p and Tl 6p states dominate at the bottom of the conduction band. The band energy dispersion related to effective masses and the charge carrier mobility is studied in detail. Crucially, the theoretical calculations reveal an indirect band gap for Tl3PbI5, which indicates a strong influence of the electron-phonon interaction on the observed optoelectronic features. The temperature measurements of the fundamental absorption have shown that the band energy gap of Tl3PbI5 increases from 2.29 to 2.39 eV when the temperature changes from 300 to 100 K.

Structural, electronic, and optical features of CuAl(S(1-x)Se(x))2 solar cell materials.

Detailed first-principles calculations of the structural, electronic, and optical properties of solid solutions of the promising solar cell material CuAl(S(1-x)Se(x))2 over the whole range of Se concentration from x = 0 to x = 1 were performed. It was established that the calculated lattice parameters, band gap, and anisotropic refractive indices vary linearly with the Se concentration. The obtained linear dependences allow for reliable estimations of all these quantities for any value of x, which determines the solid solution composition. The calculated results were compared with the experimental data available for x = 0, 0.5, and 1.0; very good agreement was demonstrated, which gives confidence in the properties calculated for other Se concentrations (x = 0.25, 0.75). The findings from the present paper can be used in a straightforward way for the successful production of CuAl(S(1-x)Se(x))2 mixed compounds with desired optoelectronic parameters, which are defined by the composition-tuned mobility of the charge carriers in the upper valence band and the conduction band. Extension of the presented approach to other materials is also possible.

Spectral kinetics of fluorescence spectra of fluoroderivatives of pyrazoloquinoline in different polymer matrices.

Three fluoro-substituted pyrazoloquinoline derivatives have been placed in polymer matrices: polycarbonate, poly(methyl methacrylate) and polystyrene. Absorption, excitation and time-resolved fluorescence spectra have been recorded and luminescence lifetime of the optically active composites has been determined. Influence of the dielectric environment the optical properties of the chromophores are discussed. Experimental data and conclusions are supported with (TD)DFT calculations.

Photoinduced features of energy bandgap in quaternary Cu2CdGeS4 crystals.

The quaternary chalcogenide crystal Cu2CdGeS4 was studied both experimentally and theoretically in the present paper. Investigations of polarized fundamental absorption spectra demonstrated a high sensitivity to external light illumination. The photoinduced changes were studied using a cw 532 nm green laser with energy density about 0.4 J cm(-2). The spectral maximum of the photoinduced anisotropy was observed at spectral energies equal to about 1.4 eV (energy gap equal to about 1.85 eV) corresponding to maximal density of the intrinsic defect levels. Spectroscopic measurements were performed for polarized and unpolarized photoinducing laser light to separate the contribution of the intrinsic defect states from that of the pure states of the valence and conduction bands. To understand the origin of the observed photoinduced absorption near the fundamental edge, the benchmark first-principles calculations of the structural, electronic, optical and elastic properties of Cu2CdGeS4 were performed by the general gradient approximation (GGA) and local density approximation (LDA) methods. The calculated dielectric function and optical absorption spectra exhibit some anisotropic behavior (shift of the absorption maxima in different polarizations) within the 0.15-0.20 eV energy range not only near the absorption edge; optical anisotropy was also found for the deeper inter-band transition spectral range. Peculiar features of chemical bonds in Cu2CdGeS4 were revealed by studying the electron density distribution. Possible intrinsic defects are shown to affect the optical absorption spectra considerably. Pressure effects on the structural and electronic properties were modeled by optimizing the crystal structure and calculating all relevant properties at elevated hydrostatic pressure. The first estimations of the bulk modulus (69 GPa (GGA) or 91 GPa (LDA)) and its pressure derivative for Cu2CdGeS4 are also reported.

Linear and nonlinear optical susceptibilities and the hyperpolarizability of borate LiBaB9O15 single-crystal: theory and experiment.

The single-crystal borate LiBaB9O15 was synthesized by a high-temperature solution reaction and structurally determined by the single-crystal X-ray diffraction technique. It crystallizes in the noncentrosymmetric space group R3c and features a three-dimensional ∞3[B9O15]3­ anionic framework, with infinite channels in which the Li+ and Ba2+ cations are located. The linear optical properties were investigated experimentally in terms of the absorption spectrum, which reveals an optical gap of 5.17 eV. In addition we have calculated the linear optical properties using state-of-the-art all-electron full potential linearized augmented plane wave method. The nonlinear optical susceptibilities, namely, the second harmonic generation and the hyperpolarizability of the single-crystal borate LiBaB9O15 are calculated and evaluated at a static limit and at λ = 1064 nm. The calculation shows there exists three second-order nonlinear optical susceptiblities tensors components. We present measurements of the IR spectra in the range 500­2000 cm­1, and the second harmonic generation was performed using a Quantel 15 ns Nd:YAG laser operating at 1064 nm.

IR laser induced spectral kinetics of AgGaGe3Se8:Cu chalcogenide crystals.

The possibility to operate by optical spectra near the absorption edge gap was discovered for the AgGaGe3Se8:Cu semiconducting chalcogenide crystals under influence of microsecond CO2 laser with pulse energy 60 mJ operating at wavelength 10.6 µm. An occurrence of substantial photoinduced optical density was observed at wavelengths in the spectral range of 610-620 nm. Introducing of Cu ions leads to substantial spectral asymmetry in the observed spectra. The process achieves its maximum value after the 80-120 s of CO2 laser treatment and relaxes with almost irreversible changes after the same time. The contribution of thermo heating did not exceed 5-6%. Only the irreversible changes of the sample's surface topography were observed during the CO2 laser treatment, which do not influence the treatment. So the surface states do not play a principal role and the effect is prevailingly originated from the. The observed effect may be used for control of the CO2 laser power density.

Influence of replacing Si by Ge in the chalcogenide quaternary sulfides Ag2In2Si(Ge)S6 on the chemical bonding, linear and nonlinear optical susceptibilities, and hyperpolarizability.

The linear and nonlinear optical properties of Ag2In2SiS6 and Ag2In2GeS6 are calculated so as to obtain further insight into the electronic properties. The influence of using different exchange correlation potentials and the effect of replacing Si by Ge on the geometry, chemical bonding, and on the optical properties are presented. There is notable increasing in the energy band gap when moving from LDA to GGA, EVGGA then to mBJ. The effect of replacing Si by Ge atom causes a geometric change, which leads to large changes in the linear as well as the nonlinear optical susceptibilities. For the linear optical properties, it causes to increase the amplitude of the left-hand hump of ε(2)(average)(ω) as well as a small shift of the main peak to lower energies. We have evaluated ε(1)(average)(0) and find that a smaller energy gap yields a larger ε1(0) value. From the calculated refractive indices we obtained the birefringence, which is important for second harmonic generation (SHG) and optical parametric oscillation (OPO) as it is defined by the phase-matching condition. The second-order nonlinear optical susceptibilities, namely, the SHG are investigated for χ(111)(2)(ω), χ(122)(2)(ω), χ(133)(2)(ω), χ(221)(2)(ω), and χ(331)(2)(ω). We find that χ(111)(2)(ω) is the dominant component. The microscopic second order hyperpolarizability, ß111, for the dominant component χ(111)(2)(ω) was obtained. We should emphasize that replacing Si by Ge enhances the linear and nonlinear optical susceptibilities so that Ag2In2GeS6 shows higher values of the linear and nonlinear optical susceptibilities and ß111 in comparison to Ag2In2SiS6.

Dispersion of linear, nonlinear optical susceptibilities and hyperpolarizability of C11H8N2O (o-methoxydicyanovinylbenzene) crystals.

Linear and nonlinear optical susceptibility dispersion and hyperpolarizability of C(11)H(8)N(2)O, o-methoxydicyanovinylbenzene, crystals were performed by means of density functional theory (DFT). The exchange and correlation potential was described within a framework of the local density approximation (CA-LDA) and gradient approximation (GGA) based on exchange-correlation energy optimization to calculate the total energy. Engel-Vosko generalized gradient approximation (EV-GGA) and the modified Becke-Johnson potential (mBJ) were used for the electronic crystal structure and optical susceptibility dispersion calculations. We have established systematically increasing energy gap from 2.25 eV (LDA), 2.34 eV (GGA), 2.50 eV (EVGGA), and 2.96 eV (mBJ). The crystal possesses a direct band gap which is an important key factor to make the crystal optically active with high linear and nonlinear optical susceptibilities and hyperpolarizability. Additionally, the studied crystal has a considerable anisotropy of birefringence which is necessary for phase matching conditions during the optical second harmonicexperiments. We have found that the theoretically evaluated second harmonic generation achieves about 5.8 × 10(-8) esu in good agreement with the experimental value (4.9 × 10(-8) esu). Additionally, we have found that our calculated value of ß(222) is about 2.3 × 10(-30) esu at zero energy and 6.6 × 10(-30) esu at λ = 1.064 µm. We should emphasize that our calculated value of ß(222) (6.60 × 10(-30) esu at λ = 1.064 µm) shows better agreement with the experimental data (5.04 × 10(-30) esu at λ = 1.064 µm) than other calculations.

Photoinduced spectra for magneto electric (1-x)BiFeO3-xCuFe2O4 nanocomposites.

In this work, we demonstrate possibility to use spectra of the parametrically tuned laser beam for operation by magnetoelectric properties of the (1-x)BiFeO(3-)(x)CuFe(2)O(4) (BFCI). The role of the photoexcited wavelength is crucial due to photoexcited phonons. It may indicate on a spectral sensitivity of the studied nanocomposites. We have studied spectral dependences of magneto-electric constant versus the magnetic field frequency for different sizes of the nanoparticles with and without the nanosecond laser pulses illumination and we have shown an occurrence of principal spectral shifts in the corresponding magneto-electric maxima. Additionally we have explored relative changes of dielectric permittivity and coercivity versus different photoinducing wavelengths. The performed experiments unambiguously show that the external laser treatment will lead to substantial shift of corresponding dielectric and magnetic parameters in the studied nanocomposites. It is principally the finding of clear spectral dependences for the mentioned dielectric and magnetic parameters. One can see their sensitivity to the photoinduced wavelength which reflects the photoexcitations of different part of wavelengths. One can see the spectral shift up to 100 nm for the two principal spectral maxima with respect to the dielectric and magnetic changes which may indicate on the two principally different contributions to the effects observed.

An ab initio density functional study of the optical functions of 9-Methyl-3-Thiophen-2-YI-Thieno [3,2e] [1,2,4] Thriazolo [4,3c] Pyrimidine-8-Carboxylic Acid Ethyl Ester crystals.

An ab initio investigation of the optical constants of 9-Methyl-3-Thiophen-2-YI-Thieno [3,2e] [1,2,4] Thriazolo [4,3c] Pyrimidine-8-Carboxylic Acid Ethyl Ester crystal is performed within a framework of local density approximation (LDA), and the Engel-Vosko generalized gradient approximation (EV-GGA) exchange correlation potentials. It is established that there are two independent molecules (A and B) exhibiting different intra-molecular interactions: C-H⋯O (A) and C-H⋯N (B). These intra-molecular interactions favor stabilization of the crystal structure for molecules A and B. It should be emphasized that there exist remarkable π-π interactions between the pyrimidine rings of the two neighbors B molecules giving extra strengths and stabilizations to the superamolecular structure. These different intra-molecular interactions C-H⋯O (A) and C-H⋯N (B) and the π-π interaction between the pyrimidine rings of the two neighbors B molecules give principal contribution to dispersion of optical properties. With a view to seek deeper insight into the electronic structure, the optical properties were investigated. Our calculations show that the optical constants are very anisotropic. The EVGGA calculation shows a blue spectral shift of around 0.024 eV with significant changes in the spectra compared to the LDA calculation. The observed spectral shifts are in agreement with the calculated band structure and corresponding electron density of states.