Thermal annealing effect on the crystallization and optical dispersion of sprayed V2O5 thin films

Polycrystalline vanadium pentoxide (V₂O₅) thin films have been deposited by spray pyrolysis technique on preheated glass substrate. The influence of thermal annealing on the crystallization of V₂O₅ has been investigated. X-ray diffraction analysis (XRD) revealed that the films deposited at T_sub=350 °C were orthorhombic structures with a preferential orientation along 〈0 0 1〉 direction. Moreover, the degree of crystallinity was improved by thermal annealing. Optical properties of these samples were studied by spectrophotometer in the wavelength range 300-2500 nm. Some of the important optical absorptions such as optical dispersion energies E_o and E_d, dielectric constant ε, ratio between number of charge carriers and effective mass N/m^*, wavelength of single oscillator λ₀, plasma frequency ω_p, single resonant frequency ω₀ and the average of oscillator strength S_o, have been evaluated. In the annealing process, the dielectric properties have weak dependencies of film thickness and annealing time. Furthermore, a value of carrier concentration was obtained of 3.02×10²⁵ m⁻³ for the as-deposited film and slight changes with annealing time.     

Planar quarter wave stacks prepared from chalcogenide Ge-Se and polymer polystyrene thin films

Planar quarter wave stacks based on amorphous chalcogenide Ge-Se alternating with polymer polystyrene (PS) thin films are reported as Bragg reflectors for near-infrared region. Chalcogenide films were prepared using a thermal evaporation (TE) while polymer films were deposited using a spin-coating technique. The film thicknesses, d∼165 nm for Ge₂₅Se₇₅ (n=2.35) and d∼250 nm for polymer film (n=1.53), were calculated to center the reflection band round 1550 nm, whose wavelengths are used in telecommunication. Optical properties of prepared multilayer stacks were determined in the range 400-2200 nm using spectral ellipsometry, optical transmission and reflection measurements. Total reflection for normal incidence of unpolarized light was observed from 1530 to 1740 nm for 8 Ge-Se+7 PS thin film stacks prepared on silicon wafer. In addition to total reflection of light with normal incidence, the omnidirectional total reflection of TE-polarized light from 8 Ge-Se+7 PS thin film stacks was observed. Reflection band maxima shifted with varying incident angles, i.e., 1420-1680 nm for 45° deflection from the normal and 1300-1630 nm for 70° deflection from the normal.     

Fabrication and characterization of sputtered titanium dioxide films

TiO₂ thin films were prepared under various conditions by using a reactive RF sputtering technique. The structural, optical and electrical characteristics of the films have been investigated. All as-deposited films were amorphous. After annealing at T > 673 K, the crystallinity of the observed tetragonal anatase phase appeared improved. The optical band gap, determined by using Tauc plot, has been found to amount to 3.38 ± 0.03 and 3.21 ± 0.03 eV for the direct and indirect transition, respectively. Also the complex optical constants for the wavelength range 300-2500 nm are reported. Using the two-point probe technique, the dark resistivity has been measured as a function of the film thickness, d. The resistivity, ρ, of the samples has been found to decrease markedly with increasing thickness, but only for d < 100 nm. The behaviour of ρd versus d was found to fit properly with the Fuchs and Sondheimer relation with parameters ρ_o = 4.95 × 10⁶ Ω cm and mean free path, l = 310 ± 2 nm. The log ρ versus 1/T curves show three distinct regions with values for the activation energy of 0.03 ± 0.01, 0.17 ± 0.01 and 0.50 ± 0.02 eV, respectively.     

Solid phase epitaxy of Ge films on CaF2/Si(1 1 1)

At room temperature deposited Ge films (thickness < 3 nm) homogeneously wet CaF₂/Si(1 1 1). The films are crystalline but exhibit granular structure. The grain size decreases with increasing film thickness. The quality of the homogeneous films is improved by annealing up to 200 °C. Ge films break up into islands if higher annealing temperatures are used as demonstrated combining spot profile analysis low energy electron diffraction (SPA-LEED) with auger electron spectroscopy (AES). Annealing up to 600 °C reduces the lateral size of the Ge islands while the surface fraction covered by Ge islands is constant. The CaF₂ film is decomposed if higher annealing temperatures are used. This effect is probably due to the formation of GeF_x complexes which desorb at these temperatures.     

Preparation and properties of spray-deposited ZnIn2Se4 nanocrystalline thin films

Zinc indium selenide (ZnIn₂Se₄) thin films have been deposited onto amorphous and fluorine doped tin oxide (FTO)-coated glass substrates using a spray pyrolysis technique. Aqueous solution containing precursors of Zn, In, and Se has been used to obtain good quality deposits at different substrate temperatures. The preparative parameters such as substrate temperature and concentration of precursors solution have been optimized by photoelectrochemical technique and are found to be 325 °C and 0.025 M, respectively. The X-ray diffraction patterns show that the films are nanocrystalline with rhombohedral crystal structure having lattice parameter a=4.05 Å. The scanning electron microscopy (SEM) studies reveal the compact morphology with large number of single crystals on the surface. From optical absorption data the indirect band gap energy of ZnIn₂Se₄ thin film is found to be 1.41 eV.     

Crystallization and electrical properties of V2O5 thin films prepared by RF sputtering

V₂O₅ thin films were prepared under various conditions by using reactive RF sputtering technique. The microstructure and electrical properties of the films are have been investigated. X-ray diffraction data revealed the films deposited at low O₂/Ar ratio are amorphous. The orthorhombic structure of film improved after post annealing at 873 K. The microstructure parameters (crystallite/domain size and macrostrain) have been evaluated by using a single order Voigt profile method. Using the two-point probe technique, the dark conductivity as a function of the condition parameters such as film thickness, oxygen content and temperature are discussed. It was also found that, the behaviour of ρd versus d was found to fit properly with the Fuchs-Sondheimer relation with the parameters: ρ_o = 2.14 × 10⁷ Ω cm and ?_o = 112 ± 2 nm. At high temperature, the electrical conductivity is dominated by grain boundaries, the values of activation energy and potential barrier height were 0.90 ± 0.02 eV and 0.92 ± 0.02 V, respectively.     

Influence of air annealing on the structural, morphological, optical and electrical properties of chemically deposited ZnSe thin films

Zinc selenide nanocrystalline thin films are grown onto amorphous glass substrate from an aqueous alkaline medium, using chemical bath deposition (CBD) method. The ZnSe thin films are annealed in air for 4 h at various temperatures and characterized by structural, morphological, optical and electrical properties. The as-deposited ZnSe film grew with nanocrystalline cubic phase alongwith some amorphous phase present in it. After annealing metastable nanocrystalline cubic phase was transformed into stable polycrystalline hexagonal phase with partial conversion of ZnSe into ZnO. The optical band gap, E_g, of as-deposited film is 2.85 eV and electrical resistivity of the order of 10⁶-10⁷ Ω cm. Depending upon annealing temperature, decrease up to 0.15 eV and 10² Ω cm were observed in the optical band gap, E_g, and electrical resistivity, respectively.     

Influence of deposition pressure on structural, optical and electrical properties of nc-Si:H films deposited by HW-CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were deposited using HW-CVD technique at various deposition pressures. Characterisation of these films from Raman spectroscopy revealed that nc-Si:H thin films consist of a mixture of two phases, crystalline phase and amorphous phase containing small Si crystals embedded therein. We observed increase in crystallinity in the films with increase in deposition pressure whereas the size of Si nanocrystals was found ∼2 nm over the entire range of deposition pressure studied. The FTIR spectroscopic analysis showed that with increasing deposition pressure the predominant hydrogen bonding in the films shifts from, Si-H to Si-H₂ and (Si-H₂)_n complexes and the hydrogen content in the films was found in the range 6.2-9.3 at% over the entire range of deposition pressure studied. The photo and dark conductivities results also indicate that the films deposited with increasing deposition pressure get structurally modified. It has been found that the optical energy gap range was between 1.72 and 2.1 eV with static refractive index between 2.85 and 3.24. From the present study it has been concluded that the deposition pressure is a key process parameter to induce the crystallinity in the Si:H thin films using HW-CVD.     

Effect of substrate temperature and annealing temperature on the structural, electrical and microstructural properties of thin Pt films by rf magnetron sputtering

Influence of both substrate temperature, T_s, and annealing temperature, T_a, on the structural, electrical and microstructural properties of sputtered deposited Pt thin films have been investigated. X-ray diffraction results show that as deposited Pt films (T_s = 300, 400 °C) are preferentially oriented along (1 1 1) direction. A little growth both along (2 0 0) and (3 1 1) directions are also noticed in the as deposited Pt films. After annealing in air (T_a = 500-700 °C), films become strongly oriented along (1 1 1) plane. With annealing temperature, average crystallite size, D, of the Pt films increases and micro-strain, e, and lattice constant, a₀, decreases. Residual strain observed in the as deposited Pt films is found to be compressive in nature while that in the annealed films is tensile. This change in the strain from compressive to tensile upon annealing is explained in the light of mismatch between the thermal expansion coefficients of the film material and substrate. Room temperature resistivity of Pt films is dependant on both the T_s and T_a of the films. Observed decrease in the film resistivity with T_a is discussed in terms of annihilation of film defects and grain-boundary. Scanning electron microscopic study reveals that as the annealing temperature increases film densification improves. But at an annealing temperature of ∼600 °C, pinholes appear on the film surface and the size of pinhole increases with further increase in the annealing temperature. From X-ray photoelectron spectroscopic analysis, existence of a thin layer of chemisorbed atomic oxygen is detected on the surfaces of the as deposited Pt films. Upon annealing, coverage of this surface oxygen increases.     

Effect of annealing on structural, optical and electrical properties of nanostructured Ge thin films

Ge thin films with a thickness of about 110 nm have been deposited by electron beam evaporation of 99.999% pure Ge powder and annealed in air at 100-500 °C for 2 h. Their optical, electrical and structural properties were studied as a function of annealing temperature. The films are amorphous below an annealing temperature of 400 °C as confirmed by XRD, FESEM and AFM. The films annealed at 400 and 450 °C exhibit X-ray diffraction pattern of Ge with cubic-F structure. The Raman spectrum of the as-deposited film exhibits peak at 298 cm⁻¹, which is left-shifted as compared to that for bulk Ge (i.e. 302 cm⁻¹), indicating nanostructure and quantum confinement in the as-deposited film. The Raman peak shifts further towards lower wavenumbers with annealing temperature. Optical band gap energy of amorphous Ge films changes from 1.1 eV with a substantial increase to ∼1.35 eV on crystallization at 400 and 450 °C and with an abrupt rise to 4.14 eV due to oxidation. The oxidation of Ge has been confirmed by FTIR analysis. The quantum confinement effects cause tailoring of optical band gap energy of Ge thin films making them better absorber of photons for their applications in photo-detectors and solar cells. XRD, FESEM and AFM suggest that the deposited Ge films are composed of nanoparticles in the range of 8-20 nm. The initial surface RMS roughness measured with AFM is 9.56 nm which rises to 12.25 nm with the increase of annealing temperature in the amorphous phase, but reduces to 6.57 nm due to orderedness of the atoms at the surface when crystallization takes place. Electrical resistivity measured as a function of annealing temperature is found to reduce from 460 to 240 Ω-cm in the amorphous phase but drops suddenly to 250 Ω-cm with crystallization at 450 °C. The film shows a steep rise in resistivity to about 22.7 KΩ-cm at 500 °C due to oxidation. RMS roughness and resistivity show almost opposite trends with annealing in the amorphous phase.     

The influence of substrate temperature and annealing on the properties of pulsed laser-deposited YIG films on fused quartz substrate

Yttrium iron garnet (YIG) thin films were deposited on fused quartz substrate at different substrate temperatures (T_s) varying from room temperature (RT) to 850 °C using pulsed laser deposition (PLD) technique. All the films in the as-deposited state were X-ray amorphous and non-magnetic at RT. The film deposited at RT after annealing at temperatures T_a?700 °C showed both X-ray peaks and the magnetic order. The films deposited at higher T_s (500–850 °C) and then annealed at 700 °C resulted in better-quality films with higher 4πM_s value. The highest value of magnetization was for the sample deposited at 850 °C and annealed at 700 °C, which is 68% of the bulk 4πM_s value.     

GeSbTe deposition for the PRAM application

GeSbTe (GST) chalcogenide thin films for the phase-change random access memory (PRAM) were deposited by an atomic layer deposition (ALD) process. New precursors for GST thin films made with an ALD process were synthesized. Among the synthesized precursors, Ge(N(CH₃)₂)₄, Sb(N(CH₃)₂)₄, and Te(i-Pr)₂ (i-Pr = iso-propyl) were selected. Using the above precursors, GST thin films were deposited using an H₂ plasma-assisted ALD process. Film resistivity abruptly changed after an N₂ annealing process above a temperature of 350 °C. Cross-sectional scanning electron microscope (SEM) photographs of the GST films on the patterned substrate with aspect ratio of 7 shows that the step coverage is about 90%.     

Characterization of PbSe1−xTex thin films

The lead salts and their alloys are extremely interesting semiconductors due to their technological importance. The fabrication of devices with alloys of these compounds possessing detecting and lasing capabilities has been an important recent technological development. The high quality polycrystalline thin films of PbSe_1−xTe_x with variable composition (0≤x≤1) have been deposited onto ultra clean glass substrates by vacuum evaporation technique. As deposited films were annealed in vacuum at 350 K. The optical, electrical and structural properties of PbSe_1−xTe_x thin films have been examined. The optical constants (absorption coefficient and bandgap) of the films were determined by absorbance measurements in the wavelength range 2500-5000 nm using Fourier transform infrared spectrophotometer. The dc conductivity and activation energy of the films were measured in the temperature range 300-380 K. The X-ray diffraction patterns were used to determine the sample quality, crystal structure and lattice parameter of the films.     

Effect of composition and thermal annealing on the absorption and electrical conduction of Se85−xTe15Sbx glasses

The optical absorption of the as-prepared and thermally annealed Se_85−xTe₁₅Sb_x (0≤x≤9) thin films was measured. The mechanism of the optical absorption follows the rule of non-direct transition. The optical energy gap (E₀) decreased from 1.12 to 0.84 eV with increasing Sb content of the as-prepared films from 0 to 9 at.%. The as-prepared Se₇₆Te₁₅Sb₉ films showed an increase in (E₀) with increasing the temperature of annealing in the range above T_g (363 K). The electrical conductivity of the as-prepared and annealed films was found to be of Arrhenius type with temperature in the range 300-360 K. The activation energy for conduction was found to decrease with increasing both the Sb content and temperature of annealing. The results were discussed on the basis of the lone-pair electron effect and of amorphous crystalline transformation.     

Solution processed amorphous InGaZnO semiconductor thin films and transistors

Amorphous indium gallium zinc oxide (a-IGZO) semiconductor thin films and transistors were deposited on alkali-free glasses by the sol–gel route. The atomic ratio of In:Ga:Zn in the solution was 0.7:0.3:1. In this study, the effects of annealing temperature on the structural, surface condition, optical transmittance, and electrical resistivity of a-IGZO semiconductor thin films were investigated. GIXRD measurements and TEM-NBD analysis indicated that all annealed IGZO thin films had an amorphous phase structure. The dried IGZO sol–gel films annealed at a temperature higher than 425 °C had a flat surface and exhibited high transparency (>89%) in the visible region. According to results from TGA, FT-IR and XPS, the residual organic compounds in the dried IGZO sol–gel films were completely removed at the annealing temperatures higher than 450 °C. Therefore, we chose the 450 °C annealed thin film as the active channel layer in the bottom-gate, bottom-contact (BGBC) thin-film transistor (TFT) in the present study. Current–voltage (I–V) characteristics of the 450 °C annealed a-IGZO TFT revealed that it operated in n-type behavior with a positive threshold voltage (enhancement mode).     

Formation of periodic structures by the space-selective precipitation of Ge nanoparticles in channel waveguides

Thermally stabilized channel waveguides with Bragg gratings were fabricated by the space-selective precipitation technique of crystalline Ge nanoparticles using KrF excimer laser irradiation. The periodic structures consisting of Ge nanoparticles were formed in Ge-B-SiO₂ thin glass films after exposure to an interference pattern of the laser followed by annealing at 600 °C. The channel waveguides with the periodic structures were fabricated by the cladding of the patterned Cr layers on the films. The diffraction peak for the TE-like mode of 11.8 dB depth was observed clearly at a wavelength of 1526.4 nm, indicating that the periodic structure also served as the optical band-pass filter in optical communication wavelength. The spectral shape, diffraction efficiency, and diffraction wavelength remained unchanged even after annealing at 400 °C. Furthermore, a low temperature dependence of the diffraction wavelength - as low as 8.1 pm/°C - was achieved. The diffraction efficiency was further enhanced after subsequent annealing at 600 °C. The space-selective precipitation technique is expected to be useful for the fabrication of highly reliable optical filters or durable sensing devices operating at high temperature.     

Structural and optical properties of thermal evaporated magnesium phthalocyanine (MgPc) thin films

X-ray powder diffraction (XRD) of MgPc indicated that the material in the powder form is polycrystalline with monoclinic structure. Miller indices, h k l, values for each diffraction peak in XRD spectrum were calculated. Thermal evaporation technique was used to deposit MgPc thin films. The XRD studies were carried out for MgPc thin films where the results confirm the amorphous nature for the as-deposited films. While, polycrystalline films orientated preferentially to (1 0 0) plane with an amorphous background were obtained for films annealed at 623 K for 3 h. Optical properties of MgPc thin films were characterised by using spectrophotometric measurements of transmittance and reflectance in the spectral range from 190 to 2500 nm. The refractive index, n, and the absorption index, k, were calculated. According to the analysis of dispersion curves, the parameters, namely; the optical absorption coefficient (α), molar extinction coefficient (?_molar), oscillator energy (E_os), oscillator strength (f), and electric dipole strength (q²) were also evaluated. The recorded absorption measurements in the UV-vis region show two well defined absorption bands of phthalocyanine molecule; namely the Q-band and the Soret (B-band). The Q-band showed its splitting characteristic (Davydov splitting), and ΔQ was obtained as 0.15 eV. The analysis of the spectral behaviour of the absorption coefficient (α), in the absorption region revealed indirect transitions. The transport and the near onset energy gaps were estimated as respectively 2.74 ± 0.02 and 1.34 ± 0.01 eV.     

Infrared optical properties of Ba(Zr0.20Ti0.80)O3 and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.20 and 0.30) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate by sol-gel method. X-ray diffraction patterns show that the thin films have a good crystallinity. Optical properties of the films in the wavelength range of 2.5-12 μm are studied by infrared spectroscopic ellipsometry (IRSE). The optical constants of the BZT thin films are determined by fitting the IRSE data using a classical dispersion formula. As the wavelength increases, the refractive index decreases, while the extinction coefficients increase. The effective static ionic charges are derived, which are smaller than that in a purely ionic material for the BZT thin films.     

Derivation of the optical constants of spin coated CeO2-TiO2-ZrO2 thin films prepared by sol-gel route

Ternary thin films of cerium titanium zirconium mixed oxide were prepared by the sol-gel process and deposited by a spin coating technique at different spin speeds (1000-4000 rpm). Ceric ammonium nitrate, Ce(NO₃)₆(NH₄)₂, titanium butoxide, Ti[O(CH₂)₃CH₃]₄, and zirconium propoxide, Zr(OCH₂CH₂CH₃)₄, were used as starting materials. Differential calorimetric analysis (DSC) and thermogravimetric analysis (TGA) were carried out on the CeO₂-TiO₂-ZrO₂ gel to study the decomposition and phase transition of the gel. For molecular, structural, elemental, and morphological characterization of the films, Fourier Transform Infrared (FTIR) spectral analysis, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), cross-sectional scanning electron microscopy (SEM), and atomic force microscopy (AFM) were carried out. All the ternary oxide thin films were amorphous. The optical constants (refractive index, extinction coefficient, band gap) and thickness of the films were determined in the 350-1000 nm wavelength range by using an nkd spectrophotometer. The refractive index, extinction coefficient, and thickness of the films were changed by varying the spin speed. The oscillator and dispersion energies were obtained using the Wemple-DiDomenico dispersion relationship. The optical band gap is independent of the spin speed and has a value of about E_g≈2.82±0.04 eV for indirect transition.     

Growth, structural and optical transport properties of nanocrystal Zn1−xCdS thin films deposited by solution growth technique (SGT) for photosensor applications

Solution Growth Technique (SGT) has been used for deposition of Zn_1−xCdS nanocrystalline thin films. Various parameters such as solution pH (10.4), deposition time, concentration of ions, composition and deposition and annealing temperatures have been optimized for the development of device grade thin film. In order to achieve uniformity and adhesiveness of thin film on glass substrate, 5 ml triethanolamine (TEA) have been added in deposition solution. The as-deposited films have been annealed in Rapid Thermal Annealing (RTA) system at various temperature ranges from 100 to 500 °C in air. The changes in structural formation and optical transport phenomena have been studied with annealing temperatures and composition value (x). As-deposited films have two phases of ZnS and CdS, which were confirmed by X-ray diffraction studies; further the X-ray analysis of annealed (380 °C) films indicates that the films have nanocrystalline size (150 nm) and crystal structure depends on the films stoichiometry and annealing temperatures. The Zn_0.4CdS films annealed at 380 °C in air for 5 min have hexagonal structure where as films annealed at 500 °C have represented the oxide phase with hexagonal structure. Optical properties of the films were studied in the wavelength range 350-1000 nm. The optical band gap (E_g=2.94-2.30 eV) decreases with the composition (x) value. The effect of air rapid annealing on the photoresponse has also been observed on Zn_1−xCdS nanocrystal thin films. The Zn_1−xCdS thin film has higher photosensitivity at higher annealing temperatures (380-500 °C), and films also have mixed Zn_1−xCdS/Zn_1−xCdSO phase with larger grain size than the as-deposited and films annealed up to 380 °C. The present results are well agreed with the results of other studies.