Films thickness effect on structural and optoelectronic properties of hydrogenated amorphous germanium (a-Ge:H)

Thin films of hydrogenated amorphous germanium (a-Ge:H) deposited at high growth rate by radiofrequency (RF) glow discharge with 1 sccm GeH₄ diluted in 40 sccm H₂ have been studied. The effect of the films thicknesses on the defect density and on the structural parameters was carefully investigated by means of infrared spectroscopy, optical transmission measurements, and the photothermal deflection spectroscopy (PDS) technique. The results of this investigation show that when the films thicknesses increase, the total hydrogen content (C_H) decreases and the hydrogen-bonding configuration changes. The results of these changes appear clearly on the defects density and on the microstructure parameter of the films, while the disorder parameter E_OV and the optical gap E_T remain practically constant (E_OV ≈ 45 ± 2 meV, E_T = 1.08 ± 0.02 eV). The improvement of these parameters is mainly due to the incorporation of the hydrogen in the bulk of the material as the monohydride groups (Ge-H) rather than the polyhydride groups (Ge-H₂ and Ge-H_2n) when the films thicknesses increase.     

Influence of the nitrogen flow rate on the order and structure of PECVD boron nitride thin films

Three sets of boron nitride (BN) thin films are deposited with different N₂/B₂H₆ flow ratios (r = 4, 10 and 25) by plasma enhanced chemical vapor deposition (PECVD). The variations of physical properties in different deposition sets are analyzed by optical (XPS, FTIR, UV–visible spectroscopies), mechanical and electrical measurements. The films are considered to be deposited in a turbostratic phase (t-BN). Evolution of bonding configurations with increasing r is discussed. Relatively higher nitrogen flow rate in the source gas mixture results in lower deposition rates, whereas more ordered films, which tend to reach a unique virtual crystal of band gap 5.93 eV, are formed. Anisotropy in the film structure and film inhomogeneity along the PECVD electrode radial direction are investigated.     

XAFS investigations of nitrided NbN–SiO2 sol–gel derived films

This work presents the results of the structural analysis of xNbN–(100-x)SiO₂ (x = 100, 80, 60 mol%) thin films by X-ray absorption spectroscopy (XAS). To prepare the films, thermal nitridation of sol–gel derived coatings have been performed. The resulting films have a granular structure with NbN grains distributed in the SiO₂ matrix. The size of the grains depends on the NbN/SiO₂ molar ratio. A detailed X-ray absorption fine structure (XAFS) data analysis shows that in all the samples both nitrogen and oxygen atoms are present as nearest neighbours of Nb. The intra-granular phase is an ordered NbN phase, whereas the shells around the grains are formed mainly by an oxide phase and, possibly, by other niobium nitride phases (probably with low nitrogen content). Two possible origins of the inter-granular oxide phase were considered: incomplete nitridation of Nb₂O₅ and addition of SiO₂. Both of them are connected with the sample preparation method. The obtained XAS results allowed us to correlate the thickness and stoichiometry of the films under study with the electronic structure of the Nb ions and with the local geometric structure in their environment.     

Crystallization of bismuth titanate and bismuth silicate grown as thin films by atomic layer deposition

Bismuth silicate and bismuth titanate thin films were deposited by atomic layer deposition (ALD). A novel approach with pulsing of two Bi-precursors was studied to control the Si/Bi atomic ratio in bismuth silicate thin films. The crystallization of compounds formed in the Bi₂O₃–SiO₂ and Bi₂O₃–TiO₂ systems was investigated. Control of the stoichiometry of Bi–Si–O thin films was studied when deposited on Si(1 0 0) and crystallization was studied for films on sapphire and MgO-, ZrO₂- and YSZ-buffered Si(1 0 0). The Bi–Ti–O thin films were deposited on Si(1 0 0) substrate. Both Bi–Si–O and Bi–Ti–O thin films were amorphous after deposition. Highly a-axis oriented Bi₂SiO₅ thin films were obtained when the Bi–Si–O thin films deposited on MgO-buffered Si(1 0 0) were annealed at 800 °C in nitrogen. The full-width half-maximum values for 200 peak were also studied. An excess of bismuth was found to improve the crystallization of Bi–Ti–O thin films and the best crystallinity was observed with Ti/Bi atomic ratio of 0.28 for films annealed at nitrogen at 1000 °C. Roughness of the thin films as well as the concentration depth distribution were also examined.     

Correlation between nitrogen incorporation and structural modification of hydrogenated carbon nitride films

The growth and microstructure of hydrogenated carbon nitride a-CN_x:H (0 ? x ? 0.10) films deposited by PECVD have been studied. Upon the analysis of FTIR spectra, Raman spectra and XPS, it is concluded that π doping could take place even at a very low percentage of nitrogen, which favors the formation of sp² carbon clusters. The C 1s peak shifts toward higher binding energy while the N 1s peak remains constant as the nitrogen content in the film increases, which can be considered as a result of the chemical shifts on charge transfer due to the strong electronegativity of the N atom. 3D profile measurements show that there were a great number of particles formed when nitrogen is incorporated in to the films and the particles coalescence when the nitrogen content increases due to enhanced surface diffusion. The stress of the films converts from compressive to tensile stress gradually with increased N content. The elimination of grain boundaries and annihilation of excess vacancies, due to columnar structure increasing by diffusion leads to volume shrinkage of the film, thus causing tensile stress. These analyses were fairly consistent to help understand the effects of nitrogen in hydrogenated carbon films.     

Optical absorption in amorphous InN thin films

Amorphous indium nitride (a-InN) thin films were deposited onto different substrates at temperatures <325 K using RF magnetron sputtering at a rate 0.3–0.4 Å/s. X-ray diffraction patterns reveal that the films grown on the substrates are amorphous. The optical absorption edge, ‘bandgap’ energy, E_g, of a-InN has been determined by spectroscopic ellipsometry over the energy range 0.88–4.1 eV. The absorption coefficient was obtained by the analysis of the measured ellipsometric spectra with the Tauc–Lorentz model. The E_g was determined using the modified Tauc and Cody extrapolations. The corresponding Tauc and Cody optical bandgaps were found to be 1.75 and 1.72 eV, respectively. These values are in excellent agreement with the values of the bandgap energy obtained as fitting parameters in the Tauc–Lorentz model: 1.72 ± 0.006 eV as well as by using spectrophotometry (1.74 eV) and photoluminescence (1.6 eV). The spectral dependence of the polarized absorptivities was also investigated. We found that there was a higher absorptivity for wavelengths <725 nm. This wavelength, ∼725 nm, therefore indicates that the absorption edge for a-InN is about 1.70 eV. Thus, the average value of the measured optical absorption of a-InN film is approximately 1.68 ± 0.071 eV.     

Optical properties of Ge–Se–Te wedge-shaped films by using only transmission spectra

Amorphous Ge₁₀Se_90?xTe_x (with x = 0, 5, 10 and 15 at.%) thin films were prepared by thermal evaporation method. The optical transmission spectra of these films were measured in the wavelength range of 500–2500 nm in order to drive the refractive index and the absorption coefficient of these films. Applying the analytical expressions proposed by Swanepoel, enabling the calculations of optical constants of thin films with non-uniform thickness with high accuracy. Furthermore, the dispersion of the refractive index is discussed in terms of the single-oscillator Wemple and DiDomenico model. It was found that, the mechanism of the optical absorption follows the rule of the allowed non-direct transition. The optical band gab, E_g, and the oscillator energy, E_o, decrease while the dispersion energy, E_d, increases by increasing Te content. The relationship between the obtained results and the chemical compositions of the Ge₁₀Se_90?xTe_x thin films were discussed in terms of the chemical bond approach, the excess of Se–Se homopolar bonds and the cohesive energy (CE).     

Electrical properties of annealed a-SiC:H thin films

In the present work the dependence of electrical properties of a-SiC:H thin films on annealing temperature, T_a, has been extensively studied. From the measurements of dark dc electrical conductivity, σ_D, in the high temperature range (from 283 up to 493 K), was found that the conductivity activation energy, E_a, is invariant for T_a ⩽ 673 K and equal to 0.64 eV, whereas for T_a from 673 up to 873 K, E_a increases at about 0.2 eV reaching to a maximum value 0.85 eV at T_a = 873 K, suggesting the optimum material quality. This behavior of E_a as a function of T_a is mainly attributed to relaxation of the strain in the amorphous network, which is possibly combined with weak hydrogen emission for temperatures up to 873 K. For further increase of T_a (>873 K) the phenomenon of hydrogen emission, causes rapid decrease of E_a down to 0.24 eV at T_a = 998 K, deteriorating the material quality. These results are also supported by the measurements of dark dc electrical conductivity in the low temperature range (from 133 up to 283 K), where the dependence of the density of gap states at the Fermi level, N(E_F), on annealing temperature presents the minimum value at T_a = 873 K. The Meyer–Nelder rule was found to hold for the a-SiC:H thin films for annealing temperatures up to 873 K. Finally, the dependence of dark dc electrical conductivity at room temperature, σ_DRT, on T_a showed to reflect directly the dependence of E_a on T_a.     

Effect of deposition pressure on microstructure and properties of hydrogenated carbon nitride films prepared by DC-RF-PECVD

Hydrogenated carbon nitride (a-CN:H films) were deposited on n-type (1 0 0) silicon substrates making use of dual direct current radio frequency plasma enhanced chemical vapor deposition (DC-RF-PECVD), at working pressure of 2–20 Pa, using a mixed gas of CH₄ and N₂ as the source gas. The growth rate, composition, bonding structure of the deposited films were characterized by means of XPS and FTIR, and the mechanical properties of the deposited films were investigated by nano-indentation test. It was found that the parameters for the DC-RF-PECVD process had significant effects on the growth rate, structure and properties of the deposited films. The growth rate of the deposited films increased at first with increasing deposition pressure, then saturated with further increase of the deposition pressure. The N/C ratio inside the deposited films increased with increasing working pressure except that it was as much as 0.50 at a working pressure of 5.0 Pa. The nano-hardness of the films decreased with increasing deposition pressure. CN radicals were remarkably formed in the deposited films at higher pressures, and their contents are related to the nitrogen concentrations in the deposited films.     

Influence of hydrogen on the thermomechanical properties of a-CNx:H and a-CNx films deposited by glow discharge and ion beam assisted deposition

The coefficient of thermal expansion (CTE), Young’s modulus, Poisson’s ratio, stress and hardness of a-CN_x and a-CN_x:H were investigated as a function of nitrogen concentration. Hydrogenated films were prepared by glow discharge, GD, and unhydrogenated films were prepared by ion beam assisted deposition, IBAD. Using nanohardness measurements and the thermally induced bending technique, it was possible to extract separately, Young’s modulus and Poisson’s ratio. A strong influence of hydrogen, in a-CN_x:H films, was observed on the CTE, which reaches about ∼9 × 10⁻⁶ C⁻¹, close to that of graphite (∼8 × 10⁻⁶ C⁻¹) for nitrogen concentration as low as 5 at.%. On the other hand, the CTE of unhydrogenated films increases with nitrogen concentration at a much lower rate, reaching 5.5 × 10⁻⁶ C⁻¹ for 33 at.% nitrogen.     

Effect of Cu additive on the electrical properties of Ge–Se alloy

Electrical measurements have been carried out on a-(Ge₂₀Se₈₀)_100−xCu_x (x = 0.0, 0.5, 1.0, 1.5 and 2.0 at.%) thin films. The dark conductivity (σ_d) and photoconductivity (σ_ph) measurements are done in the temperature range 252–349 K. The values of σ_d, σ_ph increase and dark activation energy (ΔE_d), photo activation energy (ΔE_ph) decrease as the concentration of Cu additive increases (up to 1.0 at.%). Photosensitivity (σ_ph/σ_d) increases and decay time constant (τ_d) decreases as the concentration of Cu increases (up to 1.0 at.%). The charge carrier concentration (n_σ) increases with Cu incorporation (up to 1.0 at.%). A reverse in the trend takes place in all these parameters as the Cu concentration is further increased (>1.0 at.%). These results are explained on the basis of change in the density of defect states present in the mobility gap of Ge–Se–Cu alloy.     

Carbon-K NEXAFS measurements of a-CNx films formed from decomposition of BrCN in electron cyclotron resonance plasmas of He,Ne, and Ar

Amorphous carbon nitride (a-CN_x) films were formed from the decomposition of BrCN in the electron cyclotron resonance plasmas of He, Ne, and Ar. The local structures of these films were investigated by the carbon-K near edge X-ray absorption fine structure. It was found that the density of C=C bond in the film prepared with Ar plasma was 7–9 times larger than that with He or Ne plasmas. The [N]/([C] + [N]) ratios of films were estimated from the X-ray photoelectron spectra as 0.34 ± 0.05, 0.35 ± 0.04, and 0.28 ± 0.05 for the He, Ne, and Ar plasmas, respectively. It was found that C atoms in the sp²-hybridized state were incorporated into the two-dimensional and/or one-dimensional conjugated structures composed of ? C=N? in the cases of the He and Ne plasmas and of ? C=C? in the case of the Ar plasma. The compositions and the local structures of films can be explained in terms of a model based on the cyclazine-like network structures.     

Compositional dependence of optical parameters in Se–Bi–Te–Ag thin films

Compositional dependence of optical parameters in thermally evaporated amorphous Se_80.5Bi_1.5Te_18 ? yAg_y (for y = 0, 1.0, 1.5 and 2.0 at.%) quaternary thin films has been studied using well established Swanepoel method. The optical properties like, refractive index (n), extinction coefficient (k), absorption coefficient (α) and optical band gap (E_g) have been determined from the transmission spectra in the spectral range from 500 to 2500 nm. The optical band gap (E_g) has been estimated by using Tauc's extrapolation method and is found to increase with an increase in the Ag concentration. Present study shows that the refractive index, extinction coefficient and optical band gap increase with the increasing Ag content which is in agreement with the earlier studies. While the increase in the refractive index with Ag content over the entire spectral range can be attributed to the increased polarizability of larger Ag atomic radius (153 pm) compared to the Te atomic radius (135 pm), the increase in the optical band gap with increasing Ag concentration is correlated to an increase in the cohesive energy and decrease in the electronegativity of the films under study. The dielectric constant and optical conductivity (σ) of the thin films under study are also found to increase with the Ag concentration.     

Electrodeposited and selenized CIGS thin films for solar cells

Cu(In,Ga)Se₂ polycrystalline thin films were deposited adopting the potentiostatic electrochemical method on Mo/soda lime glass substrate. All the as-deposited Cu(In,Ga)Se₂ thin films were annealed in a selenium atmosphere at 550 °C for 1 h to improve the film crystalline properties. The selenized CIGS thin films were characterized by energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and scanning electron microscopy (SEM).The results indicate Cu(In,Ga)Se₂ thin films have single chalcopyrite structure and the grain size varies from 0.8 to 2.5 μm.     

Effect of tellurium deposition rate on the properties of Cu–In–Te based thin films and solar cells

To investigate the effects of tellurium (Te) deposition rate on the properties of Cu–In–Te based thin films (Cu/In=0.30–0.31), the films were grown on both bare and Mo-coated soda-lime glass substrates at 200 °C by co-evaporation using a molecular beam epitaxy system. The microstructural properties were examined by means of scanning electron microscopy and X-ray diffraction. The crystalline quality of the films was improved with increase in the deposition rate of Te, and exhibited a single CuIn₃Te₅ phase with a highly preferred (1 1 2) orientation. Te-deficient film (Te/(Cu+In)=1.07) grown with a low Te deposition rate showed a narrow bandgap of 0.99 eV at room temperature. The solar cell performance was affected by the deposition rate of Te. The best solar cell fabricated using CuIn₃Te₅ thin films grown with the highest deposition rate of Te (2.6 nm/s) yielded a total area (0.50 cm²) efficiency of 4.4% (V_oc=309 mV, J_sc=28.0 mA/cm², and FF=0.509) without light soaking.     

Nanocrystalline silicon TFT process using silane diluted in argon–hydrogen mixtures

We have investigated the effect of Ar dilution on the deposition process of intrinsic nc-Si:H (hydrogenated nanocrystalline silicon) thin films used as active layers of top-gate TFTs, in order to improve the TFTs performances. The nc-Si:H films were deposited by plasma enhanced chemical vapor deposition (PECVD) at low temperature (165 °C) and the related TFTs were fabricated with a maximum process temperature of 200 °C. During the nc-Si:H films deposition, the SiH₄ fraction and the total flow of the diluting gases Ar + H₂ mixture was kept constant, H₂ being substituted by Ar. We have pointed out the active role played by the metastable states of excited Ar atoms in both the dissociation of SiH₄ and H₂ by quenching reactions in the plasma. The role of the atomic hydrogen during the film deposition seems to be promoted by the addition of argon into the discharge, leading to an increase of the deposition rate by a factor of about three and an enhancement of the crystalline quality of the nc-Si:H films. This effect is maximized when the Ar fraction in the Ar + H₂ gases mixture reaches 50%. The evolution with Ar addition of the carriers mobility of the related TFTs is closely connected to the evolution of the crystalline fraction of the intrinsic nc-Si:H film. Mobilities values as high as 8 cm² V^?1 s^?1 are obtained at the Ar fraction of 50%. For higher Ar fractions, the fall of the mobility comes with a degradation of the I_D–V_G transfer characteristics of the processed TFTs due to a degradation of the nc-Si:H films quality. OES measurements show that the evolution of the H_α intensity is closely connected to the evolution of the deposition rate, intrinsic films crystalline fraction and TFTs mobility, providing an interesting tool to monitor the TFTs performances.     

Formation and thermal stability of Pd-based bulk metallic glasses

The glass-forming ability and thermal stability of bulk glassy Pd₇₉Cu₆Si₁₀P₅ alloy were studied by substitution of Cu with Ag and with Au + Ag from 0 to 6 at.%. The results indicated that the small addition of Ag strongly affects the thermal stability and glass-forming ability of the Pd₇₉Cu₆Si₁₀P₅ alloy. The alloy doped with 4 at.% Ag (Pd₇₉Cu₂Ag₄Si₁₀P₅) exhibits the largest glass-forming ability among the Pd₇₉Cu_6−xAg_xSi₁₀P₅ (x = 0–6 at.%) alloys. The critical diameter for glass formation of this alloy reaches as large as 7 mm by copper mold casting. On the other hand, the multi-addition of Au + Ag does not increase the glass forming ability though the Ag and Au are similar in atomic size. The largest glass forming ability is obtained at 1 at.% Au + 2 at.% Ag among the Pd₇₉Cu_6−x−yAu_xAg_ySi₁₀P₅ (x = 1–4 at.%, y = 1–3 at.%) alloys. The critical diameter of this alloy is 5 mm by copper mold casting.     

Redox behavior and diffusion of copper in soda-lime-silica melts

Glasses with the base mol% composition xNa₂O · 10CaO · (90 ? x)SiO₂ with x = 10, 16, 20 and 26 were investigated at high temperatures using square-wave voltammetry. The recorded voltammograms exhibit two peaks. That at less negative or (depending on temperature and glass composition) even positive potential is attributed to the reduction of Cu²⁺ to Cu⁺, while that observed at more negative potential is caused by the reduction of Cu⁺ to metallic copper. For both redox steps, the peak potentials decrease linearly with temperature. Those of the composition with 10 mol% Na₂O show the most negative values. The diffusion coefficients can be fitted to Arrhenius equation. If referenced to the same viscosity, the diffusion coefficients decrease with increasing Na₂O-concentration. The effect of composition on the thermodynamics as well as on diffusivities is explained by the incorporation of the copper ions into the melt structure.     

Surface morphology of spin-coated As–S–Se chalcogenide thin films

Surface morphology and roughness of amorphous spin-coated As–S–Se chalcogenide thin films were determined using atomic force microscopy. Prepared films were coated from butylamine solutions with thicknesses d ∼ 100 nm and then annealed in a vacuum furnace at 45 °C and 90 °C for 1 h for their stabilization. The root mean square surface roughness analysis of surfaces of as-deposited spin-coated As–S–Se films indicated a very smooth film surface (with R_q values 0.42–0.45 ± 0.2 nm depending on composition). The nanoscale images of as-deposited films confirmed that surface of the films is created by domains with dimensions 20–40 nm, which corresponds to diameters of clusters found in solutions. The domain character of film surfaces gradually disappeared with increasing annealing temperature while the solvent was removed from the films. Middle-infrared transmission spectra recorded a decrease of intensities of vibration bands connected to N–H (at 3367 and 3292 cm⁻¹) and C–H (at 2965, 2935 and 2880 cm⁻¹) stretching vibrations. Temperature regions of solvent evaporation T = 60–90 °C and glass transformation temperatures T_g = 135–150 °C of spin-coated As–S–Se thin films were determined using a modulated differential scanning calorimetry.