Optical and electrical properties of p-type AgInSnxS2−x (x = 0–0.04) thin films prepared by spray pyrolysis

AgInSn_xS_2−x (x = 0–0.2) polycrystalline thin films were prepared by the spray pyrolysis technique. The samples were deposited on glass substrates at temperatures of 375 and 400 °C from alcoholic solutions comprising silver acetate, indium chloride, thiourea and tin chloride. All deposited films crystallized in the chalcopyrite structure of AgInS₂. A p-type conductivity was detected in the Sn-doped samples deposited at 375 °C, otherwise they are n-type. The optical properties of AgInSn_xS_2−x (x < 0.2) resemble those of chalcopyrite AgInS₂. Low-temperature PL measurements revealed that Sn occupying an S-site could be the responsible defect for the p-type conductivity observed in AgInSn_xS_2−x (x < 2) thin films.     

Phase relations, lattice thermal expansion in Ce1−xEuxO2−x/2 and Ce1−xSmxO2−x/2 systems and stabilization of cubic RE2O3 (RE: Eu, Sm)

The phase relations in CeO₂–Eu₂O₃ and CeO₂–Sm₂O₃ systems have been established under slow-cooled conditions from 1400 °C. The two-phase relations differ as the CeO₂–Eu₂O₃ system showed only two monophasic phase fields, namely F-type cubic and C-type cubic, whereas CeO₂–Sm₂O₃ system showed three phase fields namely F-type cubic, C-type cubic and a biphasic field comprising of C-type cubic and monoclinic phase. An interesting observation of this investigation is the stabilization of C-type rare-earth oxide after Ce⁴⁺ substitution, which is attributed to decrease in average cationic size on Ce⁴⁺ substitution at RE³⁺ site. The lattice thermal expansion behavior of F-type solid solution and C-type solid solution in CeO₂–Eu₂O₃ system was investigated by high-temperature XRD.     

Magnetism in Si1 − xMnx diluted magnetic semiconductor thin films

We have studied the electrical and magnetic properties of p-type semiconductor thin films of Si_1 − xMn_x/Si (x = 0.036 and 0.05) grown by molecular beam epitaxy. Experimental results reveal that the resistivity of the samples decreases gradually with increasing measurement temperature, which can be described well by Mott's variable-range-hopping model. All the samples exhibit the ferromagnetic ordering above room temperature. Among these samples, Si_0.95Mn_0.05 has a higher hole density and magnetization. This indicates an enhancement of hole-mediated ferromagnetic exchange interactions when the Mn-doping concentration is increased.     

Crystallization kinetics of SbxSe100−x thin films

The crystallization kinetics in Sb_xSe_100−x films with 39≤x≤58is studied by monitoring the optical transmission of the films during both isothermal and constant rate heatings. The structure of the films upon crystallization and at certain intermediate stages is studied by electron microscopy techniques. The results are analyzed in the frame of the Johnson-Mehl-Avrami theory in order to determine the kinetic parameters (Avrami exponent, activation energy and frequency factor) in addition to the crystallization temperature. The results show that film crystallization is always preceeded by a relaxation process which modifies substantially the optical properties of the amorphous material. Amorphous films with compositions close to the stoichiometric compound (Sb₂Se₃) are found to show the highest activation energy for crystallization.     

Physical and electrical properties of thin films produced by Low Energy Cluster Beam Deposition of mixed InxSb1−x clusters

We present a new gas-aggregation cluster source with two independent crucibles, one for indium and another one for antimony. This source was used to produce mixed In_xSb_1−x clusters in the nanometer range size (typically 4 nm), which were deposited at room temperature on amorphous carbon or glass substrates by low energy cluster beam deposition technique (LECBD). The film composition was analysed by energy dispersive X-ray (EDX) spectroscopy. The morphology and structure of the films were studied by transmission electron microscopy (conventional and high resolution) and selected area electron diffraction (SAED) at different compositions. Semiconducting InSb clusters could be produced by controlling the temperature of the two crucibles. The electrical properties of the films were studied at a film thickness of 20 nm. The conductivity versus temperature appeared to be thermally activated for all compositions.     

YNixMn1−xO3 thin films by pulsed laser deposition: Structure and magnetic properties

Highly oriented YNi_xMn_1−xO₃ thin films on SrTiO₃ (100) substrates were achieved by using pulsed laser deposition for x = 0.33 and x = 0.50. We used a combination of X-ray diffraction, scanning electron microscopy, atomic force microscopy, and magnetic-property measurements. The magnetic transition temperatures (T_c) of the as-grown films are higher than the corresponding bulk values (typically 85 K instead of 80 K, for x = 0.5, and 60 K instead of 50 K, for x = 0.33). Our magnetic measurements also suggest a spin-glass characteristic in the x = 0.33 films, while a cluster glasslike behavior is observed for the films with x = 0.5, which is quite different from that of the bulk samples. Finally, the influence of post-deposition heat treatment on the magnetic properties of the as-grown films is discussed.     

Study of dielectric, magnetic and ferroelectric properties in Bi1 − xGdxFeO3

Gd-doped BiFeO₃ polycrystalline ceramics were synthesized by solid-state reaction method and their dielectric and magnetic properties were investigated. X-ray diffraction pattern showed that Bi_1 − xGd_xFeO₃ (x = 0, 0.05 and 0.1) ceramics were rhombohedral. The Gd substitution has suppressed the usual impurity peaks present in the parent compound and we obtained single phase Bi_0.9Gd_0.1FeO₃ ceramic. Gd substitution reduced the antiferromagnetic Néel temperature (T_N) in Bi_1 − xGd_x FeO_3. An anomaly in the dielectric constant(ε) and dielectric loss(tan (δ)) in the vicinity of the antiferromagnetic Néel temperature (T_N) was observed. Ferroelectric and magnetic hysteresis loops measured at room temperature indicated the coexistence of ferroelectricity and magnetism. The room temperature magnetic hysteresis loops were not saturated, but the magnetic moment was found to increase with increase in Gd concentration.     

Combinatorial synthesis and rapid characterization of Mo1−xSnx (0x1) thin films

Thin films of Mo_1−xSn_x, continuously and linearly mapped for 0<x<1, have been prepared by d.c. magnetron sputter deposition under various growth conditions. X-ray diffraction results indicate that as x in high-pressure deposited Mo_1−xSn_x increases from 0 to approximately 0.45, the bcc lattice expands and no new phases are formed. At low deposition pressures, Mo₃Sn, a β-tungsten structured phase, is formed along with the bcc Mo–Sn solid solution for 0.1<x<0.3. The variation of the lattice parameter for this intermetallic phase also indicates that solid solutions, possibly of the form Mo_3+ySn, are being formed. These materials are of special interest as anode candidates in lithium-ion batteries.     

Preparation and characterization of LiNiVO4 powder and non-stoichiometric LiNixVyOz films

Inverse spinel type structured oxide, LiNiVO₄, was synthesized by using solid-state method and the crystalline powder was characterized by Rietveld refinement and X-ray photoelectron spectroscopy. Non-stoichiometric lithium nickel vanadate thin films were prepared by physical vapour deposition technique. The amorphous films were characterized by Rutherford back-scattering spectroscopy (RBS), nuclear reaction analysis (NRA), Auger electron spectroscopy (AES), X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) analytical methods. Films crystal growth at various temperatures was also studied by XRD and SEM. The HRTEM analysis of sputtered film shows nanocrystalline domains of NiO and LiNiVO₄ phases with characteristic lattice parameters of the host compound and the results correlate well with the XRD data. Electrochemical properties of the films were discussed.     

Oxidation behavior of (Ti1 − xAlx)N films perpared by r.f. reactive sputtering

(Ti, Al)N films have drawn much attention as alternatives for TiN coatings, which are oxidized easily in air above 500 °C. We have investigated the effect of Al content on the oxidation resistance of (Ti_{1 − x}Al_x)N films prepared by r.f. reactive sputtering.(Ti_{1 − x}Al_xN films (O ≤ x ≤ 0.55) were deposited onto fused quartz substrates by r.f. reactive sputtering. Composite targets with five kinds of Al-to-Ti area ratio were used. The sputtering gas was Ar (purity, 5 N) and N₂ (5 N). The flow rate of Ar and N₂ gas was kept constant at 0.8 and 1.2 sccm, respectively, resulting in a sputtering pressure of 0.4 Pa. The r.f. power was 300 W for all experiments. Substrates were not intentionally heated during deposition. The deposited films (thickness, 300 nm) were annealed in air at 600 900 °C and then subjected to X-ray diffractometer and Auger depth profiling.The as-deposited (Ti_{1 − x}Al_x)N films had the same crystal structure as TiN (NaCl type). Al atoms seemed to substitute for Ti in lattice sites. The preferential orientation of the films changed with the Al content of the film, x. Oxide layers of the films grew during annealing and became thicker as the annealing temperature increased. The thickness of the oxide layer grown on the film surface decreased with increasing Al content in the film. For high Al content films an Al-rich oxide layer was grown on the surface, which seemed to prevent further oxidation. All of the films, however, were oxidized by 900 °C annealing, even if the Al content was increased up to 0.55.     

Magnetoresistance effect in thin films of Eu1−xSmxO on silicon

In the present study, the temperature-dependence of magnetic field effect on the resistance of films of oxides of rare earth elements (Gd, Eu, and Eu-Sm solid solution) prepared by vacuum thermal evaporation was considered and analyzed at approximately the Curie temperature. It was demonstrated that the temperature range of the effect, its sign and magnitude are determined by the dependence of the magnetic moment of magnetic clusters on both the external magnetic field strength and film parameters such as the spin of the magnetic ion, exchange energy, defect density, etc.     

Structural and optical analysis of nanocrystalline thin films of mixed rare earth oxides (Y1-xErx)2O3

Nanocrystalline thin films of mixed rare earth oxides (Y_1-xEr_x)₂O₃(0.1 ≤ x ≤ 1) were deposited by electron beam evaporation technique on polished fused silica glass at different substrate temperatures (200-500 °C). The effect of the substrate temperature as well as the mixing parameter (x) on the structural and optical properties of these films has been investigated by using X-ray diffraction (XRD), energy dispersive x-ray analysis and optical spectrophotometry. XRD investigation shows that mixed rare earth oxides film (Y_1-xEr_x)₂O₃ grown at lower substrate temperature (T_s ≤ 300 °C) are poorly crystalline, whereas films grown at higher substrate temperatures (T_s ≥ 400 °C) tend to have better crystallinity. Furthermore, the mixing parameter (x) was found to stabilize the cubic phase over the entire of 0.1 ≤ x ≤ 1. The crystallite size of the films was found to vary in the range from 25 to 39 nm. Optical band gap of the films was deterimined by analysis of the absoprtion coeffifcient. For films deposited at different substrate temperatures direct and indirect transitions occur with energies varied from 5.29 to 5.94 eV and from 4.23 to 4.51 eV, respectively. However, films of different composition x, give optical band gap varied from 6.14 to 5.86 eV for direct transition and from 5.23 to 4.22 eV for indirect transitions. Consequently, one may conclude that it is possible to tune the energy band gap by relative fraction of constituent oxides. It was found that optical constants increase with increasing the substrate temperature. Nevertheless, the values of n and k decrease with increasing the mixing parameter, x.     

Composition dependence of optical constants of Ge1 − xSe2Pbx thin films

Optical constants of vacuum-evaporated thin films in the Ge_1 − xSe₂Pb_x (x = 0, 0.2, 0.4, 0.6) system were calculated from reflectance and transmittance spectra. It is found that the films exhibit a non-direct gap, which decreases with increasing Pb content. The variation in the refractive index and the imaginary part of the dielectric constant with photon energy is reported. The relationship between the optical gap and chemical composition in chalcogenide glasses is discussed in terms of the average heat of atomization.     

Photoconductors based on ZnxCd1−xS and CdSe1−ySy thin films, fabricated with multilayer structure

Photoconductors based on evaporated Zn_xCd_1−xS and CdSe_1−yS_y thin films, with a novel multilayer structure, were fabricated and characterized through spectral response measurements. The device structure is constituted by several layers of different energy gaps, sequentially deposited side by side and interconnected in series or in parallel. The influence of the preparation conditions, number of layers and electrode configuration, on the performance of the photoconductors was determined. Photoresistors with a detection range between 400 and 750 nm were developed, using four layers with energy gaps varying between 1.8 eV and 2.8 eV and interconnected in parallel.     

Random stacking in MoS2−x sputtered thin films

The structure of sputter-deposited MoS_2−x films is investigated by X-ray and electron diffraction. The diffraction spectra show important differences with respect to those of known molybdenite phases. These differences are interpreted in terms of the random-layer model usually applied to turbostratic carbon. Peak profile calculations are performed following an extension of Wilson's model, taking into account the structure factor. They show that the crystal structure of these films consists in a random stacking of S---Mo---S layers, without evidence of 2H or 3R polytypism.     

Effect of substrate temperature on ac conduction properties of amorphous and polycrystalline GaSe thin films

X-ray diffraction analysis of GaSe thin films used in the present investigation showed that the as-deposited and the one deposited at higher substrate temperature are in amorphous and polycrystalline state, respectively. The alternating current (ac) conduction properties of thermally evaporated films of GaSe were studied ex situ employing symmetric aluminium ohmic electrodes in the frequency range of 120-10⁵ Hz at various temperature regimes. For the film deposited at elevated substrate temperature (573 K) the ac conductivity was found to increase with improvement of its crystalline structure. The ac conductivity (σ_ac) is found to be proportional to (ω^s) where s < 1. The temperature dependence of ac conductivity and the parameter, s, is reasonably well interpreted by the correlated barrier-hopping (CBH) model. The maximum barrier heights W_m calculated from ac conductivity measurements are compared with optical studies of our previous reported work for a-GaSe and poly-GaSe thin films. The distance between the localized centres (R), activation energy (ΔE_σ) and the number of sites per unit energy per unit volume N(E_F) at the Fermi level were evaluated for both a-GaSe and poly-GaSe thin films. Goswami and Goswami model has been invoked to explain the dependence of capacitance on frequency and temperature.     

Microstructure and thermoelectric properties of Sn-doped Bi2Te2.7Se0.3 thin films deposited by flash evaporation method

(Bi_1 − xSn_x)₂Te_2.7Se_0.3 thermoelectric thin films with thickness of 800 nm have been deposited on glass substrates by flash evaporation method at 473 K. The structures, morphology of the thin films were analyzed by X-ray diffraction and field emission scanning electron microscopy respectively. Effects of Sn-doping concentration on thermoelectric properties of the annealed thin films were investigated by room-temperature measurement of Seebeck coefficient and electrical resistivity. The thermoelectric power factor was enhanced to 12.8 μW/cmK² (x = 0.003). From x = 0.004 to 0.01 Sn doping concentration, the Seebeck coefficients are positive and show p-type conduction. The Seebeck coefficient and electrical resistivity gradually decrease with increasing Sn doping concentration.     

Photo-induced effects on electrical properties of Ga15Se81Ag4 chalcogenide thin films

The present work deals with the study of photo-induced crystallization on thermally evaporated Ga₁₅Se₈₁Ag₄ chalcogenide thin films. It has been achieved by shining white light using 1500 W tungsten lamp. The ambient temperature during illumination process was controlled and kept at 75 °C, which is in between the glass transition and crystallization temperature of Ga₁₅Se₈₁Ag₄ glasses. The exposure time was experimentally established for different illumination times from 0 to 120 min. After various exposure times, thin films were characterized by XRD and SEM. The dc conductivities and activation energies of these thin films were measured in temperature range of 303-403 K. It is found that the activation energy in Ga₁₅Se₈₁Ag₄ chalcogenide thin films decreases with increasing the exposure time whereas the dc conductivity increases at each temperature by increasing the illumination time.     

Combinatorial pulsed laser deposition and thermoelectricity of (La1−xCax)VO3 composition-spread films

La_1−xCa_xVO₃ composition-spread film library was fabricated by combinatorial pulsed laser deposition and their thermoelectric properties were evaluated paralelly by the multi-channel probes of Seebeck coefficient and electric conductivity. Concurrent X-ray analysis verified the formation of solid soluted films in the full composition range (0x1) as judged from the linear variation of the lattice constants. The Seebeck coefficients of La_1−xCa_xVO₃ changed from a large negative value to almost zero with the increase of x, due presumably to the variation of valence in vanadium ions.The power factor in this library was as high as 0.6 μW/cm K², which was obtained at x=0, i.e. pure LaVO₃ grown at 800 °C.