Structure-composition-property dependence in reactive magnetron sputtered ZnO thin films

Thin films of zinc oxide (ZnO) were prepared by dc reactive magnetron sputtering on glass substrates at various oxygen partial pressures in the range 1×10⁻⁴–6×10⁻³ mbar and substrate temperatures in the range 548–723 K. The variation of cathode potential of zinc target on the oxygen partial pressure was explained in terms of target poisoning effects. The stoichiometry of the films has improved with the increase in the oxygen partial pressure. The films were polycrystalline with wurtzite structure. The films formed at higher substrate temperatures were (0 0 2) oriented. The temperature dependence of Hall mobility of the films formed at various substrate temperatures indicated that the grain boundary scattering of charge carriers was predominant electrical conduction mechanism in these films. The optical band gap of the films increased with the increase of substrate temperature. The ZnO films formed under optimized oxygen partial pressure of 1×10⁻³ mbar and substrate temperature of 663 K exhibited low electrical resistivity of 6.9×10⁻² Ω cm, high visible optical transmittance of 83%, optical band gap of 3.28 eV and a figure of merit of 78 Ω⁻¹ cm⁻¹.     

Synthesis and characterization of p-type transparent conducting CuAlO2 thin film by DC sputtering

P-type transparent conducting thin films of copper aluminium oxide were prepared by DC sputtering of polycrystalline CuAlO₂ target, which was fabricated by heating a stoichiometric mixture of Cu₂O and Al₂O₃ at 1375 K for 24 h. Thin films of CuAlO₂ were deposited on Si (4 0 0) and glass substrates. The sputtering was performed in Ar+O₂ (40 vol.%) atmosphere and the substrate temperature was 453 K. X-ray diffraction spectra of the films showed the peaks that could be assigned with those of the crystalline CuAlO₂. Fourier transform infrared spectra showed Cu---O, Al---O, O---Cu---O bonding. UV–Vis–NIR spectrophotometric measurement showed high transparency of the films in the visible region. Both direct and indirect band gaps were found to exist and their corresponding estimated values were 3.66 and 2.1 eV, respectively. The room temperature conductivity of the film was fairly high and was of the order of 0.08 S cm⁻¹, while the activation energy was 0.26 eV. Thermoelectric power measurement indicated positive value of Seebeck coefficient and its room temperature value was +128 μV K⁻¹. Positive value of Hall coefficient (R_H=+16.7 cm³ C⁻¹) also confirmed p-type conductivity of the films.     

A methodology for the preparation of nanoporous polyimide films with low dielectric constants

Cuprous oxide and copper thin films were potentiostatically electrodeposited in an acetate bath. Voltammetric curves were used to investigate the growth parameters; deposition potential, pH and temperature of the bath. Deposition potential dependency on the structural, morphological, optical and electronic properties of the films were investigated by the X-ray diffraction measurements, scanning electron micrographs, absorption measurements and dark and light current–voltage characterisations. It was observed that single phase polycrystalline Cu₂O can be deposited from 0 to − 300 mV Vs saturated calomel electrode (SCE) and co-deposition of Cu and Cu₂O starts at − 400 mV Vs SCE. Further increase in deposition potential from − 700 mV Vs SCE produces single phase Cu thin films. Single phase polycrystalline Cu₂O thin films with cubic grains of 1–2 μm can be possible within the very narrow potential domain around − 200 mV Vs SCE. Enhanced photoresponse in a photoelectrochemical cell is produced by the Cu₂O thin film prepared at − 400 mV Vs SCE, where Cu is co-deposited with Cu₂O with random distribution of Cu spheres on the Cu₂O surface. This study reveals that a single deposition bath can be used to deposit both Cu and Cu₂O separately and an admixture of Cu–Cu₂O by controlling the deposition parameters.     

Transparent conductive In2O3:Mo thin films prepared by reactive direct current magnetron sputtering at room temperature

An amorphous transparent conductive oxide thin film of molybdenum-doped indium oxide (IMO) was prepared by reactive direct current magnetron sputtering at room temperature. The films formed on glass microscope slides show good electrical and optical properties: the low resistivity of 5.9 × 10^− 4 Ω cm, the carrier concentration of 5.2 × 10²⁰ cm^− 3, the carrier mobility of 20.2 cm² V^− 1 s^− 1, and an average visible transmittance of about 90.1%. The investigation reveals that oxygen content influences greatly the carrier concentration and then the photoelectrical properties of the films. Atomic force microscope evaluation shows that the IMO film with uniform particle size and smooth surface in terms of root mean square of 0.8 nm was obtained.     

Preparation and characterization of chemically deposited PbSnS3 thin films

High-quality and well-reproducible PbSnS₃ thin films have been prepared by a simple and inexpensive chemical-bath deposition method from an aqueous medium, using thioacetamide as a sulphide ion source. X-ray diffraction analysis of the deposited films revealed that the as-deposited films were amorphous, however, an amorphous-to-crystalline phase transition was observed as the result of thermal annealing at 425 K for 1 h. The X-ray structure analysis of the collected powder from the bath annealed at 425 K for 1.5 h revealed an orthorhombic phase.

Analysis of the optical absorption data of crystalline PbSnS₃ films revealed that both direct and indirect optical transitions exist in the photon energy range 1.24–2.48 eV with optical band gaps of 1.68 and 1.42 eV, respectively. However, a forbidden direct optical transition with a band gap value of 1.038 eV dominates at low energy (<1.24 eV). The refractive index changes from 3.38 to 2.16 in the range 500–1300 nm. The high frequency dielectric constant and the carrier concentration to the effective mass ratio calculated from the refractive index analysis were found to be 4.79 and 2.3×10²⁰ cm⁻³, respectively. The temperature dependence of the electrical resistivity of the deposited films follows the semiconductor behaviour with extrinsic and intrinsic conduction. The determined activation energies range are 0.35–0.42 and 0.76–85 eV, respectively.     

Structural, electrical, and optical studies on rapid thermally processed ferroelectric BaTiO3 thin films prepared by metallo-organic solution deposition technique

Polycrystalline BaTiO₃ thin films having the perovskite structure were successfully produced on platinum coated silicon, bare silicon, and fused quartz substrate by the combination of the metallo-organic solution deposition technique and post-deposition rapid thermal annealing treatment. The films exhibited good structural, electrical, and optical properties. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) and metal-ferroelectric-semiconductor (MFS) capacitors. The typical measured small signal dielectric constant and dissipation factor at a frequency of 100 kHz were 255 and 0.025, respectively, and the remanent polarization and coercive field were 2.2 μC cm⁻² and 25 kV cm⁻¹, respectively. The resistivity was found to be in the range 10¹⁰–10¹² Ω·cm, up to an applied electric field of 100 kV cm⁻¹, for films annealed in the temperature range 550–700 °C. The films deposited on bare silicon substrates exhibited good film/substrate interface characteristics. The films deposited on fused quartz were highly transparent. An optical band gap of 3.5 eV and a refractive index of 2.05 (measured at 550 nm) was obtained for polycrystalline BaTiO₃ thin film on fused quartz substrate. The optical dispersion behavior of BaTiO₃ thin films was found to fit the Sellmeir dispersion formula well.     

Enhanced ferroelectric properties of multilayer SrBi2Ta2O9/SrBi2Nb2O9 thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉/SrBi₂Nb₂O₉ (SBT/SBN) multilayer thin films with various stacking periodicity were deposited on Pt/TiO₂/SiO₂/Si substrate by pulsed laser deposition technique. The X-ray diffraction patterns indicated that the perovskite phase was fully formed with polycrystalline structure in all the films. The Raman spectra showed the frequency of the O–Ta–O stretching mode for multilayer and single layer SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBNT) samples was 827–829 cm⁻¹, which was in between the stretching mode frequency in SBT (813 cm⁻¹) and SBN (834 cm⁻¹) thin films. The dielectric constant was increased from 300 (SBT) to 373 at 100 kHz in the double layer SBT/SBN sample with thickness of each layer being 200 nm. The remanent polarization (2P_r) for this film was obtained 41.7 μC/cm², which is much higher, compared to pure SBT film (19.2 μC/cm²). The coercive field of this double layer film (67 kV/cm) was found to be lower than SBN film (98 kV/cm).     

Effect of deposition temperature on the structural and thermoelectric properties of bismuth telluride thin films grown by co-sputtering

Thermoelectric bismuth telluride thin films were prepared on SiO₂/Si substrates by radio-frequency (RF) magnetron sputtering. Co-sputtering method with Bi and Te targets was adopted to control films' composition. Bi_xTe_y thin films were elaborated at various deposition temperatures with fixed RF powers, which yielded the stoichiometric Bi₂Te₃ film deposition without intentional substrate heating. The effects of deposition temperature on surface morphology, crystallinity and electrical transport properties were investigated. Hexagonal crystallites were clearly visible at the surface of films deposited above 290 °C. Change of dominant phase from rhombohedral Bi₂Te₃ to hexagonal BiTe was confirmed with X-ray diffraction analyses. Seebeck coefficients of all samples have negative value, indicating the prepared Bi_xTe_y films are n-type conduction. Optimum of Seebeck coefficient and power factor were obtained at the deposition temperature of 225 °C (about − 55 μV/K and 3 × 10^− 4 W/K²·m, respectively). Deterioration of thermoelectric properties at higher temperature could be explained with Te deficiency and resultant BiTe phase evolution due to the evaporation of Te elements from the film surface.     

Solid polymer electrolytes based on poly(vinylchloride)–lithium sulfate

Ionic conductivity studies in the temperature range 304–373 K for PVC---Li₂SO₄---dibutylphthalate polymer electrolyte systems are reported and discussed. Poly(vinylchloride) (PVC) has an electrical conductivity 10⁻⁸ S cm⁻¹. The prepared films were studies by X-ray diffraction, Fourier transformation infrared, scanning electron microscopy and thermal analysis. The temperature dependence of the conductivity of the polymer films obeys the Vogel–Tammann–Fulcher relation.     

Optically active Er–Yb codoped Y2O3 films produced by pulsed laser deposition

Optically active Er³⁺:Yb³⁺ codoped Y₂O₃ films have been produced on c-cut sapphire substrates by pulsed laser deposition from ceramic Er:Yb:Y₂O₃ targets having different rare-earth concentrations. Stoichiometic films with very high rare-earth concentrations (up to 5.5 × 10²¹ at cm^− 3) have been achieved by using a low oxygen pressure (1 Pa) during deposition whereas higher pressures lead to films having excess of oxygen. The crystalline structure of such stoichiometric films was found to worsen the thicker the films are. Their luminescence at 1.53 μm and up-conversion effects have been studied by pumping the Yb³⁺ at 0.974 μm. The highest lifetime value (up to 4.6 ms) is achieved in films having Er concentrations of ≈ 3.5 × 10²⁰ at cm^− 3 and total rare-earth concentration ≈ 1.8 × 10²¹ at cm^− 3. All the stoichiometric films irrespective of their rare-earth concentration or crystalline quality have shown no significant up-conversion.     

Characterization of SnS films prepared by constant-current electro-deposition

SnS films have been prepared on the indium tin oxide coated glass substrates by the constant-current electro-deposition. By investigating the influence of the deposition parameters on the composition of the deposited films, we obtained the optimum deposition parameters with pH = 2.7, Sn²⁺ / S₂O₃²⁻ = 1 / 5, J = 3.0 mA/cm² and t = 1.5 h. Many nearly stoichiometric SnS films were prepared. These films were characterized with X-ray diffraction and scanning electron microscopy analysis, and they were polycrystalline with orthorhombic structure. Their direct band gaps were estimated to be 1.211.42 eV from optical measurements. The films have p-type conductivity with a resistivity of 7.520 Ω·cm.     

Thermal conductivity of BaWO4 single crystal

Barium tungstate (BaWO₄) single crystal has been grown using Czochralski technique. It belongs to the scheelite structure, forming the space group I4₁/a at room temperature and the primitive cell contains two formular units. The thermal expansion, specific heat and thermal diffusivity were measured, and then the thermal conductivity was calculated. These results show that BaWO₄ possesses large anisotropic thermal expansion and its thermal expansion coefficients are _a = 1.10 × 10⁻⁵/K, _b = 1.08 × 10⁻⁵/K, and _c = 3.51 × 10⁻⁵/K in the temperature range from 303 to 1423 K. However, its thermal conductivity shows small anisotropic in the temperature range from 297 to 563 K and even displays isotropic at about 428 K. The calculated thermal conductivities are 2.59 and 2.73 W m⁻¹ K⁻¹ at room temperature, along [1 0 0] and [0 0 1] directions, respectively.     

Deep levels in GaInAs grown by molecular beam epitaxy and their concentration reduction with annealing treatment

X-ray diffraction (XRD), current–voltage (IV), capacitance–voltage (CV), deep-level transient Fourier spectroscopy (DLTFS) and isothermal transient spectroscopy (ITS) techniques are used to investigate the thermal annealing behaviour of three deep levels in Ga_0.986In_0.014As heavily doped with Si (6.8 × 10¹⁷ cm⁻³) grown by molecular beam epitaxy (MBE). The thermal annealing was performed at 625 °C, 650 °C, 675 °C, 700 °C and 750 °C for 5 min. XRD study shows good structural quality of the samples and yields an In composition of 1.4%. Two main electron traps are detected by DLTFS and ITS around 280 K, with activation energies of 0.58 eV and 0.57 eV, capture cross sections of 9 × 10⁻¹⁵ cm² and 8.6 × 10⁻¹⁴ cm² and densities of 2.8 × 10¹⁶ cm⁻³ and 9.6 × 10¹⁵ cm⁻³, respectively. They appear overlapped and as a single peak, which divides into two smaller peaks after annealing at 625 °C for 5 min.

Annealing at higher temperatures further reduces the trap concentrations. A secondary electron trap is found at 150 K with an activation energy of 0.274 eV, a capture cross section of 8.64 × 10⁻¹⁵ cm² and a density of 1.38 × 10¹⁵ cm⁻³. The concentration of this trap level is also decreased by thermal annealing.     

Boron phosphide films prepared by co-evaporation technique: Synthesis and characterization

We report the physical and electronic properties of BP films of 1:1, 1:1.15 and 1.25:1 stoichiometry prepared by co-evaporating B and P onto glass and Si (100) substrates. Compositional information was obtained from X-ray photoelectron spectroscopy measurements. Optical studies indicated allowed indirect transition at  2.08 eV. The room temperature photoluminescence peak at  2.01 eV was due to band gap transitions which shifted to higher energy value when recorded at lower temperature. Fourier transformed infrared (FTIR) spectra were dominated by the characteristic peak of the B–P located at  810 cm^− 1 which could be identified as arising due to transverse optical vibration mode (k  0) while the shoulder at  850 cm^− 1 may be due to longitudinal optical (k  0) vibration mode. Other characteristic peaks for B–O, P–O and B–H vibration modes were also present in the FTIR spectra. Characteristic Raman peaks for BP located at  415 cm^− 1 and 806 cm^− 1 were observed in these films.     

Implantation effect of diamond-like carbon films by 110 keV nitrogen ions

Diamond-like carbon films, grown on microscope slides by a dual-ion beam sputtering system, were implanted by 110 keV N⁺ under the doses of 1 × 10¹⁵, 1 × 10¹⁶ and 1 × 10¹⁷ions cm⁻² respectively. The implantation induced changes in electrical resistivity of the films and in infrared (IR) transmittance of the specimens were investigated as a function of implantation dose. The structural changes of the films were also studied using IR spectroscopy and Raman spectroscopy. It was observed that, with the increase of implantation dose, the diamond-like carbon films display two different stages in electrical and optical behaviours. The first is the increase of both the film resistivity and the IR transmittance of specimen at the dose of 1 × 10¹⁵ ions cm⁻² which, we consider, is attributed to the implantation-induced increase sp³ C---H bonds. However, when the doses are higher than 1 × 10¹⁵ ions cm⁻², the film resistivity and the IR transmittance of specimen decrea significantly and the decrease rates at dose range of 1×10¹⁶ to 1×10¹⁷ ions cm⁻² are smaller than those between 1×10¹⁵ and 1 × 10¹⁶ ions cm⁻². We conclude that the significant reductions of the two parameters at high doses are caused by the decreases of bond-angle disorder and of sp³ C---H bonds, the increases of sp² C---C bonds dominated the crystallite size and/or number and also the sp² C---H bonds. The smaller decrease rates at a dose range of 1 × 10¹⁶ to 1 × 10¹⁷ ions cm⁻² may be caused by further recombination of some retained hydrogen atoms to carbon atoms.     

Properties of tantalum oxide thin films grown by atomic layer deposition

Thin tantalum oxide films were deposited using atomic layer deposition from TaCl₅ and H₂O at temperatures in the range 80–500 °C. The films deposited at temperatures below 300 °C were predominantly amorphous, whereas those grown at higher temperatures were polycrystalline containing the phases TaO₂ and Ta₂O₅. The oxygen to tantalum mass concentration ratio corresponded to that of TaO₂ at all growth temperatures. The optical band gap was close to 4.2 eV for amorphous films and ranged from 3.9 to 4.5 eV for polycrystalline films. The refractive index measured at λ = 550 nm increased from 1.97 to 2.20 with an increase in growth temperature from 80 to 300 °C. The films deposited at 80 °C showed low absorption with absorption coefficients of less than 100 cm⁻¹ in the visible region.     

Optical gain calculation of mid-infrared InAsN/GaSb quantum-well laser for tunable absorption spectroscopy applications

We report on optical gain calculations of a dilute-nitride mid-infrared laser structure designed to be grown on InAs substrate. The active region is composed of several strain-compensated type-II “W”-like InAsN/GaSb/InAsN quantum wells adapted to operate near 3.3 μm at room temperature. For typical injected carrier density σ = 1.1012 cm^− 2, the theoretical laser structure performances reveal a gain value at around 1000 cm^− 1 at 300 K, inducing a modal gain value equal to 50 cm^− 1. Low radiative current densities lower than 100 A/cm² are predicted, indicating that this dilute-nitride structure could operate at 300 K with small threshold current density.     

Analysis of VUV and optical spectra of Cs2NaYF6 crystals doped with Tm

This study presents a detailed interpretation and analysis of the reported interconfigurational spectra of Tm³⁺ in Cs₂NaYF₆ [V.N. Makhov, N.M. Khaidukov, D. Lo, J.C. Krupa, M. Kirm, E. Negodin, Opt. Mater. 27 (2005) 1131]. Since only spin-forbidden d–f emission bands are observed for Tm³⁺ in this host, it is unsuitable for use as a scintillator because the emission lifetime is too long. The d–f emission spectrum is well-explained by calculation and most of the intensity is located in one band: 4f¹¹5d¹ (high-spin) → 4f^{12 3}H₆. Measurements from the bands in the d–f excitation spectrum do not provide the accurate separation energy of the high and low-spin states. Strict O_h point group selection rules are operative for the optical spectra. The electronic states of the 4f¹¹5d¹ configuration (briefly, d-electron states, hereafter) are calculated to span from 58,318 cm⁻¹ to 86,900 cm⁻¹. At least five structured bands are observed in the excitation spectrum and their intensities are fairly well simulated by calculation. The 4f¹² → 4f¹³ (np₆)⁻¹ charge transfer band is assigned between 140 and 120 nm (83,000–71,000 cm⁻¹) and excitation into this band leads to f–f emission, bypassing the d-electron states.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Structure and properties of SnS films prepared by electro-deposition in presence of EDTA

SnS thin films were deposited onto indium tin oxide (ITO) glass substrates by constant potential cathodic electro-deposition from aqueous solution containing stannous sulfate, ethylenediamine tetraacetate acid and sodium thiosulfate. The co-deposited potential was explored by cyclic voltammetry and the deposition potential (E) was roughly determined to be more negative than −0.70 V (vs. saturated calomel electrode, SCE). The analysis of the composition of the as-deposited films by X-ray fluorescence spectrometer indicated that stoichiometric SnS films could be obtained under the condition of E = −0.95 to −1.00 V. The films deposited at E = −1.00 V were characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), and their transmission and reflectance spectra were measured. The as-deposited films were polycrystalline SnS compound with orthorhombic crystalline structure and the ratio of Sn and S was nearly 1. The films were uniform and compact with small grains. The direct band gap of the films was estimated to be about 1.10–1.43 eV with an absorption coefficient near the fundamental absorption edge larger than 4 × 10⁴ cm⁻¹.