Characterization and properties of ZnO1−xSx alloy films fabricated by radio-frequency magnetron sputtering

A series of ZnO_1−xS_x alloy films (0 ≤ x ≤ 1) were grown on quartz substrates by radio-frequency (rf) magnetron sputtering of ZnS ceramic target, using oxygen and argon as working gas. X-ray diffraction measurement shows that the ZnO_1−xS_x films have wurtzite structure with (0 0 2) preferential orientation in O-rich side (0 ≤ x ≤ 0.23) and zinc blende structure with (1 1 1) preferential orientation in S-rich side (0.77 ≤ x ≤ 1). However, when the S content is in the range of 0.23 < x < 0.77, the ZnO_1−xS_x film consists of two phases of wurtzite and zinc blende or amorphous ZnO_1−xS_x phase. The band gap energy of the films shows non-linear dependence on the S content, with an optical bowing parameter of about 2.9 eV. The photoluminescence (PL) measurement reveals that the PL spectrum of the wurtzite ZnO_1−xS_x is dominated by visible band and its PL intensity and intensity ratio of UV to visible band decrease greatly compared with undoped ZnO. All as-grown ZnO_1−xS_x films behave insulating, but show n-type conductivity for w-ZnO_1−xS_x and maintain insulating properties for β-ZnO_1−xS_x after annealed. Mechanisms of effects of S on optical and electrical properties of the ZnO_1−xS_x alloy are discussed in the present work.     

Structural and electrical properties of CdSexTe1−x thin films

The ternary semiconductors compounds are found to be very useful in the fabrication of thin film devices. This paper reports the preparation of CdSe_xTe_1?x films (1 ? x ? 0) in the thickness range 1000–3000 Å by vacuum evaporation technique onto glass and mica substrates held at temperatures, 303 to 623 K in a vacuum better than 5 × 10^?6 torr. The films were characterised by determining their composition and structure. The structure of the films, examined using XRD and TEM techniques, was found to be cubic (zincblende) in the entire composition range. The electrical resistivity and Hall mobilities have been determined as a function of film composition and deposition temperature.     

Buffer-less Cu(In,Ga)Se2 solar cells by band offset control using novel transparent electrode

Cu(In,Ga)Se₂ (CIGS) solar cells without buffer layers have been demonstrated. Currently, CdS, Zn(O,S,OH), ZnS, or InS buffer layers are used in high efficiency CIGS solar cells to suppress interface recombination. One of the important parameters to reduce the recombination is the conduction band offset (CBO) between the buffer and CIGS layers. In this study, we have proposed the use of a novel transparent conductive oxide (TCO) which can control the CBO to reduce interface recombination and eliminate the buffer layers. The device simulation was used to verify the effect of CBO control theoretically. Then, the novel TCO material of ZnO_1?xS_x:Al prepared by co-sputtering of ZnO:Al₂O₃ and ZnS targets was fabricated to verify the CBO effect experimentally. The efficiency of a CIGS solar cell with a ZnO:Al/CIGS/Mo/soda-lime glass structure, i.e. buffer-less structure using a conventional TCO, was significantly low because of severe shunting. In contrast, the use of ZnO_1-xS_x:Al instead of ZnO:Al increased the shunt resistance of the CIGS solar cell, resulting in higher open-circuit voltage and efficiency. The result is the first proof of the concept of the buffer-less CIGS solar cells.     

连续离子层吸附反应沉积后硫化法制备柔性铜锌锡硫薄膜太阳电池

在柔性钼箔衬底上采用连续离子层吸附反应法(successive ionic layer absorption and reaction)制备ZnS/Cu2SnSx叠层结构的预制层薄膜,预制层薄膜在蒸发硫气氛、550 C温度条件下进行退火得到Cu2ZnSnS4吸收层.分别采用EDS,XRD,Raman,SEM表征吸收层薄膜的成分、物相和表面形貌.结果表明,退火后薄膜结晶质量良好,表面形貌致密.用在普通钠钙玻璃上采用相同工艺制备的CZTS薄膜表征薄膜的光学和电学性能,表明退火后薄膜带隙宽度为1.49 eV,在可见光区光吸收系数大于104cm 1,载流子浓度与电阻率均满足薄膜太阳电池器件对吸收层的要求.用上述柔性衬底上的吸收层制备Mo foil/CZTS/CdS/i-ZnO/ZnO:Al/Ag结构的薄膜太阳电池得到2.42%的效率,是目前报道柔性CZTS太阳电池最高效率.     

Electrical resistivity and thermal conductivity of UP1−xSx

UP, US, and their solid solutions of several compositions were prepared, and the electrical resistivities of these samples were measured from liquid nitrogen temperature to 1000 K and the thermal diffusivities from 300 to 1000 K. It was shown that the resistivity of UP_1?xS_x at the paramagnetic region arose mainly from the scattering of conduction electrons by disordered spins localized at uranium ion sites. The resistivity of UP_0.4S_0.6 showed another anomaly below the transition temperature. A gentle hump of the thermal diffusivity of UP was observed at about 650 K. This was concluded to be due to the anomalous negative temperature coefficient of electrical resistivity observed above the Néel temperature up to about 550 K. The composition dependence of thermal conductivity of UP_1?xS_x was compared with that of UC_1?xN_x by separating the total conductivity into electronic and phonon contributions.     

Structural, magnetic and transport properties of Ni-doped ZnO films

In this work, Ni-doped ZnO (Zn_1−xNi_xO, x=0, 0.03, 0.06, 0.11) films were prepared using magnetron sputtering. X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), temperature dependence electrical resistance, Hall and magnetic measurements were utilized in order to study the properties of the Ni-doped ZnO films. XRD and XAS results indicate that all the samples have a ZnO wurtzite structure and Ni atoms incorporated into ZnO host matrix without forming any secondary phase. The Hall and electrical resistance measurements revealed that the resistivity increased by Ni doping, and all the Ni-doped ZnO films exhibited n-type semiconducting behavior. The magnetic measurements showed that for the samples with x=0.06 and 0.11 are room-temperature ferromagnetic having a saturation magnetization of 0.33 and 0.39 μ_B/Ni, respectively. The bound-magnetic-polaron mediated exchange is proposed to be the possible mechanism for the room-temperature ferromagnetism in this work.     

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.     

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.     

Ge1-xCx double-layer antireflection and protection coatings

The antireflection Germanium carbide (Ge_1-xC_x) coating, deposited using RF reactive sputtering, on both sides of ZnS substrate wafer has been developed. The infrared (IR) transmittance spectra show that the IR transmittance in the wavelength region between 8 and 12 μm for the designed system Ge_1-xC_x/ZnS/Ge_1-xC_x is greatly enhanced compared to that for ZnS substrate. In addition, the double-layer coated ZnS substrate is approximately four times as hard as uncoated ZnS substrate. This investigation indicates that a double-layer Ge_1-xC_x coating can be used as an effective antireflection and protection coating on ZnS infrared window.     

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.     

Room temperature growth of InxGa1−xN thin films by mixed source modified activated reactive evaporation

Polycrystalline In_xGa_1−xN thin films were prepared by mixed source modified activated reactive evaporation (MARE) technique. The films were deposited at room temperature on glass substrates without any buffer layer. All the films crystallize in the hexagonal wurtzite structure. The indium concentration calculated from XRD peak shift using Vegard's law was found to be varying from 2% to 92%. The band gap varies from 1.72 eV to 3.2 eV for different indium compositions. The indium rich films have higher refractive indices as compared to the gallium rich films. The near infra-red absorption decreases with gallium incorporation into InN lattice which is mainly due to decrease in the free carrier concentration in the alloy system. This fact is further supported from Hall effect measurements. MARE turns out to be a promising technique to grow In_xGa_1−xN films over the entire composition range at room temperature.     

Influence of indium content on the optical, electrical and crystallization kinetics of Se100−xInxthin films deposited by flash evaporation technique

Thin films of Se _100−xIn_x (x=10, 20 and 30 at%) have been prepared by the flash evaporation technique. The effect of the indium content on optical band gap of the Se_100−x In_x films has been investigated by the optical characterization. The optical band gap values of the Se_100−x In_x thin films were determined and are found to decrease with increasing indium content. This indium content changes the width of localized states in the optical band gaps of the thin films. It was found that the optical band gap, E_g, of the Se_100−x In_x films changes from 1.78 to 1.37 eV with increasing indium content from 10 to 30 at%, while the width of localized states in optical band gap changes from 375 to 342 meV. The temperature dependence of the dark electrical conductivity were studied in the temperature range 303-433 K and revealed two activation energies providing two electrical conduction mechanisms. The activation energy of the Se_100−x In_x films in the high temperature region changes from 0.49 to 0.32 eV with increasing indium content from 10 to 30 at%, while the hopping activation energy in the lower temperature region changes from 0.17 to 0.22 meV. The change in the electrical conductivity with time during the amorphous-to-crystalline transformation is recorded for amorphous Se_100−xIn_x films at two points of isothermal temperatures 370 and 400 K. The formal crystallization theory of Avrami has been used to calculate the kinetic parameters of crystallization.     

The microstructure, optical, and electrical properties of sol–gel-derived Sc-doped and Al–Sc co-doped ZnO thin films

Transparent conductive ZnO:Al–Sc (1:0.5, 1:1, 1:1.5 at.% Al–Sc) thin films were prepared on glass substrates by sol–gel method. The microstructure, optical, and electrical properties of ZnO:Sc and ZnO:Al–Sc films were investigated. Results show that Sc-doping alone obviously decreases grain size and degrades the crystallinity; there is an amorphous phase on the surface of ZnO grains; the transmittance spectra fluctuate dramatically with a large absorption valley at about 430–600 nm. However, Al–Sc co-doping can stabilize grain size and improve the microstructure; an average visible transmittance of above 73% is obtained with no large absorption valley; the amorphous phase does not appear. The optical band gaps of ZnO:Sc and ZnO:Al–Sc films (3.30–3.32 eV) are blue-shifted relative to pure ZnO film (3.30 eV). Hall effects show that the lowest resistivity of 2.941 × 10⁻² Ω cm and the maximum Hall mobility of 24.04 cm²/V s are obtained for ZnO:Al–Sc films while ZnO:Sc films do not exhibit any electrical conductivity. Moreover, there is an optimum atomic ratio with Al to Sc of 1:0.5–1 at.%. Although the resistivities are increased compared with that of ZnO:Al film, the Hall mobilities are raised by one order of magnitude.     

Studies on growth and characterization of ternary CdS1−xSex alloy thin films deposited by chemical bath deposition technique

Ternary alloyed CdS_1−xSe_x thin films of variable composition ‘x’ were grown by the simple and economical chemical bath deposition technique. The as-grown thin films were characterized for structural, compositional, surface morphological, optical and electrical studies. The X-ray diffraction (XRD) patterns of the sample indicated that all the samples were polycrystalline in nature with hexagonal structure. Scanning electron microscopy (SEM) micrographs showed uniform morphology with spherical shaped grains distributed over entire glass substrate. EDAX studies confirmed that the CdS_1−xSe_x films were having approximately same stoichiometry initially as well as finally. Room temperature optical measurements showed that band gap engineering could be realized in CdS_1−xSe_x thin films via modulation in composition ‘x’. Electrical resistivity of CdS_1−xSe_x thin films for various compositions was found to be low. The broad and fine tunable band gap properties of ternary CdS_1−xSe_x thin films have potential applications in opto-electronic devices.     

AlNxOy thin films deposited by DC reactive magnetron sputtering

AlN_xO_y thin films were produced by DC reactive magnetron sputtering, using an atmosphere of argon and a reactive gas mixture of nitrogen and oxygen, for a wide range of partial pressures of reactive gas. During the deposition, the discharge current was kept constant and the discharge parameters were monitored. The deposition rate, chemical composition, morphology, structure and electrical resistivity of the coatings are strongly correlated with discharge parameters. Varying the reactive gas mixture partial pressure, the film properties change gradually from metallic-like films, for low reactive gas partial pressures, to stoichiometric amorphous Al₂O₃ insulator films, at high pressures. For intermediate reactive gas pressures, sub-stoichiometric AlN_xO_y films were obtained, with the electrical resistivity of the films increasing with the non-metallic/metallic ratio.     

Effect of substrate temperature on the morphology, structural and optical properties of Zn1−xCoxO thin films

Zn_1−xCo_xO thin films with c-axis preferred orientation were deposited on sapphire (0 0 0 1) by pulsed laser deposition (PLD) technique at different substrate temperatures in an oxygen-deficient ambient. The effect of substrate temperature on the microstructure, morphology and the optical properties of the Zn_1−xCo_xO thin films was studied by means of X-ray diffraction (XRD), atomic force microscopy (AFM), UV-visible-NIR spectrophotometer, fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted as substrate temperature rose. The structure of the samples was not distorted by the Co incorporating into ZnO lattice. The surface roughness of all samples decreased as substrate temperature increased. The Co concentration in the film was higher than in the target. Emission peak near band edge emission of ZnO from the PL spectra of the all samples was quenched because the dopant complexes acted as non-radiative centers. While three emission bands located at 409 nm (3.03 eV), 496 nm (2.5 eV) and 513 nm (2.4 eV) were, respectively, observed from the PL spectra of the four samples. The three emission bands were in relation to Zn interstitials, Zn vacancies and the complex of V_O and Zn_i (V_OZn_i). The quantity of the Zn interstitials maintained invariable basically, while the quantity of the V_OZn_i slightly decreased as substrate temperature increased.     

A TIN-119 Mössbauer and electrical conductivity study of the system SnxGe1-xSe (0 ⩽ x ⩽ 1)

¹¹⁹Sn Mössbauer parameters and electrical conductivity data for phases in the system Sn_xGe_1-xSe (0 ? x ? 1) are reported. The Mössbauer data for the material Sn_0.8Ge_0.2Se show that the electron distribution around the Sn at this composition is anomalous. There is, however, little indication of the presence of such an anomaly in the electrical conductivity and Hall Effect data. The implications of these observations are discussed.     

Properties of Dy-doped ZnO nanocrystalline thin films prepared by pulsed laser deposition

Highly transparent conductive Dy₂O₃ doped zinc oxide (ZnO)_1-x(Dy₂O₃)_x nanocrystalline thin films with x from 0.5% to 5% have been deposited on glass substrate by pulsed laser deposition technique. The structural, electrical and optical properties of Dy₂O₃ doped thin films were investigated as a function of the x value. The experimental results show that the Dy concentration in Dy-doped ZnO thin films has a strong influence on the material properties especially electrical properties. The resistivity decreased to a minimum value of 5.02 × 10⁻⁴ Ω cm with x increasing from 0.5% to 1.0%, then significantly increased with the further increasing of x value. On the contrary, the optical direct band gap of the (ZnO)_1-x(Dy₂O₃)_x films first increased, then decreased with x increasing. The average transmission of Dy₂O₃ doped zinc oxide films in the visible range is above 90%.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

Electrical resistivity of narrow-band ferromagnetic Fe1−xCoxS2

The electrical resistivity of metallic ferromagnet Fe_1−xCo_xS₂ shows an anomalous temperature dependence below Curie point. As the temperature lowers, the resistivity increases for x < 0.9, while it decreases for x > 0.9 with a hump.