Optical energy gaps of undoped and Co-doped ZnIn2Se4 single crystals

Single crystals of undoped and Co-doped ZnIn₂Se₄ were grown by the vertical Bridgman technique. The optical energy gaps of the single crystals were investigated in the temperature range of 10–300 K from the optical absorption measurements. The indirect optical energy gaps of the single crystals were found to be 1.624 eV for undoped ZnIn₂Se₄ and 1.277 eV for Co-doped one at 300 K. Also, the direct optical energy gaps were given by 1.774 and 1.413 eV for undoped ZnIn₂Se₄ and co-doped one, respectively. The temperature dependence of the optical energy gaps was well fitted by the Varshni equation.     

Optical characterization of CuIn5S8 crystals by ellipsometry measurements

Optical properties of CuIn₅S₈ crystals grown by Bridgman method were investigated by ellipsometry measurements. Spectral dependence of optical parameters; real and imaginary parts of the pseudodielectric function, pseudorefractive index, pseudoextinction coefficient, reflectivity and absorption coefficients were obtained from the analysis of ellipsometry experiments performed in the 1.2–6.2 eV spectral region. Analysis of spectral dependence of the absorption coefficient revealed the existence of direct band gap transitions with energy 1.53 eV. Wemple–DiDomenico and Spitzer–Fan models were used to find the oscillator energy, dispersion energy, zero-frequency refractive index and high-frequency dielectric constant values. Structural properties of the CuIn₅S₈ crystals were investigated using X-ray diffraction and energy dispersive spectroscopy analysis.     

Optical absorption and dispersion characterizations of CuGaSe2 thin films prepared by flash evaporation technique

Thin films of CuGaSe₂ have been prepared by flash evaporation technique. The optical properties of the prepared films were investigated using spectrophotometric measurements of the transmittance and reflectance at normal incidence of light in the wavelength range from 400 to 2500 nm. The optical constants as refractive index, n, and absorption index, k, were calculated and found to be independent of film thickness in the range of the film thickness 132–423 nm. The analysis of the photon energy against the absorption coefficient showed three direct optical transitions (one of them is allowed while the others are forbidden). This direct transition was ascribed to the crystal field and spin orbital splitting of the upper most valence band. The crystal field and spin orbital splitting of CuGaSe₂ were found to be ? 0.15 eV and 0.45 eV, respectively. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple–DiDomenico (WD) model. The single oscillator energy (E_o), the dispersion energy (E_d), the high frequency dielectric constant (ε_∞), the lattice dielectric constant (ε_L) and the ratio of free charge carrier concentration to the effective mass (N / m*) were estimated. The capacitance–voltage measurements of CuGaSe₂/p-Si heterojunction showed that the diode is abrupt junction diode. The carrier concentration and the built-in voltage were estimated. The current–voltage characteristics of the device under illumination were investigated and photovoltaic properties of the device were evaluated.     

Electronic excitations and luminescence of SrAlF5 crystals doped with Ce3+ ions

This paper reports the results of a time-resolved photoluminescence and energy transfer processes study in Ce³⁺ doped SrAlF₅ single crystals. Several Ce³⁺ centers emitting near 4 eV due to 5d-4f transitions of Ce³⁺ ions substituting for Sr²⁺ in non-equivalent lattice sites were identified. The lifetime of these transitions is in the range of 25–35 ns under intra-center excitation in the energy region of 4–7 eV at T = 10 K. An effective energy transfer from lattice defects to dopant ions was revealed in the – 7–11 eV energy range. Both direct and indirect excitation channels are efficient at room temperature. Excitons bound to dopants are revealed at T = 10 K under excitation in the fundamental absorption region above 11 eV, as well as radiative decay of self-trapped excitons resulting in luminescence near 3 eV.     

Correlation between phosphorus concentration and opto-electrical properties of doped a-Si:H films

Phosphorus doped hydrogenated amorphous silicon (a-Si:H) films were prepared by decomposition of silane using RF plasma glow discharge. Both DC dark conductivity measurements, and spectrophotometric optical measurements through the range 200–3000 nm were recorded for the prepared films. The DC conductivity activation energy E_a decreased from 0.8 eV for the undoped sample to 0.34 eV for the highest used doping value. The optical energy gap E_g decreased ranging from 1.66 eV to 1.60 eV. The refractive index n, the density of charge carriers N/m* and the plasma frequency ω_p showed an opposite behavior, i.e. an increase in value with doping. Fitting the dispersion values to Sellmeier equation led to the determination of the material natural frequency of oscillating particles. A correlation between the changes in these parameters with the doping has been attempted.     

Photoluminescence study of polycrystalline CsSnI3 thin films: Determination of exciton binding energy

We report on the determination of exciton binding energy in perovskite semiconductor CsSnI₃ through a series of steady state and time-resolved photoluminescence measurements in a temperature range of 10–300 K. A large binding energy of 18 meV was deduced for this compound having a direct band gap of 1.32 eV at room temperature. We argue that the observed large binding energy is attributable to the exciton motion in the natural two-dimensional layers of SnI₄ tetragons in this material.     

Optical bandgap and electrical conductivity studies on near stoichiometric LiNbO3 crystals prepared by VTE process

Vapour transport equilibrium (VTE) technique was used to prepare near stoichiometric LiNbO₃ (NSLN) crystals. Simultaneous occurrence of reduction has been observed during the Li-enrichment that results in the weak absorption bands centred at 1.7, 2.6 and 3.7 eV in the absorption spectrum. Annealing in oxygen atmosphere resulted in decrease in the intensity of these bands. The indirect and direct band-gap energies for NSLN crystals evaluated from absorption studies are reported. The energy of the phonon involved in the indirect transition is ～85 meV (685 cm^?1). Near room temperature ac-conductivity measurements reveal lower conductivity for oxygen annealed NSLN crystal in comparison to as prepared NSLN and CLN specimens. The activation energies for ac-conductivity along the z-direction for NSLN and CLN crystals in the temperature range 500–1100 K are 1.03 eV and 0.96 eV, respectively.     

Optical and dielectric studies of solution grown glycinium maleate single crystal

Bulk single crystals of glycinium maleate have been grown from aqueous solution by slow evaporation method by optimizing the growth parameters within a period of 15 days. From X-ray diffraction analysis, the crystal was found to crystallize in monoclinic structure (space group C_2/c) with a = 17.866 Å, b = 5.684 Å, c = 17.408 Å and β = 112.65°. Presence of characteristic functional groups was confirmed in FTIR analysis. UV–Vis spectral analysis has revealed the absence of any high absorbance region between the wavelengths ranging from 300 to 900 nm. The optical band gap was calculated and found to be 3.91 eV. The activation energy for conduction at different frequencies was calculated and found to decrease from 0.54 eV to 0.41 eV as frequency increased from 100 Hz to 2 MHz. The dielectric behavior, conduction mechanism and the optical characterization of the glycinium maleate single crystals are being reported for the first time.     

Electronic and optical properties of defect chalcopyrite HgAl2Se4

The structural, electronic and optical properties of HgAl₂Se₄ are investigated using the full potential linear augmented plane wave method based on density functional theory. The calculated structural parameters using LDA are in excellent agreement with the available experimental result. The obtained energy band gap (2.24 eV) using EV-GGA approximation is in excellent agreement with experimental data (2.20 eV). Variation in the energy band gap as a function of the unit cell lattice parameter has been studied. The optical properties show a considerable anisotropy, which makes this compound very useful for various linear–nonlinear optical devices.     

Low-temperature photoluminescence spectra of CdO–In2O3 thin films prepared by sol–gel

(CdO)_1?x–(InO_3/2)_x thin films were deposited on glass substrates by the sol–gel method. The precursor solutions for the mixed oxide films were obtained from the mixture of the precursor solutions for CdO and In₂O₃ prepared separately. The investigated In atomic concentrations in the solution, x, were 0.0, 0.16, 0.33, 0.50, 0.67, 0.84, and 1. X-ray diffraction measurements showed that the films were mainly constituted of CdO, In₂O₃, and CdIn₂O₄. CdO and In₂O₃ were obtained for x=0 and 1, respectively. For x=0.67, which is the stoichiometric composition of the CdIn₂O₄ compound, only this oxide was formed. CdO and CdIn₂O₄ crystals were obtained in the Cd-rich region, whereas In₂O₃ and CdIn₂O₄ crystals were formed in the In-rich region. The PL spectra at 15 K for CdO showed the presence of two main emission bands at energies close to 2.2 and 3.0 eV. A blue-shift of these bands took place for increasing In concentration, which is related to the increase in the band gap energy of the mixed system in going from CdO, with a band gap energy of 2.46 eV, to CdIn₂O₄, with 3.2 eV, to In₂O₃, with 3.6 eV.     

Effect of annealing on structure and optical properties of Ga5Se95 films

To investigate the effect of annealing on the structural and optical properties of a binary compound Ga₅Se₉₅, thin films of Ga₅Se₉₅ have been deposited on quartz substrates at room temperature by the thermal evaporation technique. X-ray diffraction patterns showed that the films before and after annealing at 573 K have polycrystalline texture and exhibit tetragonal structure. The dependences of the optical constants, the refractive index n and extinction coefficient k were studied in the spectral range of 200 nm to 2500 nm. The normal dispersion of the refractive index of the films could be described using the Wemple–DiDomenco single-oscillator model. Analysis of absorption index data reveals that as-deposited Ga₅Se₉₅ films has indirect transitions with optical energy gap of 1.685 eV.     

Experimental and theoretical studies on bis(glycine) lithium nitrate (BGLiN): A physico-chemical approach

Good quality and bulk size single crystal (size: 20×13×8 mm³) of bis(glycine) lithium nitrate (BGLiN) was grown by a slow evaporation solution technique from the aqueous solutions at constant temperature i.e. 27 °C using synthesized materials. Crystal system and lattice parameters were determined by single crystals as well as powder X-ray diffraction analysis. The lattice parameters of the titled compound are a=10.0223 Å, b=5.0343 Å, c=17.0510 Å, and V=860.312 Å³ and it crystallized in an orthorhombic system with space group Pca2₁ obtained by single crystal XRD. Elemental composition was confirmed by energy dispersive X-ray spectroscopic analysis. Optical absorption spectrum was recorded and various optical parameters such as optical transmission (~60%), and optical band gap (4.998 eV) were calculated. Photoluminescence study shows that the grown crystal is free from major defects. Crystalline perfection of the grown crystal was assessed and found good. Ground state optimized geometry has been obtained by using DFT with 6-31G(d,p) basis set. HOMO and LUMO energy gap was found to be 6.01 eV and dipole moment was 1.65 D.     

Structure,optical spectroscopy and dispersion parameters of ZnGa2Se4 thin films at different annealing temperatures

Thin films of ZnGa₂Se₄ were deposited by thermal evaporation method of pre-synthesized ingot material onto highly cleaned microscopic glass substrates. The chemical composition of the investigated compound thin film form was determined by means of energy-dispersive X-ray spectroscopy. X-ray diffraction XRD analysis revealed that the powder compound is polycrystalline and the as-deposited and the annealed films at T_a = 623 and 673 K have amorphous phase, while that annealed at T_a = 700 K is polycrystalline with a single phase of a defective chalcopyrite structure similar to that of the synthesized material. The unit-cell lattice parameters were determined and compared with the reported data. Also, the crystallite size L, the dislocation density δ and the main internal strain ε were calculated. Analyses of the AFM images confirm the nanostructure of the prepared annealed film at 700 K. The refractive index n and the film thickness d were determined from optical transmittance data using Swanepoel's method. It was found that the refractive index dispersion data obeys the single oscillator model from which the dispersion parameters were determined. The electric susceptibility of free carriers and the carrier concentration to the effective mass ratio were determined according to the model of Spitzer and Fan. The analysis of the optical absorption revealed both the indirect and direct energy gaps. The indirect optical gaps are presented in the amorphous films (as-deposited, annealed at 623 and 673 K), while the direct energy gap characterized the polycrystalline film at 700 K. Graphical representations of ε₁, ε₂, tan δ, ? Im[1/ε*] and ? Im[(1/ε* + 1)] are also presented. ZnGa₂Se₄ is a good candidate for optoelectronic and solar cell devices.     

Transparent CdO/n-GaN(0001) heterojunction for optoelectronic applications

Undoped CdO films were prepared by sol–gel method. Transparent heterojunction diodes were fabricated by depositing n-type CdO films on the n-type GaN (0001) substrate. Current–voltage (I–V) measurements of the device were evaluated, and the results indicated a non-ideal rectifying characteristic with I_F/I_R value as high as 1.17×10³ at 2 V, low leakage current of 4.88×10⁻⁶ A and a turn-on voltage of about 0.7 V. From the optical data, the optical band gaps for the CdO film and GaN were calculated to be 2.30 eV and 3.309 eV, respectively. It is evaluated that interband transition in the film is provided by the direct allowed transition. The n-GaN (0001)/CdO heterojunction device has an optical transmission of 50–70% from 500 nm to 800 nm wavelength range.     

Microstructure and optical characterizations of mechanosynthesized nanocrystalline semiconducting ZrTiO4 compound

A ZrO₂–TiO₂ solid solution is obtained by high energy ball milling of equimolar mixture of monoclinic (m) ZrO₂ and anatase (a) TiO₂. Nanocrystalline orthorhombic ZrTiO₄ compound is initiated from the nucleation of TiO₂–ZrO₂ solid solution with isostructural s-TiO₂ (srilankite) base after 30 min of milling. After 12 h of milling, 95 mol% non-stoichiometric ZrTiO₄ phase is formed. Post-annealing of 12 h ball-milled powder mixture at 1073 K for 1 h in open air results in complete formation of stoichiometric ZrTiO₄ compound. Microstructures of all powder mixtures milled for different durations have been characterized by Rietveld's structure and microstructure refinement method using X-ray powder diffraction data. HRTEM images of 12 h milled and annealed samples provide direct evidence of the results obtained from the Rietveld analysis. Optical bandgaps of ball milled and annealed ZrTiO₄ compounds lie within the semiconducting region (~2.0 eV) and increases with increase in milling time.     

Luminescent vacuum ultraviolet spectroscopy of Cr3+ ions in nanostructured aluminum oxide

Impurity Cr³⁺ centers in submicron and nanostructured Al₂O₃ crystals of different phase compositions at temperatures of 300 and 7.5 K were studied by a luminescent vacuum ultraviolet (VUV) spectroscopy method. Photoluminescence (PL) spectra and the energies of ²E, ⁴T₂, and ⁴T₁ excited states of Cr³⁺ ion depend on the type of crystalline samples phase. The PL excitation spectrum of R-line in α-Al₂O₃ nanoscale crystals is formed by intracenter transitions (2.5–5.5 eV region), by charge transfer band (6.9 eV) and by effective formation of impurity-bound excitons (9.0 eV region). Such impurity-bound excitons correspond to O₂p→Al₃s electron transition in surroundings of an impurity Cr³⁺ center. The efficiency of impurity-bound excitons formation decreases with the increase of the grain size above 100 nm. The size dependence is noticeably shown in PL excitation spectra in VUV region. Excitons bound to impurity centers do not appear in nanostructured δ+θ-Al₂O₃ crystals. The effect of the electron excitation multiplication is observed distinctly in nanostrucured α-Al₂O₃ at an excitation energy above 19 eV (more than 2E_g).     

Near-infrared photoluminescence and thermally stimulated current in Cu3Ga5Se9 layered crystals: A comparative study

Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu₃Ga₅Se₉ layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35–1.46 eV and the temperature range of 15–115 K (PL) and 10–170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu₃Ga₅Se₉ crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature.     

Structural,optical and dispersion characteristics of nanocrystalline GaN films prepared by MOVPE

In this work, nanocrystalline GaN film was grown on a c-plane sapphire substrate by metal-organic vapor phase epitaxy (MOVPE). The structural and optical properties of the nanocrystalline GaN thin film were studied. The morphological and structural properties of GaN film were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. According to the X-ray diffraction spectrum, a GaN film was formed with a wurtzite structure, which is the stable phase. The optical parameters were determined using spectrophotometric measurements of transmittance and reflectance in the wavelength range 200–2500 nm. The analysis of the spectral behavior of the absorption coefficient in the intrinsic absorption region reveals a direct allowed transition with a band gap of 3.34 eV. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple–Didomenico (WD) model. The single oscillator energy (E_o), the dispersion energy (E_d), the high frequency dielectric constant (ε_∞), the lattice dielectric constant (ε_L) and the free charge carrier concentration (N) were estimated. From the optical dielectric analysis, the optical conductivity, volume and surface energy loss functions were calculated. Moreover, the third-order nonlinear optical susceptibility χ⁽³⁾ was also considered.     

Structural,dielectric and impedance properties of NaCa2V5O15 ceramics

Polycrystalline sample of NaCa₂V₅O₁₅ (NCV) with tungsten bronze structure was prepared by a mixed oxide method at relatively low temperature (i.e. 630 °C). Preliminary structural analysis of the compound showed an orthorhombic crystal structure at room temperature. Microstructural study showed that the grains are uniformly and densely distributed over the surface of the sample. Detailed studies of dielectric properties showed that the compound has dielectric anomaly above the room temperature (i.e. 289 °C), and shows hysteresis in polarization study. The electrical parameters of the compound were studied using complex impedance spectroscopy technique in a wide temperature (23–500 °C) and frequency (10²–10⁶ Hz) ranges. The impedance plots showed only bulk (grain) contributions, and there is a non-Debye type of dielectric dispersion. Complex modulus spectrum confirms the grain contribution only in the compound as observed in the impedance spectrum. The activation energy, calculated from the ac conductivity of the compound, was found to be 0.20–0.30 eV. These values of activation energy suggest that the conduction process is of mixed type (i.e. ionic–polaronic).     

Synthesis,crystal growth and characterization of a semiorganic material: Calcium dibromide bis(glycine) tetrahydrate

Single crystals of semiorganic material calcium dibromide bis(glycine) tetrahydrate were grown from aqueous solution. The crystal belongs to monoclinic system, with a = 13.261(5) Å, b = 6.792(2) Å, c = 15.671(9) Å and β = 91.68(4)°. The presence of the elements in the title compound was confirmed by energy dispersive X-ray analysis. The solubility and metastable zone width were found. The grown crystals were tested by powder XRD, FTIR, Thermo Gravimetric and Differential Thermal Analysis, UV–vis–NIR analysis, dielectrical and mechanical studies. The transmittance of calcium dibromide bis(glycine) tetrahydrate crystal has been used to calculate the refractive index n, the extinction coefficient K and both the real ɛ_r and imaginary ɛ_i components of the dielectric constant as functions of wavelength. The optical band gap of calcium dibromide bis(glycine) tetrahydrate is 3.23 eV.