High-pressure condition of SiH4+Ar+H2 plasma for deposition of hydrogenated nanocrystalline silicon film

The characteristics of 13.56-MHz discharged SiH₄+Ar+H₂ plasma at high pressure (2–8 Torr), used for the deposition of hydrogenated nanocrystalline silicon (nc-Si:H) films in a capacitively coupled symmetric PECVD system, has been investigated. Plasma parameters such as average electron density, sheath field and bulk field are extracted from equivalent circuit model of the plasma using outputs (current, voltage and phase) of RF V–I probe under different pressure conditions. The conditions of growth in terms of plasma parameters are correlated with properties of the hydrogenated nanocrystalline silicon films characterized by Raman, AFM and dc conductivity. The film deposited at 4 Torr of pressure, where relatively low sheath/bulk field ratio is observed, exhibits high crystallinity and conductivity. The crystalline volume fraction of the films estimated from the Raman spectra is found to vary from 23% to 79%, and the trend of variation is similar to the RF real plasma impedance data.     

Preparation of dense and uniform La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) films for fundamental studies of SOFC cathodes

Thin films of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) were deposited on (1 0 0) silicon and on GDC electrolyte substrates by rf-magnetron sputtering using a single-phase oxide target of LSCF. The conditions for sputtering were systematically studied to get dense and uniform films, including substrate temperature (23–600 °C) background pressure (1.2 × 10⁻² to 3.0 × 10⁻² mbar), power, and deposition time. Results indicate that to produce a dense, uniform, and crack-free LSCF film, the best substrate temperature is 23 °C and the argon pressure is 2.5 × 10⁻² mbar. Further, the electrochemical properties of a dense LSCF film were also determined in a cell consisting of a dense LSCF film (as working electrode), a GDC electrolyte membrane, and a porous LSCF counter electrode. Successful fabrication of high quality (dense and uniform) LSCF films with control of thickness, morphology, and crystallinity is vital to fundamental studies of cathode materials for solid oxide fuel cells.     

MgH2 thin films deposited by one-step reactive plasma sputtering

The morphology, crystal structure, hydrogen content, and sorption properties of magnesium hydride thin films prepared by reactive plasma-assisted sputter deposition were investigated. Few micrometers-thick films were deposited on Si and SiO₂/Si substrates, at low pressure (0.4 Pa) and close to room temperature using (Ar + H₂) plasma with H₂ fraction in the range 15–70%. The microstructure and hydrogen content of the films are closely related to the surface temperature and hydrogen partial pressure during the deposition process. Operating in pulsed-plasma mode allows the hydrogenation rate of the MgH₂ thin film to top up to 98%, thereby producing a nearly fully hydrogenated film in a single-step process. The positive effect of the pulsed process is explained by the significant decrease in the whole energy flux incident on the surface and the favourable impact of the transient process for the rearrangement/relaxation of the materials. As for the hydrogen storage properties, desorption experiments and cycling of the films show the destabilizing effect of Mg₂Si formation at the interface between the film and the Si substrate resulting in a drastically increased desorption kinetics compared to less reactive SiO₂ substrate. However, the reaction is regrettably not reversible upon hydrogenation and the hydrogen storage capacity is consequently reduced upon cycling. Nevertheless, the deposition process carried out on inert substrates would offer true potential for reversible storage. Finally, our experimental results, which show the possibility to preferentially grow the metastable medium pressure γ-MgH₂ phase, open possibilities for the synthesis of more complex metastable phases such as magnesium-based ternary compounds.     

Influence of silane flow on structural, optical and electrical properties of a-Si:H thin films deposited by hot wire chemical vapor deposition (HW-CVD) technique

The electrical, structural and optical properties of hydrogenated amorphous silicon (a-Si:H) films deposited from pure silane (SiH₄) using hot wire chemical vapor deposition (HW-CVD) technique are systematically studied as a function of silane flow rate between 5 and 30 sccm. We found that the properties are greatly affected by the silane flow rate over the range we studied. The device quality a-Si:H films with a photosensitivity >10⁵ were deposited by HW-CVD at a deposition rate >10 Å s⁻¹ using low silane flow rate. However, a-Si:H films deposited at higher silane flow rate and/or higher deposition rates show degradation in their structural and electrical properties. The FTIR studies indicate that the hydrogen bonding in a-Si:H films shifts from mono-hydrogen (Si–H) to di-hydrogen (Si–H₂) and (Si–H₂)_n complexes when films were deposited at higher silane flow rate. The hydrogen content in the a-Si:H films increases with increase in silane flow rate and was found to be less than 10 at.%. The Raman spectra show increase in disorder and the Rayleigh scattering with increase in silane flow rate. The optical band gap also shows an increasing trend with silane flow rate. Therefore, only the hydrogen content cannot be accounted for the increase in the optical band gap. We think that the increase in the optical band gap may be due to the increase in the voids. These voids reduce the effective density of material and increase the average Si–Si distance, which is responsible for the increase in the band gap. Silane flow rate of 5 sccm, appears to be an optimum flow rate for the growth of mono-hydrogen (Si–H) bonded species having low hydrogen content (4.25 at%) in a-Si:H films at high deposition rate (12.5 Å s⁻¹), high photosensitivity (10⁵) and small structural disorder.     

Co-deposition of TiO2/CdS films electrode for photo-electrochemical cells

A densely packed TiO₂ thin film onto an indium doped–tin oxide (ITO) substrate was synthesized at room temperature by chemical deposition and a CdS thin film was deposited onto the pre-deposited TiO₂ film by a doctor blade route (powder of CdS was obtained from chemical deposition). TiO₂/CdS film was annealed at 300 °C for 1 h in air for crystallinity improvement. The first grown TiO₂ film was nanocrystalline, whereas the CdS film was polycrystalline as evidenced by X-ray diffraction (XRD) and selected area electron diffraction (SAED). Scanning electron microscopy (SEM) images show formation of mono-dispersed CdS spherical grains onto compact, densely packed spherical nanocrystalline grains of TiO₂. The TiO₂/CdS bilayer film was used in a photo-electrochemical cell as a working electrode, and a platinum electrode as a counter electrode (0.1 M lithium iodide electrolyte) under 80 mW/cm² light illumination intensity.     

Effects of deposition variables on spray-deposited MnO2 thin films prepared from Mn(C2H3O2)2·4H2O

Undoped MnO₂ thin films have been prepared by a modified spray pyrolysis technique under various deposition conditions and the effects of different variables on electrical and optical properties have been studied in detail. It is found that substrate temperature, spray rate, solution concentration, carrier air pressure and post-deposition heat-treatment, spray outlet to substrate distance play important role in obtaining optimum films.Electrical conductivity study shows an anomaly in conductivity at a temperature 323 K and its thickness dependent resistivity follows Fuchs–Sondheimer theory. The Hall effect and thermoelectric studies indicate that the deposited sample is an n-type semiconductor. Optical study in the entire wavelength 0.3–2.5 μm range exhibits a high transmittance in the visible as well as in the near infrared. Calculation from optical data, the sample exhibits a band gap at 0.28 eV, which also supports the value obtained from the Hall effect study. These studies may be of importance for the applications of this material in energy efficient surface coating devices.     

Optical and electrochemical properties of V2O5:Ta Sol–Gel thin films

Vanadium and tantalum-doped vanadium pentoxide, V₂O₅ and V₂O₅:Ta thin films (2.5 and 5 mol% of Ta) were prepared using sol–gel dip-coating technique.The coating solutions were prepared by reacting vanadium (V) oxytripropoxide and tantalum ethoxide (V) as precursors using anhydrous isopropyl alcohol as solvent.The films were deposited on a transparent glass substrate with ITO conducting film by dip-coating technique, with a withdrawal of 20 cm/min from the vanadium–tantalum solution and heat treated at 300 °C for 1 h. The resulting films were characterized by cyclic voltammetry, optical spectroscopy and by X-ray diffraction analysis (XRD). XRD data show that the films thermally treated at 300 °C were crystalline.A charge density of 70 mC/cm² was obtained for the film with 5 mol% of Ta, with an excellent stability up to 1500 cycles.     

Improvement of a-Si solar cell properties by using SnO2:F TCO films coated with an ultra-thin TiO2 layer prepared by APCVD

TiO₂-overcoated SnO₂:F transparent conductive oxide films were prepared by atmospheric pressure chemical vapor deposition (APCVD) and an effect of TiO₂ layer thickness on a-Si solar cell properties was investigated. The optical properties and the structure of the TiO₂ films were evaluated by spectroscopic ellipsometry and X-ray difractometry. a-Si thin film solar cells were fabricated on the SnO₂:F films over-coated with TiO₂ films of various thicknesses (1.0, 1.5 and 2.0 nm) and I–V characteristics of these cells were measured under 1 sun (100 mW/cm² AM-1.5) illumination. It was found that the TiO₂ film deposited by APCVD has a refractive index of 2.4 at 550 nm and anatase crystal structure. The conversion efficiency of the a-Si solar cell fabricated on the 2.0 nm TiO₂-overcoated SnO₂:F film increased by 3%, which is mainly attributed to an increase in open circuit voltage (V_oc) of 30 mV.     

Optical and electrical properties of flash-evaporated amorphous CuInSe2 films

Amorphous films of CuInSe₂ were deposited on glass substrate by flash evaporation of source materials. The films were found to be p-type semiconductors. The direct optical band-gap energy was obtained to be 1.21–1.41 eV. The film DC conductivity ranged from 1.2–5.7 S cm⁻¹ at 285 K for different film thickness with corresponding activation energy of 55.5–301 meV. From temperature dependence of conductivity, the carrier transport was interpreted to be due to band conduction above 270 K.     

Direct synthesis of MgH2 nanofibers at different hydrogen pressures

This paper describes the direct synthesis of magnesium hydride (MgH₂) nanofibers by hydriding chemical vapor deposition (HCVD), in which the effect of hydrogen pressure on the production rate, the composition and the shape of products obtained were examined by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET). The XRD patterns showed that the main product in each case was MgH₂; in particular, the products formed at 2, 3 and 4 MPa were highly pure. In contrast, at a hydrogen pressure of 1 MPa, unhydrided Mg was deposited along with MgH₂. The SEM images also revealed orientation of the as-deposited products; higher pressures of 3 and 4 MPa caused the formation of straight and curved nanofibers, and lower ones of 1 and 2 MPa, highly curved nanofibers and nanorods with a few straight nanofibers. With pressurizing hydrogen, not only the BET specific surface areas of the products but also the production rate increased. The results also appealed that HCVD could control the shape/size of MgH₂ nanofibers by changing the pressure via only a single operation.     

Pyrite (FeS2) thin films prepared by spray method using FeSO4 and (NH4)2Sx

A simple spray method for the preparation of pyrite (FeS₂) thin films has been studied using FeSO₄ and (NH₄)₂S_x as precursors for Fe and S, respectively. Aqueous solutions of these precursors are sprayed alternately onto a substrate heated up to 120°C. Although Fe–S compounds including pyrite are formed on the substrate by the spraying, sulfurization of deposited films is needed to convert other phases such as FeS or marcasite into pyrite. A single-phase pyrite film is obtained after the sulfurization in a H₂S atmosphere at around 500°C for 30 min. All pyrite films prepared show p-type conduction. They have a carrier concentration (p) in the range 10¹⁶–10²⁰ cm⁻³ and a Hall mobility (μ_H) in the range 200–1 cm²/V s. The best electrical properties (p=7×10¹⁶ cm⁻³, μ_H=210 cm²/V s) for a pyrite film prepared here show the excellence of this method. The use of a lower concentration FeSO₄ solution is found to enhance grain growth of pyrite crystals and also to improve electrical properties of pyrite films.     

Studies on microstructure of silicon thin films and its effect on solar cells

Intrinsic microcrystalline silicon films have been deposited at high-power–high-pressure regime. Effects of pressure and hydrogen dilution on the microstructures of the films have been investigated. Crystalline size decreases at high pressure although the deposition rate increases up to 10 Å/s. Microstructure depends sensitively on pressure as well as on hydrogen dilution of silane. Single junction solar cells have been fabricated with Si films having different degrees of crystallinity and grain size and the performances have been studied.     

Preparation and characterization of RuO2 thin films

We report on the preparation and characterization of RuO₂ thin films by metal-organic chemical vapor deposition (MOCVD) method and reactive sputtering under various conditions. The Auger electron spectroscopy depth profile shows good compositional uniformity across the thickness of the films. As confirmed by X-ray investigations, the films crystallize with the correct rutile structure. The results of the electrical and optical studies of the films show a metallic character of the films deposited at substrate temperature higher than 100°C. The grain-boundary scattering model fits well for the films with an average grain size of about 12–50 nm. The red shift and broadening of the line width of the Raman peaks are analyzed by the spatial correlation model. The results of Raman investigation indicate that a nearly strain free and high-quality RuO₂ thin film could be deposited on a Si substrate.     

Optical and electrochromic properties of oxygen sputtered tungsten oxide (WO3) thin films

Thin films of tungsten oxide (WO₃) were deposited onto glass, ITO coated glass and silicon substrates by pulsed DC magnetron sputtering (in active arc suppression mode) of tungsten metal with pure oxygen as sputter gas. The films were deposited at various oxygen pressures in the range 1.5×10⁻²−5.2×10⁻² mbar. The influence of oxygen sputters gas pressure on the structural, optical and electrochromic properties of the WO₃ thin films has been investigated. All the films grown at various oxygen pressures were found to be amorphous and near stoichiometric. A high refractive index of 2.1 (at λ=550 nm) was obtained for the film deposited at a sputtering pressure of 5.2×10⁻² mbar and it decreases at lower oxygen sputter pressure. The maximum optical band gap of 3.14 eV was obtained for the film deposited at 3.1×10⁻² mbar, and it decreases with increasing sputter pressure. The decrease in band gap and increase in refractive index for the films deposited at 5.2×10⁻² mbar is attributed to the densification of films due to ‘negative ion effects’ in sputter deposition of highly oxygenated targets. The electrochromic studies were performed by protonic intercalation/de-intercalation in the films using 0.5 M HCl dissolved in distilled water as electrolyte. The films deposited at high oxygen pressure are found to exhibit better electrochromic properties with high optical modulation (75%), high coloration efficiency (CE) (141.0 cm²/C) and less switching time at λ=550 nm; the enhanced electrochromism in these films is attributed to their low film density, smaller particle size and larger thickness. However, the faster color/bleach dynamics is these films is ascribed to the large insertion/removal of protons, as evident from the contact potential measurements (CPD) using Kelvin probe. The work function of the films deposited at 1.5 and 5.2×10⁻² mbar are 4.41 and 4.30 eV, respectively.     

Microcrystallisation in Si:H: the effect of gas pressure in Ar-diluted SiH4 plasma

Using noble gas argon as a diluent of SiH₄ in RF glow discharge, undoped μc-Si:H thin films have been developed at a low power density of 30 mW/cm². It has been found that the gas pressure is a critical factor for the growth of μc-Si:H films. Undoped μc-Si:H films having σ_D10⁻⁶ S/cm and ΔE<0.57 eV have been obtained at and above a critical pressure of 0.8 Torr. When the RF power density is increased to 90 mW/cm², a more crystalline as well as highly conducting (σ_D10⁻⁴ S/cm) μc-Si:H film has been achieved at a deposition rate of 30 Å/min, which is much higher than that attained from H₂-diluted SiH₄ plasma, by conventional approach. The crystallinity of the films has been identified by the sharp Raman peak at 520 cm⁻¹ and a large number of micrograins in the TEM micrographs. The metastable state of Ar, denoted as Ar^*, plays the crucial role in inducing microcrystallisation by transferring its de-excitation energy at the surface of the growing film. A mechanism has been proposed to explain the dependence of the formation of μc-Si:H film on the working gas pressure in the plasma.     

Preparation of In2O3:F thin films grown by spray pyrolysis technique

Transparent conducting fluorine doped indium oxide (In₂O₃:F) thin films have been deposited on Corning 7059 glass substrates by the spray pyrolysis technique. The structural, electrical, and optical properties of these films were investigated as a function of substrate temperature. The X-ray diffraction pattern of the films deposited at lower substrate temperature (T_s=300 °C) showed no peaks of In₂O₃:F. In the useful range for deposition (i.e. 425–600 °C), the orientation of the films was predominantly [400]. For the 4500 Å thick In₂O₃:F deposited with an F content of 10-wt%, the minimum sheet resistance was 120 Ω and average transmission in the visible wavelength rang (400–700 nm) was 88%.     

Oxidative photoelectrochemical technology with Ti/TiO2 anodes

Rutile and anatase TiO₂ films have been grown on Ti plates by thermal (500–800°C) and anodic oxidation followed by thermal annealing (400–500°C), respectively. The photoelectrochemical efficiency of these photoanodes, evaluated by current density measurements in the photooxidation of 4-methoxybenzyl alcohol in deaerated CH₃CN, has been determined. The photocurrent efficiency increases with the thickness of the TiO₂ rutile film up to 1 μm (the most efficient thickness). At the wavelengths furnished by the irradiation apparatus similar thicknesses of anatase and rutile films show nearly the same efficiencies. Anodic bias produces similar relative increases of current intensity in both crystalline forms.     

Electrophoretic deposition of dense BaCe0.9Y0.1O3−x electrolyte thick-films on Ni-based anodes for intermediate temperature solid oxide fuel cells

Proton conducting BaCe_0.9Y_0.1O_3−x (BCY10) thick films are deposited on cermet anodes made of nickel–yttrium doped barium cerate using electrophoretic deposition (EPD) technique. BCY10 powders are prepared by the citrate–nitrate auto-combustion method and the cermet anodes are prepared by the evaporation and decomposition solution and suspension method. The EPD parameters are optimized and the deposition time is varied between 1 and 5 min to obtain films with different thicknesses. The anode substrates and electrolyte films are co-sintered at 1550 °C for 2 h to obtain a dense electrolyte film keeping a suitable porosity in the anode, with a single heating treatment. The samples are characterized by field emission scanning electron microscopy (FE-SEM) and energy dispersion spectroscopy (EDS). A prototype fuel cell is prepared depositing a composite La_0.8Sr_0.2Co_0.8Fe_0.2O₃ (LSCF)–BaCe_0.9Yb_0.1O_3−δ (10YbBC) cathode on the co-sintered half cell. Fuel cell tests that are performed at 650 °C on the prototype single cells show a maximum power density of 174 mW cm⁻².     

Optical analysis of the microstructure of a Mo back contact for Cu(In,Ga)Se2 solar cells and its effects on Mo film properties and Na diffusivity

The microstructures of molybdenum (Mo) thin films deposited at pressures from 3.3 to 10.3 mTorr were characterized, and the relationships between these microstructures and the properties of the films (residual stress and electrical resistivity) were investigated. In the low deposition pressure regime (region I, below 7 m Torr), the residual stress in the tensile direction increases with increasing pressure and the electrical resistivity increases gradually, but at high deposition pressures (region II, above 7 m Torr) the residual stress is reduced and the resistivity increases more steeply. These variations of the properties of the Mo films in the low pressure regime are due to the variation in grain size; the carrier mobility decreases due to increased grain boundary (GB) scattering and the tensile stress increases due to increased atomic attraction across the GBs. In contrast, the porosity of the Mo films increases significantly in the high pressure regime, as demonstrated with variable angle spectroscopic ellipsometry (VASE). Most of these pores are believed to be present along the grain boundaries of the Mo films, so their presence reduces the GB attraction and thus the tensile stress and enhances the carrier scattering. The high porosity of the Mo back contact was shown with secondary ion mass spectroscopy profiling to accelerate the Na diffusion from soda-lime glass into the Cu(In,Ga)Se₂ (CIGS) film.     

Influence of sputtering conditions on the solar and luminous optical properties of amorphous LixWoy thin films

Thin films of amorphous tungsten oxide were deposited by sputtering onto glass substrates coated by conductive indium–tin oxide. The films were sputtered at different oxygen-to-argon flow ratios with different pressure and power. Elastic recoil detection analysis determined the density and the stoichiometry. X-ray diffraction measurements showed that the films were amorphous. The films were electrochemically intercalated with lithium ions. At several intercalation levels of each film, the optical reflectance and transmittance were measured in the wavelength range 0.3–2.5 μm. We study the effect of various sputtering conditions on the coloration efficiency of the films and on the luminous and solar optical properties. The O₂/Ar ratio and the sputter pressure determine to a large extent the optical absorption. As-deposited sputtered tungsten oxide with sufficiently little oxygen exhibits an absorption peak similar to the case of lithium intercalation.