Research on the novel GeSe2-In2Se3-KBr chalcohalide optic glasses

(1 − x)(0.75GeSe₂-0.25In₂Se₃) − x(1/3In₂Se₃-2/3KBr) (x = 0, 0.15, 0.3, 0.45, 0.525) chalcohalide glasses were prepared by traditional melt-quenching method and its glass-forming region was determined. The physical, thermal and optical properties of the GeSe₂-In₂Se₃-KBr ternary glass system are reported. The results show that the GeSe₂-In₂Se₃-KBr glass system has relatively high glass transition temperature (T_g = 286-335 °C) and good thermal stability. With increasing KBr content from 0 to 35 mol%, a blue-shift from 750 to 620 nm at the visible absorbing cutting-off edge is observed. The red-shifting of the transmission cutting-off edge at the long-wave IR band occurs linearly with increasing KBr. The allowed direct transition and indirect transition of samples were calculated according to the classical Tauc equation. The direct optical band gaps and indirect optical band gaps were in the range from 1.649 to 1.931 eV and 1.513 to 1.863 eV, respectively.     

Optical, electrical and thermal studies on (As2Se3)3−x(As2Te3)x glasses

Optical properties and conductivity of glassy (As₂Se₃)_3−x(As₂Te₃)_x were studied for 0 ≤ x ≤ 3. The films of the above mentioned compound were prepared by thermal evaporation with thickness of about 250 nm. The optical-absorption edge is described and calculated using the non-direct transition model and the optical band gap is found to be in the range of 0.92 to 1.84 eV. While, the width of the band gap tail exhibits opposite behaviour and is found to be in the range of 0.157 to 0.061 eV, this behaviour is believed to be associated with cohesive energy and average coordination number. The conductivity measurement on the thin films is reported in the temperature range from 280 to 190 K. The conduction that occurs in this low-temperature range is due to variable range hopping in the band tails of localized states, which is in reasonable agreement with Mott's condition of variable range hopping conduction. Some parameters such as coordination number, molar volume and theoretical glass transition temperature were calculated and discussed in the light of the topological bonding structure.     

Fabrication and characterisation of Cu(In,Ga)Se2 solar cells on polyimide

Solar cells with the structure ZnO:Al/i-ZnO/CdS/Cu(In,Ga)Se₂/Mo/polyimide were examined using a range of techniques. The elemental composition of the Cu(InGa)Se₂ (CIGS) layers, their crystalline structure and optical properties were studied. Photoluminescence (PL) spectra of the CIGS absorber layers were studied as functions of temperature (4.2-240 K) and excitation power density. The band gap energy E_g of the CIGS layers was determined by employing photoluminescence excitation (PLE) spectroscopy. The influence of sodium incorporation on the PL properties of CIGS was analysed. Correlations of the optical properties of the CIGS absorber layers and the photovoltaic parameters of the solar cells were revealed.     

Study on sulfur diffusion in CuInSe2 thin films using two thermal profiles

An insurmountable disadvantage of CuInSe₂ is the low band gap, which limits the open-circuit voltage to value well below 500 mV in solar cells. The incorporation of sulfur into CuInSe₂ thin film was investigated to establish a scientific basis for the graded band gap CuIn(Se_1 − x,S_x)₂ thin films. CuIn(Se_1 − x,S_x)₂ thin films were obtained by reactive annealing of Cu₁₁In₉ precursors in a mixture of sulfur and selenium atmosphere while post-sulfurization of single phase CuInSe₂ did not result in CuIn(Se_1 − x,S_x)₂ thin films. A band gap of 1.36 eV, was obtained for the prepared CuIn(Se_1 − x,S_x)₂.     

Z-scan measurement for the nonlinear absorption of Bi2.55La0.45TiNbO9 thin films

Bi_2.55La_0.45TiNbO₉ (BLTN-0.45) thin films with layered aurivillius structure were fabricated on fused silica substrates by pulsed laser deposition technique. Their structure, fundamental optical constants, and nonlinear absorption characteristics have been studied. The film exhibits a high transmittance (> 60%) in visible-infrared region. The optical band gap energy was found to be 3.44 eV. The optical constant and thickness of the films were characterized using spectroscopic ellipsometric (SE) method. The nonlinear optical absorption properties of the films were investigated by the single-beam Z-scan method at a wavelength of 800 nm laser with a duration of 80 fs. We obtained the nonlinear absorption coefficient β = 4.64 × 10^− 8 m/W. The results show that the BLTN-0.45 thin film is a promising material for applications in absorbing-type optical device.     

The system Ag2Se-Ho2Se3 in the 0-50 mol.% Ho2Se3 range and the crystal structure of two polymorphic forms of AgHoSe2

The phase diagram of the Ag₂Se-Ho₂Se₃ system in the range of 0-50 mol.% Ho₂Se₃ was constructed with the results of XRD and differential thermal analysis. A dimorphous compound exists in the system at the equimolar ratio of the components. The investigated part of the Ag₂Se-AgHoSe₂ diagram is of the eutectic type with the eutectic coordinates 7 mol.% Ho₂Se₃ and 1125 K. The crystal structure of the high-temperature modification of AgHoSe₂ was studied by X-ray powder diffraction method. α-AgHoSe₂ is described as a NaCl structure (space group ) with the lattice parameter а = 5.7623(3) Å. Atomic parameters were calculated in the isotropic approximation (R_I = 0.0434 and R_Р = 0.0636). The crystal structure of β-AgHoSe₂ was determined by X-ray structure analysis and was refined to R = 0.0487.     

Lateral features of Cu(In0.7Ga0.3)Se2-heterodiodes in the μm-scale by confocal luminescence and focused light beam induced currents

Polycrystalline Cu(In,Ga)Se₂ films (CIGSe) show substantial local variations of properties not only in regime of 10-100 nm but also in the scale length of few microns. We have analyzed optoelectronic properties of CIGSe heterodiodes by confocal luminescence and focused light beam induced currents (LBIC) versus temperature and excitation level with < 1 μm lateral resolution and we observe a strong dependence of the size of local patterns on excitation flux and a considerable dependence of the yield and the spectral shape of luminescence and of microscopic LBI currents on temperature. From experiments we derive activation energies for rates of non-radiative recombination of (2-7) meV and for minority carrier mobilities of about (60-70) meV. These energies are compared with local variations of band edges resulting from potential fluctuations which are formulated after an approach from literature and which has been fitted to experimental shifts of PL peaks and squeezing of PL spectra versus excitation flux. We estimate tunnel barriers for radiative transitions of trapped electrons of about (30-70) meV. Correlating our different results we attribute the activation energy for minority transport in CIGSe reflecting local variations of the conduction band edge mainly to spatial fluctuations of the optical band gap as a consequence of spatially varying elemental composition, and to variations of splitting of the quasi-Fermi levels introduced by spatially varying defect densities.     

Photoluminescence and Raman study of Cu2ZnSn(SexS1 − x)4 monograins for photovoltaic applications

The quaternary semiconductors Cu₂ZnSnSe₄ and Cu₂ZnSnS₄ have attracted a lot of attention as possible absorber materials for solar cells due to their direct bandgap and high absorption coefficient (> 10⁴ cm⁻¹). In this study we investigate the optical properties of Cu₂ZnSn(Se_xS_1 − x)₄ monograin powders that were synthesized from binary compounds in the liquid phase of potassium iodide (KI) flux materials in evacuated quartz ampoules. Radiative recombination processes in Cu₂ZnSn(Se_xS_1 − x)₄ monograins were studied by using low-temperature photoluminescence (PL) spectroscopy. A continuous shift from 1.3 eV to 0.95 eV of the PL emission peak position with increasing Se concentration was observed indicating the narrowing of the bandgap of the solid solutions. Recombination mechanisms responsible for the PL emission are discussed. Vibrational properties of Cu₂ZnSn(Se_xS_1 − x)₄ monograins were studied by using micro-Raman spectroscopy. The frequencies of the optical modes in the given materials were detected and the bimodal behaviour of the A₁ Raman modes of Cu₂ZnSnSe₄ and Cu₂ZnSnS₄ is established.     

Local fluctuations of absorber properties of Cu(In,Ga)Se2 by sub-micron resolved PL towards “real life” conditions

We analyze Cu(In,Ga)Se₂ absorber layers for solar cells in a confocal microscope setup by photoluminescence (PL) experiments. We present results on lateral inhomogeneities of absorbers in terms of local fluctuations of the splitting of quasi-Fermi levels (E_Fn − E_Fp), which determines the local open circuit voltage (V_oc) of the polycrystalline cell. These results can be extracted from spectrally resolved PL scans across several tens of microns. Excitation fluxes amount to 10² − 5 × 10⁴ suns equivalent at 83-300 K. We analyze the statistical distribution of the occurring fluctuations of (E_Fn − E_Fp) which we plot in histograms, seemingly showing Gaussian-like shapes. The width of these — showing substantial dependence on excitation flux and temperature — has been extrapolated towards 1 sun equivalent light fluxes. Furthermore, we use these results to correct the absolute values (E_Fn − E_Fp) which can be derived from non-laterally resolved, calibrated PL-studies at 300 K and 1 sun equivalent on comparatively large areas (1 mm²). The latter ones provide access to the spatially averaged PL-yields (∑Y_PL,xi) and their respective quasi-Fermi level splitting ((E_Fn − E_Fp)~ ln(∑Y_PL,xi)), while the average of the (E_Fn − E_Fp) from laterally resolved measurements reads (∑ln(Y_PL,xi)). We show a comparison of the two magnitudes and thus strongly appeal for sufficient high spatial resolution for a consistent quantitative interpretation of luminescence experiments.     

Structural study by X-ray diffraction and transmission electron microscopy of the misfit compound (SbS1−xSex)1.16(Nb1.036S2)2

In the Sb-Nb-S-Se system, a new misfit layer compound (MSL) has been synthesized and its structure was determined by combining single crystal X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. It presents a composite crystal structure formed by (SbS_1−xSe_x) slabs stacking alternately with double NbS₂ layers and both can be treated as separate monoclinic subsystems. The (SbS_1−xSe_x) slabs comprise a distorted, two-atom-thick layer with NaCl-type structure formed by an array of {SbX₅} square pyramids joined by edges (X: S, Se); the NbS₂ layers consist of {NbS₆} trigonal prisms linked through edge-sharing to form sheets, just as in the 2H-NbS₂ structure type. Both sublattices have the same lattice parameters a = 5.7672(19) Å, c = 17.618(6) Å and β = 96.18(3)°, with incommensurability occurring along the b direction: b₁ = 3.3442(13) Å for the NbS₂ subsystem and b₂ = 2.8755(13) Å for the (SbS_1−xSe_x) subsystem. The occurrence of diffuse scattering intensity streaked along c^* indicates that the (SbS_1−xSe_x) subsystem is subjected to extended defects along the stacking direction.     

Growth of single-phase Cu(In,Al)Se2 photoabsorbing films by selenization using diethylselenide

Selenization growth of purely single-phase, polycrystalline CuIn_1 − xAl_xSe₂ (0 ≤ x ≤ 0.26) alloy films was demonstrated using a less-hazardous metal-organic selenide, diethylselenide [(C₂H₅)₂Se: DESe], by simple thermal annealing of metal precursor. Approximately 2.0 µm thick alloy films exhibited X-ray diffraction peaks originating exclusively from the chalcopyrite structure. Transitions seen in the low temperature photoluminescence spectra were attributed to characteristic donor-acceptor pair emissions of the state-of-the-art CuIn_1 − xAl_xSe₂ photoabsorbing layers.     

Electrical properties of crystalline PbxSn1−xTe0.5Se0.5 thin films

Electrical conductivity in the dark, σ, and thermoelectric power, S, of Pb_xSn_1−xTe_0.5Se_0.5 films with x = 0.4, 0.6, 0.8, and 1 were studied for films annealed at 473 K in the temperature range 300-473 K, while the Hall voltage was investigated at room temperature. The temperature dependence of σ revealed an intrinsic conduction mechanism above 370 K, while for temperatures less than 370 K an extrinsic conduction is dominant. Both activation energy, ΔE₁, and the energy gap, E_g, were found to decrease with increasing Sn content. This decrease of E_g with increasing Sn content revealed that band inversion exists. The variation of S with temperature revealed that the investigated samples are non-degenerate semiconductors with p-type conduction. Also, the Fermi energy, E_F, was determined from the linear variation of S with 1/T in the intrinsic range. The compositional dependence of the room temperature Hall constant, R_H (0.21-0.38 cm³/Coul.), hole carrier's concentration, p (2.9-1.6 × 10¹⁹ cm⁻³), Hall mobility, μ_H (0.88-0.03 cm²/V s), and effective mass, m^∗/m_e (0.28-0.78) are given.     

Materials with layered structures XIII: electrical and optical properties of layered chalcogenides in the system CoIn2S4-CoIn2Se4

The system CoIn₂S_4xSe_4(1−x) has been investigated by X-ray powder methods on samples quenched at 700 °C. The spinel type phase has a phase width of 1≥x>0.9. A new layered compound is formed for 0.9>x>0.45 which crystallizes with the α-FeGa₂S₄-type with a=392.6 pm and c=1270.3 pm (x=0.5) for the hexagonal cell. Platelike crystals of the layered phase are obtained by transport reactions with iodine in a temperature gradient 750→700 °C. The band gaps of these crystals measured by optical absorption vary from 1.2 to 1.4 eV. The electrical conductivities of the crystals are found in the order of 10⁻⁵ Ω⁻¹ cm⁻¹.     

Materials properties of electrodeposited SnS0.5Se0.5 films and characterization of photoelectrochemical solar cells

Thin films of tin sulfoselenide (SnS_0.5Se_0.5) have been electrodeposited from an aqueous solution on tin oxide coated glass substrates by potentiostatic technique. XRD pattern of SnS_0.5Se_0.5 films showed polycrystalline nature and orthorhombic structure. The presence of Sn, S, and Se of the films were confirmed by XPS analysis. All films showed an indirect band gap. Surface morphological studies were carried out using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) analyses. Mott-Schottky plots have been drawn (in the dark condition) to evaluate the semiconductor parameters which confirmed the p-type nature of the films. The photoelectrochemical behavior of the SnS_0.5Se_0.5 films was studied in the electrolyte containing 0.1 M (FeCl₂/FeCl₃) + 0.05 M H₂SO₄ and the results are reported.     

Nanocomposite thin films of Ga5Sb10Ge25Se60 chalcogenide glass for optical limiting applications

We report a low-cost, scalable method to fabricate optical grade composite thin films for nonlinear optical applications. The transmission and reflection spectra of prepared Ga₅Sb₁₀Ge₂₅Se₆₀/PVA composite films were investigated. Optical band gap of the thin films were calculated using Tauc’s extrapolation method. The band gap of the nanocomposite thin films were found to be tunable depending on the grain size of the films. Nonlinear optical characterization of samples were studied by the Z-scan technique using an Nd:YAG laser (532 nm, 7 ns, 10 Hz). Sequential Z-scan traces were made in four regimes of intensity for films with three different grain sizes. The Z-scan spectra reveal a strong nonlinear absorption depending on the grain size of the films suggesting that the new materials are promising candidates for the development of nonlinear optical devices and are extremely perspective as optical limiters of intense short pulse radiation.     

Preparation of ultra-long Sb2Se3 nanoribbons via a short-time solvothermal process

Large-scale antimony selenide (Sb₂Se₃) nanoribbons with uniform size have been prepared by solvothermal method using antimony chloride (SbCl₃), tartaric acid (C₄H₆O₆) and selenium metal powder (Se) as raw materials, N, N-dimethylformamide (DMF) as the solvent at 180 °C for 4 h. The powder X-ray diffraction (XRD) pattern shows the Sb₂Se₃ crystals belong to the orthorhombic phase with calculated lattice constants a = 1.159, b = 1.172 and c = 0.3978 nm. The quantification of EDS analysis peaks gives an atomic ratio of 2:3 for Sb:Se. Transmission electron microscopic (TEM) studies reveal the appearance of as-prepared Sb₂Se₃ is ribbon-like with the typical width of ca. 20 nm. Finally the influences of the reaction conditions are discussed and a possible mechanism for the formation of Sb₂Se₃ nanoribbons is proposed.     

Calorimetric and optical study of amorphous Se85 − xTe15Bix glassy alloy

Bulk samples of Se_85 − xTe₁₅Bi_x (where x = 0, 1, 2, 3, 4, 5) glassy alloys are obtained by melt quenching technique. Differential scanning calorimetric (DSC) technique has been applied to determine the thermal properties of Se-rich Se_85 − xTe₁₅Bi_x glassy alloys in the glass transition and crystallization regions at four heating rates (5, 10, 15, 20 K min^− 1). The glass transition temperature (T_g) and peak crystallization temperature(T_p) are found to shift to a higher temperature with increasing heating rate. With Bi addition, the value of (T_g)increases. (T_p) is found to increase as Bi is introduced to the Se-Te host, however further increase in Bi concentration is responsible for the reduction of. Thin film of bulk samples are deposited on glass substrate using thermal evaporation technique under vacuum for optical characterization. Optical band gap is estimated using Tauc's extrapolation and is found to decrease from 1.46 to 1.24 eV with the Bi addition.     

Influence of laser-irradiation on the optical constants Se75S25 − xCdx thin films

Amorphous thin films of glassy alloys of Se₇₅S_25 − xCd_x (x = 2, 4 and 6) were prepared by thermal evaporation onto chemically cleaned glass substrates. Optical absorption and reflection measurements were carried out on as-deposited and laser-irradiated thin films in the wavelength region of 500-1000 nm. Analysis of the optical absorption data shows that the rule of no-direct transitions predominates. The laser-irradiated Se₇₅S_25 − xCd_x films showed an increase in the optical band gap and absorption coefficient with increasing the time of laser-irradiation. The results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. The value of refractive index increases decreases with increasing photon energy and also by increasing the time of laser-irradiation. With the large absorption coefficient and change in the optical band gap and refractive index by the influence of laser-irradiation, these materials may be suitable for optical disc application.     

Growth and Properties of CuGa<Subscript>5</Subscript>Se<Subscript>8</Subscript> Single Crystals

CuGa₅Se₈ single crystals were grown by the Bridgman-Stockbarger method (vertical geometry), and their composition and structure were determined. The melting point of CuGa₅Se₈ was established by differential thermal analysis, and its band gap was evaluated using transmission and reflection measurements near its intrinsic edge at 80 and 300 K. The thermal expansion of CuGa₅Se₈ was studied by dilatometry using single-crystal samples oriented parallel and perpendicular to the tetragonal axis.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 6, 2005, pp. 650–655.Original Russian Text Copyright © 2005 by Bodnar.     

Physical,photoelectrochemical properties of CuIn3Se5 and relevance for hydrogen production

CuIn₃Se₅, prepared by the fusion technique crystallizes in the P-chalcopyrite structure and exhibits n-type conduction ascribed to indium excess. The electrical conductivity follows an Arrhenius-type law with activation energy of 0.35 eV and an electron mobility of 10⁻⁴ cm² V⁻¹ s⁻¹ in conformity with small polaron hopping. The optical gap (1.19 eV), determined from the diffuse reflectance spectrum, is properly matched to the sun spectrum. CuIn₃Se₅ is chemically stable and a corrosion rate of only 1.2 μmol year⁻¹ is found at neutral pH. The slope and the intercept to C⁻² = 0 of the Mott Schottky plot gives respectively an electron density of 3.75 × 10¹⁶ cm⁻³ and a flat band potential of −0.22 V_SCE. The conduction band (−0.74 V_SCE) therefore lies below the potential of H₂O/H₂ couple and as application, H₂ photo-production is successfully achieved over CuIn₃Se₅. The best performance is obtained in S₂O₃²⁻ solution (10⁻² M, pH ∼ 7) with an evolution rate of 0.54 mL g⁻¹ min⁻¹. The conversion efficiency (0.13%) is due to the formation of small depletion width (230 nm) and a large diffusion length compared to a very large penetration depth (∼1 μm). Attempts have been made to improve the photoactivity and the hetero-system CuIn₃Se₅/WO₃ is compared favorably with respect to CuIn₃Se₅. The photoactivity is ascribed to electrons transfer from the sensitizer CuIn₃Se₅-conduction band (CB), acting as electrons pump, to WO₃-CB (−0.4 V_SCE) resulting in the enhanced water reduction.