Properties of CuIn(SxSe1−x)2 polycrystalline thin films prepared by chemical spray pyrolysis

CuIn(S_xSe_1−x)₂ thin polycrystalline films were grown by the chemical spray pyrolysis method on the glass substrate at 280-400°C. The alloy composition in the film was studied with relation to that in the splay solution. Films were characterized by X-ray diffraction, optical absorption, Raman spectroscopy, resistivity and surface morphology. The CuInSe₂-rich alloy films grown at high substrate temperature had chalcopyrite structure, while, the CuInS₂-rich films grown at low substrate temperature exhibited sphalerite structure. Optical-gap energies were smaller than that of the bulk crystal by 0.1-0.2 eV for CuInS₂-rich films. Raman spectra exhibited both CuInSe₂-like and CuInS₂-like A₁ modes, and their relative changed systematically with alloy composition.     

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.     

Growth, structural and optical properties of non-stoichiometric CuIn(S1−xSex)2 thin films deposited by solution growth technique for photovoltaic application

Polycrystalline thin films of p-CuIn(S_1−xSe_x)₂ have been deposited by a solution growth technique. The deposition parameters such as pH, temperature and time have been optimized. In order to achieve uniformity of thin film, triethanolamine (TEA) has been used. As deposited films have been annealed at 450 °C in air for 5 min. The surface morphology, compositional ratio, structural properties have been studied by SEM, EDAX and XRD technique, respectively. It has been found that films have chalcopyrite structure with the lattice parameters a=5.28 Å and c=11.45 Å at composition x=0.5. The grain size of all composition x measured from SEM and XRD is varied in between 450 and 520 nm. The optical transmittance spectra have been recorded in the range 350-1000 nm. The absorption coefficient has been calculated at the absorption edge for each of the composition x and it is in the range of 10⁴ cm⁻¹. The material shows the direct allowed band gap, which varies from 1.07 to 1.44 eV with change in composition (0≤x≤1.0). These parameters are useful for the photovoltaic application.     

Structural and electrical characterization of SxSe100−x thin films

Thin films of samples of the glassy S_xSe_100−x system with 0 ≤ x ≤ 7.28 have been prepared by thermal evaporation technique at room temperature (300 K). X-ray investigations show that the structure of pure selenium (Se) does change seriously by the addition of small amount of sulphur S ≤7.28%. The lattice parameters were determined as a function of sulphur content. Results of differential thermal analysis (DTA) of the glassy compositions of the system S_xSe_100−x were discussed. The characteristic temperatures (T_g, T_c and T_m) were evaluated. Dark electrical resistivities, ρ, of S_xSe_100−x thin films with different thicknesses from 100 to 500 nm, were measured in the temperature range from 300 to 423 K. Two distinct linear parts with different activation energies were observed. The variation of electrical resistivity of examined compositions has been discussed as a function of the film thickness, temperature and the sulphur content. The application of Mott model for the phonon assisted hopping of small polarons gave the same two activation energies obtained from the resistivity temperature calculations.     

Preparation and characterization of electrodeposited Sb2Se3 thin films from non-aqueous media

Semiconducting Sb₂Se₃ thin films have been prepared onto the stainless steel and fluorine doped tin oxide coated glass substrates from non-aqueous media using an electrodeposition technique. The electrodeposition potentials for different bath compositions and concentrations of solution have been estimated from the polarization curves. SbCl₃ and SeO₂ in the volumetric proportion as 1:1 with their equimolar solution concentration of 0.05 M form good quality films. The films are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and optical absorption techniques. The SEM studies show that the film covers the total substrate surface with uneven surface morphology. The XRD patterns of the films obtained by varying compositions and concentrations show that the as-deposited films are polycrystalline with relatively higher grain size for 1:1 composition and 0.05 M concentration. The optical band gap energy for indirect transition in Sb₂Se₃ thin films is found to be 1.195 eV.     

Microstructures and coercivities of SmCox and Sm(Co,Cu)5 films prepared by magnetron sputtering

We have investigated the influence of composition and annealing conditions on the magnetic properties and microstructural features of SmCo_x films that were prepared by sputtering and subsequent annealing. A huge in-plane coercivity of 5.6 T was obtained from an optimally annealed Sm–Co film, which was attributed to the nanometer sized polycrystalline microstructure of the highly anisotropic SmCo₅ phase. Although a high density of planar defects were observed in the films that were annealed at high temperatures, they did not act as strong pinning sites for domain wall motion. The effect of Cu on [SmCo_4.5(9 nm)/Cu(xnm)]₁₀ multilayer thin films was also studied. An appropriate Cu content increased the coercivity.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.     

Structural and optical properties of In35Sb45Se20−xTex phase-change thin films

Physical properties of In₃₅Sb₄₅Se_20−xTe_x thin films with different compositions (x=2.5, 5, 7.5, 10, 12.5 and 15 at %) prepared by electron beam evaporation method are studied. X-ray diffraction results indicate that the as-evaporated films depend on the Te content and the crystallized compounds consist mainly of Sb₂Se₃ with small amount of Sb₂SeTe₂. Transmittance and reflectance of the films are found to be thickness dependent. Optical-absorption data indicate that the absorption mechanism is direct transition. Optical band gap values decrease with increase in Te content as well as with increase in film thickness.     

Effects of substrate bias and nitrogen flow ratio on the surface morphology and binding state of reactively sputtered ZrNx films before and after annealing

ZrN_x films were sputtered in an Ar + N₂ atmosphere, with different substrate biases (0 to −200 V) at various nitrogen flow ratios (%N₂ = 0.5-24%). The surface morphology, resistivity, crystllinity, and bonding configuration of ZrN_x films, before and after vacuum annealing, were investigated. As compared with ZrN_x films grown without substrate bias, before and after annealing, the resistivity of 1% and 2% N₂ films decreases with increasing substrate biases. Simultaneously, if the applied bias is too high, the crystallinity of ZrN_x film will decrease. The surfaces of 1% and 2% N₂ flow films deposited without bias have small nodules, whereas the surface morphology of films deposited at −100 V of substrate bias exhibits large nodules and rugged surface. Once a −200 V of substrate bias is applied to the substrate, the surface morphology of ZrN_x films, grown at 1% and 2% nitrogen flow ratios, is smooth. Furthermore, there are two deconvoluted peaks in XPS spectra (i.e., Zr-O and Zr-N) of ZrN_x films deposited at −200 V of substrate bias before and after annealing. On the other hand, the surface morphology changes dramatically from rugged surfaces for film deposited at lower nitrogen flow ratio (%N₂ < 1%) to smoother and denser surfaces for film grown at higher nitrogen flow ratio (%N₂ ≥ 1%). The Zr-N bonding in 2% N₂ films still exist after annealing at 700 °C, while the Zr-N bonding in 0.5% and 16% N₂ flow film vanish at the same temperature. The connection between the resistivity, crystallinity, surface morphology, and bonding configuration of ZrN_x films and how they are influenced by the substrate bias and nitrogen flow ratio are discussed in this paper.     

Magnetic, electric, and optical functionalities of (PLZT)x(BiFeO3)1−x ferroelectric-ferromagnetic thin films

We have prepared a series of (PLZT)_x(BiFeO₃)_1−x transparent thin films with thickness of 300 nm by a thermal pyrolysis method. Only films with x≦0.10 formed a single phase of perovskite structure. The film where x=0.10 exhibited both ferromagnetic and ferroelectric properties at room temperature with spontaneous magnetization and coercive magnetic fields of 0.0027μ_B and 5500 G, respectively. The remanent electric polarization and coercive electric field for the film where x=0.10 were 3.0 μC/cm² and 24 kV/cm, respectively. Additionally, films with 0.02≦x≦0.10 showed both magneto-optical effects and the second harmonic generation of transmitted light.     

Structural and optical properties of a-Si1−xCx:H films synthesized by dc magnetron sputtering technique

Hydrogenated amorphous SiC films (a-Si_1−xC_x:H) were prepared by dc magnetron sputtering technique on p-type Si(1 0 0) and corning 9075 substrates at low temperature, by using 32 sprigs of silicon carbide (6H-SiC). The deposited a-Si_1−xC_x:H film was realized under a mixture of argon and hydrogen gases. The a-Si_1−xC_x:H films have been investigated by scanning electronic microscopy equipped with an EDS system (SEM-EDS), X-ray diffraction (XRD), secondary ions mass spectrometry (SIMS), Fourier transform infrared spectroscopy (FTIR), UV-vis-IR spectrophotometry, and photoluminescence (PL). XRD results showed that the deposited film was amorphous with a structure as a-Si_0.80C_0.20:H corresponding to 20 at.% carbon. The photoluminescence response of the samples was observed in the visible range at room temperature with two peaks centred at 463 nm (2.68 eV) and 542 nm (2.29 eV). In addition, the dependence of photoluminescence behaviour on film thickness for a certain carbon composition in hydrogenated amorphous SiC films (a-Si_1−xC_x:H) has been investigated.     

The structure of ordered Au films on TiOx

The growth of Au on an ultra-thin, ordered Mo(1 1 2)-(8 × 2)-TiO_x, was investigated using scanning tunneling microscopy (STM), low energy ion scattering spectroscopy (LEISS), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption (TPD). Wetting of the TiO_x surface by Au was observed with STM and LEISS, and the ordering of the Au films was atomically resolved with STM. TPD showed that Au binds more strongly to the reduced TiO_x film than to bulk TiO₂, but more weakly than to the Mo substrate. The Au-TiO_x binding energy is greater than Au-Au in bulk Au. The oxidation state of Ti in the TiO_x film was deduced by XPS and from the Ti-O phonon shifts relative to bulk TiO₂. The TiO_x/Mo(1 1 2) film structure and those for the (1 × 1)- and (1 × 3)-Au/TiO_x/Mo(1 1 2) surfaces are discussed.     

Epitaxial growth of bcc-FexCo100-x thin films on MgO(1 1 0) single-crystal substrates

Fe_xCo_100-x (x=100, 65, 50 at%) epitaxial thin films were prepared on MgO(1 1 0) single-crystal substrates heated at 300 °C by ultra-high vacuum molecular beam epitaxy. The film structure and the growth mechanism are discussed. FeCo(2 1 1) films with bcc structure grow epitaxially on MgO(1 1 0) substrates with two types of variants whose orientations are rotated around the film normal by 180° each other for all compositions. Fe_xCo_100-x film growth follows the Volmer Weber mode. X-ray diffraction analysis indicates the out-of-plane and the in-plane lattice spacings are in agreement with the values of respective bulk Fe_xCo_100-x crystals with very small errors less than ±0.4%, suggesting the strains in the films are very small. High-resolution cross-sectional transmission electron microscopy shows that periodical misfit dislocations are preferentially introduced in the film at the Fe₅₀Co₅₀/MgO interface along the MgO[1 1¯ 0] direction. The presence of such periodical dislocations decreases the large lattice mismatch of about −17% existing at the FeCo/MgO interface along the MgO[1 1¯ 0] direction.     

Electric, thermoelectrical and photoelectric properties of CuGaxIn1−xSe2 thin films

The electrical conductivity σ, Hall effect R_H, and thermoelectric power Q of CuGa_0.25In_0.75Se₂ thin films with different growth conditions have been measured at temperature 300-520 K. These properties were also measured at room temperature for different composition of CuGa_xIn_1−xSe₂ (0.75≥x≥0) deposited at the same evaporation conditions. All investigated films are p-type over the whole temperature range. Electrical conduction was studied in order to establish its mechanism.The room temperature photoelectric response of those films were measured as a function of wavelength (2.5≥λ≥0.3) μm. It is found that the energy gap values follow a second order equation in x giving a downward bowing parameter of about 0.31 eV.     

Study of polycrystalline bulk CuIn1-xGaxTe2

Polycrystalline CuIn_1−xGa_xTe₂ bulk films were synthesized by reacting, in stoichiometric proportions, high purity Cu, In, Ga and Te in a vacuum sealed quartz ampoule. The phase structure and composition of the bulk films were analysed by X-ray diffraction and energy-dispersive X-ray analysis, respectively. The bulk samples, of p-type conductivity, are found to be near-stoichiometric, polycrystalline, with tetragonal chalcopyrite structure, predominantly oriented along a direction perpendicular to the (1 1 2) plane. Photoluminescence spectra were recorded at 7 K and 700 mW to characterize the defects and the structural quality. The main peak as a function of composition has been studied.     

Structural and optical properties of CuIn1−xAlxSe2 thin films prepared by four-source elemental evaporation

CuIn_1−xAl_xSe₂ (CIASe) thin films with x=0.25, 0.5 and 0.65 were prepared by four-source elemental evaporation. The structural and optical properties were investigated by X-ray diffraction, scanning electron microscopy, energy dispersive analysis, and optical transmission. The results showed that these films contain chalcopyrite structure with preferred orientation along (112) direction. The morphology, grain distribution and composition of CIASe films were studied and compared for different Al content. The optical studies revealed that the films were highly absorbing and the energy band gap calculated from transmission spectra for x=0.25, 0.5 and 0.65 were 1.2, 1.51 and 1.73 eV, respectively. The variation of Al content in the CIASe composition offered a very effective change in the optical band gap.     

Effect of Cu deficiency on the optical properties and electronic structure of CuIn1−xGaxSe2

Spectroscopic ellipsometry measurements of CuInSe₂ (CIS) and CuIn_1−xGa_xSe₂ (CIGS) over a range of Cu compositions reveal that there are important differences in electronic and optical properties between α-phase CIS/CIGS and Cu-poor CIS/CIGS. We find a reduction in the imaginary part of the dielectric function ?₂ in the spectral region, 1-3 eV. This reduction can be explained in terms of the Cu-3d density of states. An increase in band gap is found for Cu-poor CIS and CIGS due to the reduction in repulsive interaction between Cu-3d and Se-4p states. We also characterize the dielectric functions of polycrystalline thin-film α-phase CuIn_1−xGa_xSe₂ (x=0.18 and 0.36) to determine their optical properties and compare them with similar compositions of bulk polycrystalline CuIn_1−xGa_xSe₂. The experimental results have important implications for understanding the functioning of polycrystalline optoelectronic devices.     

Short-range order analysis and some physical properties of InxSe1−x glasses

Bulk In_xSe_1−x (with x=5-25 at%) glasses were prepared using the melt-quench technique. Short range order(SRO) was examined by the X-ray diffraction using Cu(k_α) radiation in the wave vector interval 0.28≤k≤6.5 A⁰⁻¹.The SRO parameters have been obtained from the radial distribution function. The inter-atomic distance obtained from the first and second peak are r₁=0.263 and r₂=0.460 nm, which is equivalent In-Se and Se-Se bond length. The fundamental structural unit for the studied glasses is In₂Se₃ pyramid. Using the differential scanning calorimetry (DSC), the crystallization mechanism of In_xSe_1−x chalcogenide glass has been studied. The glass transition activation energy (E_g) is 289±0.3 kj/mol.There is a correlation amongst the glass forming ability, bond strength and the number of lone pair electrons. The utility of the Gibbs-Di Marzio relation was achieved by estimating T_g theoretically.     

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.     

Surface free energy of CrNx films deposited using closed field unbalanced magnetron sputtering

CrN_x thin films have attracted much attention for semiconductor IC packaging molding dies and forming tools due to their excellent hardness, thermal stability and non-sticking properties (low surface free energy). However, few data has been published on the surface free energy (SFE) of CrN_x films at temperatures in the range 20-170 °C. In this study CrN_x thin films with CrN, Cr(N), Cr₂N (and mixture of these phases) were prepared using closed field unbalanced magnetron sputtering at a wide range of Cr⁺² emission intensity. The contact angles of water, di-iodomethane and ethylene glycol on the coated surfaces were measured at temperatures in the range 20-170 °C using a Dataphysics OCA-20 contact angle analyzer. The surface free energy of the CrN_x films and their components (e.g., dispersion, polar) were calculated using the Owens-Wendt geometric mean approach. The influences of CrN_x film surface roughness and microstructure on the surface free energy were investigated by atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. The experimental results showed that the lowest total SFE was obtained corresponding to CrN at temperature in 20 °C. This is lower than that of Cr(N), Cr₂N (and mixture of these phases). The total SFE, dispersive SFE and polar SFE of CrN_x films decreased with increasing surface temperature. The film roughness has an obvious effect on the SFE and there is tendency for the SFE to increase with increasing film surface roughness.