Characterization of Cu(In,Ga)Se2 thin films prepared by evaporationfrom ternary compounds

Thin films of Cu(In,Ga)Se₂ were fabricated by evaporation from ternary CuGaSe₂ and CuInSe₂ compounds for photovoltaic device applications and their properties were investigated. From XRF analysis, the Cu:(In+Ga):Se atomic ratio in all thin films was approximately 1:1:2. The Ga/(In+Ga) atomic ratio in the thin films changed linearly from 0 to 1.0 with increasing the [CGS]/([CGS]+[CIS]) mole ratio in the evaporating materials. However, for thin films prepared at the [CGS]/([CGS]+[CIS]) mole ratio above 0.4, the composition by EPMA analysis was not consistent with that by XRF analysis. The result of EPMA analysis showed that the surface of a thin film was Cu-rich. XRD studies demonstrated that the thin films prepared at the [CGS]/([CGS]+[CIS]) mole ratio under 0.2 had a chalcopyrite Cu(In,Ga)Se₂ structure and the preferred orientation to the 112 plane. On the other hand, XRD patterns of the thin films produced at the [CGS]/([CGS]+[CIS]) mole ratio above 0.6 showed the diffraction lines from a chalcopyrite Cu(In,Ga)Se₂ and a foreign phase. The separation of a peak was observed near 2θ=27°, indicative the graded Ga concentration in Cu(In,Ga)Se₂ thin film.     

Reaction kinetics of α-CuInSe2 formation from an In2Se3/CuSe bilayer precursor film

The reaction pathway and kinetics of α-CuInSe₂ formation from a glass/In₂Se₃/CuSe polycrystalline bilayer precursor film were investigated using time-resolved, in situ high-temperature X-ray diffraction. Bilayer glass/In₂Se₃/CuSe precursor films were deposited on thin glass substrates in a migration enhanced molecular beam epitaxial deposition system. These films were then temperature ramp annealed or isothermally soaked while monitoring the phase evolution. The initial In₂Se₃ and CuSe reactant phases were directly transformed to α-CuInSe₂ without any detectable intermediate phase. Kinetic parameters were estimated using the Avrami and parabolic diffusion controlled reaction models. The parabolic reaction model fitted the experimental data better than the Avrami model over the entire temperature range (230-290 °C) of the set of isothermal experiments, with an estimated activation energy of 162 (±5) kJ/mol.     

Band-gap grading in Cu(In,Ga)Se2 solar cells

The quaternary system Cu(In,Ga)Se₂ (CIGS) allows the band gap of the semiconductor to be adjusted over a range of 1.04-1.67 eV. Using a non-uniform Ga/In ratio throughout the film thickness, additional fields can be built into p-type CIGS-based solar cells, and some researchers have asserted that these fields can enhance performance. The experimental evidence that grading improves device performance, however, has not been compelling, mostly because the addition of Ga itself improves device performance and hence a consistent separation of the grading benefit has not always been achieved. Numerical modeling tools are used in this contribution to show that (1) there can be a beneficial effect of grading, (2) in standard thickness CIGS cells the benefit is smaller than commonly believed, (3) there is also the strong possibility of reduced rather than of increased device performance, and (4) thin-absorber cells derive more substantial benefit.     

In situ pressure-induced solid-state amorphization in Sm2(MoO4)3, Eu2(MoO4)3 and Gd2(MoO4)3 crystals: chemical decomposition scenario

The effect of pressure on the phase transformations in Sm₂(MoO₄)₃, Gd₂(MoO₄)₃ and Eu₂(MoO₄)₃ crystals has been studied in situ using synchrotron radiation. All three isostructural compounds undergo a structural phase transition at 2.2-2.8 GPa to a new phase, which is interpreted as a possible precursor of amorphization. Amorphization in these crystals occurs irreversibly over a wide pressure range, and its mechanism, interpreted as a chemical decomposition, is found to be weakly affected by the degree of hydrostaticity.     

Epitaxial Cu(In,Ga)S2 thin film solar cells

Epitaxial layers of the quaternary compound Cu(In,Ga)S₂ and the ternary compound CuInS₂ were grown on Si(111) substrates via Molecular Beam Epitaxy. The layers were investigated for their morphological and structural properties using Rutherford backscattering spectroscopy, atomic force microscopy, reflection high-energy electron diffraction and X-Ray diffraction. Furthermore, complete solar cell devices were processed from these layers and their photovoltaic properties were investigated by means of I(U)-curves under illumination. Thus, efficiencies up to η=3.2% were achieved. The comparatively low performance of the solar cell devices is attributed to certain heterogeneities of the samples as a result of the growth process.     

Zn incorporation and (CuIn)1−xZn2xSe2 thin film formation during the selenization of evaporated Cu and In precursors on Al:ZnO coated glass substrates

CuInSe₂ thin films with typical 1.0 eV gap energy and tetragonal chalcopyrite structure have been obtained on soda–lime glass substrates by the reaction of sequentially evaporated Cu and In layers with elemental selenium vapor, at 500 °C in flowing Ar. When analogous deposition and reaction processes were performed on Al:ZnO coated glasses, some increment in the band gap energy and diminution in the crystalline interplanar spacings have been detected for the resulting films with an extent that depends on the Cu/In atomic ratio of the evaporated precursor layers. This fact has been related to Zn incorporation into the selenized film, with quaternary (CuIn)_1−xZn_2xSe₂ compound formation that is influenced by the presence of copper selenide phases during the reaction process. Such deductions are supported by the optical, structural and compositional characterizations that have been performed comparatively on samples prepared by selenization of evaporated metallic precursors with two different Cu/In ratios (0.9 and 1.1) on bare and Al:ZnO coated glass substrates.     

X-ray diffraction, Cs and H NMR and thermal studies of CdZrCs1.5(H3O)0.5(C2O4)4·xH2O displaying Cs and water dynamic behavior

A novel mixed cadmium zirconium cesium oxalate with an open architecture has been synthesized from precipitation methods at room pressure. It crystallizes with an hexagonal symmetry, space group P3₁12 (no. 151), a=9.105(5) Å, c=23.656(5) Å, V=1698(1) Å³ and Z=3. The structure displays a [CdZr(C₂O₄)₄]²⁻ helicoidal framework built from CdO₈ and ZrO₈ square-based antiprisms connected through bichelating oxalates, which generates channels along different directions. Cesium cations, hydronium ions and water molecules are located inside the voids of the anionic framework. They exhibit a dynamic disorder which has been further investigated by ¹H and ¹³³Cs solid-state NMR. Moreover a phase transition depending both upon ambient temperature and water vapor pressure was evidenced for the title compound. The thermal decomposition has been studied in situ by temperature-dependent X-ray diffraction and thermogravimetry. The final product is a mixture of cadmium oxide, zirconium oxide and cesium carbonate.     

High pressure X-ray diffraction study of ReS2

The high-pressure behavior of rhenium disulfide (ReS₂) has been investigated to 51.0 GPa by in situ synchrotron X-ray diffraction in a diamond anvil cell at room temperature. The results demonstrate that the ReS₂ triclinic phase is stable up to 11.3 GPa, at which pressure the ReS₂ transforms to a new high-pressure phase, which is tentatively identified with a hexagonal lattice in space group P6?m2. The high-pressure phase is stable up to the highest pressure in this study (51.0 GPa) and not quenchable upon decompression to ambient pressure. The compressibility of the triclinic phase exhibits anisotropy, meaning that it is more compressive along interlayer directions than intralayer directions, which demonstrates the properties of the weak interlayer van der Waals interactions and the strong intralayer covalent bonds. The largest change in the unit cell angles with increasing pressures is the increase of β, which indicates a rotation of the sulfur atoms around the rhenium atoms during the compression. Fitting the experimental data of the triclinic phase to the third-order Birch-Murnaghan EOS yields a bulk modulus of K_OT=23±4 GPa with its pressure derivative K_OT′= 29±8, and the second-order yields K_OT=49±3 GPa.     

Multicomponent GeSe2-CdI2-TeO2 (Bi2O3) systems: glass formation and properties

The glass-forming regions of the GeSe₂-CdI₂-TeO₂ (I), GeSe₂-CdI₂-Bi₂O₃ (II) and GeSe₂-TeO₂-Bi₂O₃ (III) systems have been determined. The obtained glassy phases have been characterized by their basic physicochemical parameters such as temperatures of glass transition, crystallization, and melting, density and microhardness. The phase T-X diagram of the GeSe₂-CdI₂ system, which is the basic joint line for systems I and II, has been specified. Three non-variant equilibria (two eutectic and one syntectic) have been observed at temperatures 350, 280 and 375 °C for compositions containing 15, 95 and 33.3 mol% GeSe₂, respectively. A new intermediate phase with probable composition of 2CdI₂·GeSe₂ has been formed.     

Thermochemical behavior of metallic citrate precursors for the production of pure LaAlO3

Pure LaAlO₃ nanoparticles were synthesized, using a citrate-precursor technique. La(NO₃)₃, Al(NO₃)₃, and C₃H₄(OH)(COOH)₃, in a molar ratio of 1:1:4.5, were dissolved in deionized water. The pH of the aqueous solution was adjusted using NH₄OH. After drying, the citrate precursors were charred at 350 °C, followed by calcination at different temperatures. The thermochemical behavior of the charred citrate precursor to form LaAlO₃ was investigated using X-ray diffractometry, infrared spectroscopy, thermogravimetric analysis, and differential thermal analysis. While the charred specimen obtained at pH=2 (without NH₄OH addition) was composed of LaAl(OOCH₂)₃, the charred specimens obtained at pH>2 were composed of LaAlO_3−x−y(CO₃)_x(OH)_2y. All these metallic salts were decomposed at temperatures between 600 and 780 °C to form crystalline LaAlO₃ but calcining the specimens in air at ?800 °C were required to remove all residual chars to produce pure LaAlO₃. At 900 °C, the citrate-derived particles obtained at pH>2 were composed of LaAlO₃ crystallites with an average size of ∼30 nm.     

Preparation of CuInGeSe4 thin films by selenization method using the Cu-In-Ge evaporated layer precursors

CuInGeSe₄ quaternary compounds are known to have a chalcopyrite-like structure and have band gaps of about 1.3 eV, suitable for optimum conversion efficiency for solar cells. We have prepared the CuInGeSe₄ thin films by the selenization method using the Cu-In-Ge evaporated layer precursors. The analyses of X-ray diffraction show that the single phase of CuInGeSe₄ is obtained by the selenization of precursors at 450-500 °C. The SEM observation of film surface shows that the grain sizes are in the order of 1-2 μm. The band gaps of selenized films close to 1.6 eV are wider than that of bulk crystals (about 1.3 eV). These films have p-type conduction and higher electrical resistivities than more 10⁵ Ω cm at room temperature.     

Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)3N)]Sb4S7

The chromium(II) antimony(III) sulphide, [Cr((NH₂CH₂CH₂)₃N)]Sb₄S₇, was synthesised under solvothermal conditions from the reaction of Sb₂S₃, Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction, elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2₁/n with a=7.9756(7), b=10.5191(9), c=25.880(2) Å and β=90.864(5)°. Alternating SbS₃³⁻ trigonal pyramids and Sb₃S₆³⁻ semi-cubes generate Sb₄S₇²⁻ chains which are directly bonded to Cr(tren)²⁺ pendant units. The effective magnetic moment of 4.94(6)μ_B shows a negligible orbital contribution, in agreement with expectations for Cr(II):d⁴ in a ⁵A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides.     

Room temperature stable structures and phase transition of Na2Al2B2O7

By Rietveld refinement of the X-ray diffraction (XRD) data of powdered Na₂Al₂B₂O₇ samples aged for over 3 months, we found that Na₂Al₂B₂O₇ at room temperature is a mixture of two phases with space group and P6₃/m, respectively. The structures of the two phases can be refined with identical cell parameters of a=4.80760(11) Å, c=15.2684(5) Å and are composed by [Al₂B₂O₇]²⁻_∝ double layers stacking alternatively with Na⁺ ions along the c-direction, but differ at in-plane bond orientations of the BO₃/AlO₄ groups within the double layers: in P6₃/m phase B-O₁/Al-O₁ bonds of the two layers are perfectly aligned, whereas in phase they are twisted by 46.4/41.6° around c-axis against each other. It is also found that a freshly prepared sample contains only the phase, but part of the phase will transfer to P6₃/m phase slowly at room temperature and the transition can be reversed by heating the aged sample above 220 °C.     

Glass formation in the As2Se3-As2Te3-Sb2Te3 system

Chalcogenide glasses from the As₂Se₃-As₂Te₃-Sb₂Te₃ system were synthesized for the first time. The glass-forming region was determined by X-ray diffraction and electron microscopic analyses.The basic physicochemical parameters such as density (d), microhardness (HV) and temperatures of phase transformations (glass transition T_g, crystallization T_cr and melting T_m) were measured. Compactness and some thermomechanical characteristics such as volume (V_h) and formation energy (E_h) of micro-voids in the glassy network as well as the elasticity module (E) were calculated. The glass-forming ability was evaluated according to Hruby's criteria (K_G). The correlation between composition and properties of the (As₂Se₃)_x(As₂Te₃)_y(Sb₂Te₃)_z glasses was established and comprehensively discussed.     

Intermediate-temperature polymorphic phase transition in KH2PO4: A synchrotron X-ray diffraction study

We have used synchrotron X-ray diffraction to investigate the structural and chemical changes undergone by polycrystalline KH₂PO₄ (KDP) upon heating within the 30-250 °C temperature interval. Our data show evidence of a polymorphic transition at T∼190 °C from the room-temperature tetragonal KDP phase to a new intermediate-temperature monoclinic KDP modification (spacegroup P2₁/m and lattice parameters a=7.590, b=6.209, c=4.530 Å, and β=107.36°). The monoclinic RDP polymorph remains stable upon further heating to 235 °C, and is isomorphic to its RbH₂PO₄ and CsH₂PO₄ counterparts.     

IR operated novel Ag0.98Cu0.02GaGe3Se8 single crystals

In this work, we report on the structural and optical properties of novel Ag_0.98Cu_0.02GaGe₃Se₈ single crystals that were synthesized by the Bridgman–Stockbarger technique. We have performed illumination by 10.6 μm CO₂ pulsed laser working in the microsecond time duration regime. Such illumination allows causing substantial changes for both pure electronic nonlinear optical effects like optical second harmonic generation as well as piezooptical effects described by the fourth rank tensors. The measurements of the piezo-optical effects were carried out at different temperatures. The effects are observed only during the IR CO₂ laser illumination and are disappeared after switching off the illumination. Simultaneously the IR induced optical second harmonic generation at Er:glass laser fundamental wavelength 1540 nm was performed during illumination by nanosecond Nd:YAG and Er³⁺:glass laser. The observed effects allow to use the studied materials as promising for IR-optoelectronic devices.     

Effect of Ga incorporation on valence band splitting of OVC CuIn3Se5 thin films

Polycrystalline thin films of CuIn_2.95Ga_0.05Se₅ produced by the incorporation of Ga into the ordered vacancy compound CuIn₃Se₅ by a two-stage vacuum evaporation process were structurally, compositionally and optically characterized using X-ray diffraction, energy dispersive analysis of X-rays and optical absorbance measurements. From the X-ray diffraction data of the films, the structural parameters like lattice constants, tetragonal deformation, bond lengths and anion displacement were evaluated and their effect on the optical behavior of films was discussed. The Hopfields quasi-cubic model adapted for chalcopyrites with tetragonal deformation was used to elucidate the crystal field and spin orbital splitting parameters in the uppermost valence band of the compound, using the three energy gaps 1.649, 1.718 and 1.92 eV corresponding to the threefold absorption in the fundamental absorption region of the optical spectra of these films. The percentage contributions of Se p and Cu d orbitals to p-d hybridization in this compound were calculated using linear hybridization of orbitals model and the effects of p-d hybridization on the band gaps were studied.     

Photoelectrochemical properties of electrochemically deposited CdIn2S4 thin films

Thin films of CdIn₂S₄ have been deposited on to stainless steel and fluorine-doped tin oxide (FTO)-coated glass substrates from aqueous acidic bath using an electrodeposition technique. Ethylene diamine tetra-acetic acid (EDTA) disodium salt is used as complexing agent to obtain good-quality deposits by controlling the rate of the reaction. The different preparative parameters like concentration of bath, deposition time, bath temperature, pH of the bath have been optimized by the photoelectrochemical (PEC) technique in order to get good-quality photosensitive material. Different techniques have been used to characterize CdIn₂S₄ thin films. Optical absorption shows the presence of direct transition with band gap energy 2.17 eV. The X-ray diffraction (XRD) analysis of the as-deposited and annealed films showed the presence of polycrystalline nature. Energy-dispersive analysis by X-ray (EDAX) study for the sample deposited at optimized preparative parameters shows that the In-to-Cd ratio is almost 2 and S-to-Cd ratio is almost 4. Scanning electron microscopy (SEM) for samples deposited at optimized preparative parameters reveals that spherical grains are uniformly distributed over the surface of the substrate indicates the well-defined growth of polycrystalline CdIn₂S₄ thin film. PEC characterization of the films is carried out by studying photoresponse, spectral response and photovoltaic output characteristics. The fill factor (ff) and power conversion efficiency (η) of the cell are 69 and 2.94%, respectively.     

Synthesis, crystal structure, Cu doped EPR, thermal and voltammetric studies of [Ni(isonicotinamide)2(H2O)4]·(sac)2 single crystal

The single crystal of [Ni(ina)₂(H₂O)₄]·(sac)₂, (NINS), (ina is isonicotinamide and sac is saccharinate) complex has been prepared and its structural, spectroscopic and thermal properties have been determined. The title complex crystallizes in monoclinic system with space group P2₁/c, Z=2. The octahedral Ni(II) ion, which rides on a crystallographic centre of symmetry, is coordinated by two monodentate ina ligands through the ring nitrogen and four aqua ligands to form discrete [Ni(ina)₂(H₂O)₄] unit, which captures two saccharinate ions in up and down positions, each through intermolecular hydrogen bands. The magnetic environment of copper(II) doped NINS crystal has also been identified by electron paramagnetic resonance (EPR) technique. The g and A values of Cu²⁺ doped NINS single crystal were calculated from the EPR spectra recorded in three mutually perpendicular planes. These values indicated that the paramagnetic centre has a rhombic symmetry with the Cu²⁺ ion having distorted octahedral environment. The complex exhibits only metal centred electroactivity in the potential range of −2.00, 1.25 V versus Ag/AgCl reference electrode.     

Crystallization study of sol-gel un-doped and Pd-doped TiO2 materials

Sol-gel nanostructured titania materials have been reported to have applications in areas ranging from optics via solar energy to gas sensors. In order to enhance the photocatalytic activity, there are many studies regarding the doping of titanium dioxide (TiO₂) material with either non-metals (S, C, N, P) or metals (Ag, Pt, Nd, Fe). The present work has studied some un-doped and Pd-doped sol-gel TiO₂ materials (films and gels), with various surface morphologies and structures, obtained by simultaneous gelation of both precursors Ti(OEt)₄ and Pd(acac)₂. Their structural evaluation and crystallization behavior with thermal treatment were followed by DTA/TG analysis, infrared (IR) spectroscopy, Fourier transform infrared (FTIR), spectroellipsometry (SE), X-ray diffraction (XRD) and atomic force microscope (AFM). The influence of Pd on TiO₂ crystallization for both supported and un-supported materials was studied (lattice parameters, crystallite sizes, internal microstrains). The changes in the optical properties of the TiO₂-based vitreous materials were correlated with the changes of the structure. The hydrophilic properties of the films were also connected with their structure, composition and surface morphology.