Analysis of semiconductor thin films deposited using a hollow cathode plasma torch

The hollow cathode plasma torch has been used for several years. One of the major applications has been the deposition of dielectric thin films. However, this technique has also been used to deposit metals where high-speed deposition is needed. It has proven to be useful in deposition of coatings onto the inside of substrates of complex shape, high-speed etching, and deposition of thin films at atmospheric pressure. In recent years, we have adapted the technique to deposit high-quality amorphous and polycrystalline semiconducting films. A large variety of measurement techniques have been employed to determine the film properties and the results are reported here.     

Thin films of a-SiGe:H with device quality properties prepared by a novel hollow cathode deposition technique

Using a novel hollow cathode plasma-jet reactive sputtering system in which an intense plasma, ignited in an Ar/H₂ flow, is directed through silicon and germanium nozzles, a series of a-SiGe:H thin films have been prepared on silicon and on glass substrates. These films have been optically characterized by infrared (IR) spectroscopy, surface Raman spectroscopy and spectroscopic ellipsometry (335–1000 nm). Total hydrogen concentrations, as determined by FTIR, varied with deposition conditions and ranged from 2.5×10²¹ to 1.6×10²² atom cm⁻³ and correlated with secondary ion mass spectrometry (SIMS) elemental analyses to within 10%. The ellipsometric spectra of the films have been fitted with a modified Tauc–Lorentz model for the determination of film properties, including thickness (ranging from 400 to 1100 nm) along with film uniformity and surface roughness. Conductivity measurements in the dark and under simulated AM1 solar illumination have indicated that the films grown exhibit device-quality properties. The light-to-dark conductivity ratio has consistently been greater than 1000 for films with bandgaps down to 1.3 eV. Relationships between deposition parameters, light-and-dark conductivity properties, and chemical structural features are discussed.     

Optical characterization of a-C:N thin films deposited by RF sputtering

In this work we present the main results of the optical properties study of amorphous carbon nitride (a-C:N) thin films prepared by reactive radio frequency (RF) sputtering. The a-C:N films were deposited, at room temperature, onto glass substrates, from a graphite target, in a pure nitrogen plasma. During the deposition, the pressure of nitrogen and the power density were maintained at 10⁻² mbar and 0.79 W cm⁻², respectively. Optical properties of these films were deduced from optical transmission spectra in the ultraviolet–visible–near infrared (UV–Vis–NIR) range. The refractive index follows well the Cauchy law with an extrapolated value of 1.68 in the far IR region. The optical band gap of the a-C:N films is about 1.2 eV. This value is relatively high in comparison with that of amorphous carbon films (0.8 eV) obtained in similar conditions. The incorporation of nitrogen in the amorphous carbon network leads to an increase of the optical band gap.     

Ab initio study of hydrogen storage on metal-decorated GeC monolayers

Bidimensional nanostructures have been proposed as hydrogen-storage systems owing to their large surface-to-volume ratios. Germanium carbide monolayers (GeC-MLs) can offer attractive opportunities for H₂ adsorption compared to graphene. However, this possibility has not been explored in detail. In this work, the adsorption of H₂ molecules on GeC-MLs decorated with alkali metal (AM) and alkaline earth metal (AEM) adatoms was investigated using the density functional theory. Results showed that the AM adatoms were chemisorbed on the GeC-ML, whereas AEM adatoms were physisorbed. The H₂ molecules presented negligible adsorption energies on the weakly adsorbed AEM adatoms. Conversely, the AM adatoms improved the H₂ adsorption, possibly due to a large charge transfer from the adatoms to the GeC-ML. The potassium-decorated GeC-ML exhibited the most optimal H₂ storage capacity, adsorbing up to six molecules and with a lower possibility of forming metal clusters than the other studied cases. These results may aid in the development of new efficient hydrogen-storage materials.     

Some physical properties of ZnO thin films prepared by RF sputtering technique

ZnO thin films were deposited with RF sputtering using pure Zn target. In order to generate oxidation process of Zn, Ar:O₂ gas mixing in (9:1), (7:3) and (5:5) ratios of Ar:O₂ was used. To characterize ZnO thin films thickness and transparency were measured using optical method, and refractive index and band gap energies were calculated. Electrical conductivity of the ZnO thin films was also determined. AFM images were used to determine surface morphology of produced ZnO thin films.     

The influence of the nitrogen-ion flux on structure and ionic conductivity of vapor deposited lithium phosphorus oxynitride films

Thin films of lithium phosphorus oxynitride (Lipon) have been grown using a plasma-assisted, directed vapor deposition (PA-DVD) technique. In this approach, a high voltage electron beam is used to vaporize a Li₃PO₄ source and a supersonic, nitrogen-doped, helium gas jet then transport the vapor towards a substrate. A hollow cathode technique was then used to create an argon plasma just above the substrate. This sufficiently ionized the nitrogen in the gas jet to allow its incorporation into the Li₃PO₄ film reactively forming lithium phosphorus oxynitride. Increasing the nitrogen flux in the gas jet also increased the deposition rate from 113 to 178 nm min⁻¹ for the deposition conditions used here, significantly reduced the pore volume fraction in the films and increased the N/P ratio from 0 to 0.75 as the gas jet nitrogen flux was increased from zero to 4.3 × 10¹⁸ molecules cm⁻² s⁻¹. Using substrate rotation, pore and columnar-free dense Lipon films could be grown by this method. The Li-ion conductivity increased from 3.7 × 10⁻⁹ to 5.2 × 10⁻⁷ S cm⁻¹ as the nitrogen concentration was increased from zero to 2.1 × 10¹⁸ molecules cm⁻² s⁻¹ and was correlated with an increase in the film's Li/P ratio. An optimum nitrogen flux has been identified. As the nitrogen flux was increased above this value, the Lipon films suffered lithium loss and partial crystallization, resulting in a decrease in their Li-ion conductivity.     

空心阴极气流溅射法快速沉积具有高活性光催化作用的TiO_2薄膜(下)

<正>图4a和4b分别为在UV-近红外光谱,刚沉积和经后退火工艺两种情况下的Ti O2膜。以上两种情况在可见光区域透射比几乎相同,与后退火无关。O2流量为10~50 sccm时,沉积的Ti O2膜在可见光区域具有的高透射比约为0.70。图5a为Ti O2膜在暗处停留60 min后,相应乙醛(CH3CHO)浓度与UV照射时间的关系。O2流量为10 sccm时,沉积的Ti O2膜相应CH3CHO     

Optical properties of TiO2 thin films deposited by DC sputtering and their photocatalytic performance in photoinduced process

TiO₂ thin films were deposited by DC Sputtering varying the deposit time. These films were characterized by XRD, AFM, photoluminescence, UV–Vis, ellipsometry and XPS. The optical properties of TiO₂ thin films with different thickness, influenced their photocatalytic behavior in two photoinduced process. When TiO₂ thin films were irradiated with a UV light, midgap states were generated and the electrons were placed in lower energies than its band gap, favoring the photocatalytic hydrogen production and CO₂ photoreduction. From PL technique analyses it was observed that electrons occupied midgap states between the bands, with lower energies than the band gap. With these results it was possible to propose an energy diagram in order to correlate with photoinduced processes results. The presence of Ti³⁺ species was reconfirmed by means of XPS analyses. These species could be found in the midgap states, generated by the interaction between the UV irradiation and the film surface, which contributed to the photocatalytic activity of the films. The hydrogen production was similar for all the thin films studied (33–35 μmol) associated to the presence of similar energy midgap states. In the case of CO₂ photoreduction, all films produced CH₂O (8951 and 6252 μmol/g) and the films with a thickness of 330 and 420 nm generated CH₃OH (970 and 292 μmol/g). The extinction coefficient confirmed the XRD results for the film with greatest deposited time, which exhibited the highest crystallinity. All photocatalytic results did not show any dependence with the thin film thickness.     

Electrical and optical properties of Al doped cadmium oxide thin films deposited by radio frequency magnetron sputtering

Cadmium oxide thin films with different percentages of aluminum doping have been synthesized via radio frequency magnetron sputtering technique. Thin films were deposited on glass and silicon substrates with different percentages of aluminum at a substrate temperature of 573 K and pressure of 0.1 mbar in Ar+O₂ atmosphere. The deposited films were characterized by studying their structural, electrical and optical properties. The X-ray diffraction pattern revealed good crystallinity with preferred (1 1 1) orientation in the films. Aluminum doping in CdO thin films were confirmed by X-ray photoelectron spectroscopic studies and actual doping percentages were also measured from it. The optical band gap was found to decrease first and then increase with increasing percentages of aluminum concentrations. The electrical conductivity was found to increase with increase of aluminum doping concentration up to 5% but for higher doping concentration (>5%) the conductivity was found to decrease.     

Structural, compositional, and optical properties of electrochemically deposited stoichiometric CdSe thin films from non-aqueous bath

In the recent years, cadmium chalcogenide compounds have been extensively investigated because of their potential applications in solar energy conversion. Thin films of CdSe have been deposited onto the stainless steel and fluorine doped tin oxide (FTO) coated glass substrates using simple and inexpensive electrodeposition technique. The non-aqueous solvent ethylene glycol (CH₂OHCH₂OH) containing precursors of Cd and Se with ethylenediaminetetraacetic acid (EDTA) tetra sodium salt as a complexing agent is used to obtain stoichiometric deposits. Deposition potential was estimated from polarization curves and other preparative parameters such as bath temperature and concentration of solution were optimized. X-ray diffraction (XRD) analysis reveals that the films are polycrystalline with cubic structure. PEC study shows the CdSe films are photoactive. Optical absorption study shows the presence of direct transition with band gap energy 1.72 eV. The energy dispersive analysis by X-rays (EDAX) reveals that the substrate is well covered with large number of grains indicating compact structure. The average ratio of the atomic percentage of Cd:Se is 50.31:49.69, showing that the deposited films are almost stoichiometric.     

Properties of fluorine doped ZnO thin films deposited by magnetron sputtering

Fluorine doped ZnO (FZO) films were deposited on Corning glass by radio frequency (rf) magnetron sputtering of pure ZnO target in CF₄ containing gas mixtures, and the compositional, electrical, optical, and structural properties of the as-grown films as well as the vacuum-annealed films were investigated. The fluorine content in FZO films increased with increasing CF₄ content in sputter gas. FZO films deposited at elevated temperature of 150 °C had considerably lower fluorine content and showed a poorer electrical properties than the films deposited at room temperature. Despite high fluorine contents in the films, for all the FZO films, the carrier concentration remained below 2×10²⁰ cm⁻³, leading to fairly low doping efficiency level. Vacuum-annealing of the FZO films deposited at room temperature resulted in substantial increase of Hall mobilities, reaching as high as 43 cm²/Vs. This was attributed partly to the removing of oxygen vacancies and/or the forming chemical bonds with interstitial zinc atoms by fluorine interstitials and partly to the passivation effect of excess fluorine atoms by filling in the dangling bonds at the grain boundaries. For all the films with thickness of around 300 nm, the optical transmissions in visible were higher than 80%, and increased with increasing fluorine content up to 85% for the film with highest fluorine content.     

Synthesis and characterization of hollow metal oxide micro-tubes using a biomaterial template

Various hollow metal oxide micro-tubes (SnO₂, ZrO₂, ZnO, and NiO) were prepared by a simple impregnation method using Ceiba pentandra (L.) Gaertn. (kapok) as a biomaterial template. Calcination heat treatment was successfully used for the removal of the kapok template. Field emission scanning electron microscopy (FE-SEM) was used to study the uniform morphology of the hollow metal oxide micro-tubes, which had an average diameter of 15–20 μm. The hollow metal oxide micro-tubes were further characterized by thermal gravity analysis (TGA), X-ray diffraction (XRD), and X-ray photo-electron spectroscopy (XPS). This synthesis method provides a new facile route for the fabrication of hollow metal oxide micro-tubes.     

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.     

Characteristics of zirconium-doped indium tin oxide thin films deposited by magnetron sputtering

ITO:Zr thin films were deposited on glass substrates by co-sputtering with an ITO target and a zirconium target. The experiment parameters such as substrate temperature and oxygen flow rate have an important influence on the properties of ITO:Zr thin films. XRD spectra and AFM reveal the crystalline structure and surface roughness of ITO:Zr thin films. Better optical–electrical characteristics of the films can be achieved at low substrate temperatures, and the increasing substrate temperature remarkably improves the optical–electrical characteristics of the films. Certain oxygen flow rates can enhance the properties of ITO:Zr thin films, but excessive oxygen can worsen the optical–electrical characteristics. The obvious Burstin–Moss effect can be revealed by the transmittance spectra with different parameters, and the direct transition models show the change of optical band gap. As the optimum parameters are selected, ITO:Zr thin films with sheet resistance of 10–20 Ω/sq and optical transmittance of beyond 85% (including glass substrates) can be obtained.     

Effects of sputtering pressure on properties of Al doped ZnO thin films dynamically deposited by rf magnetron sputtering

Abstract

Aluminium doped zinc oxide (AZO) films were dynamically deposited by rf magnetron sputtering under various sputtering pressures in the range of 0·3–2·0 Pa. The effect of the Ar sputtering pressure on the structural, electrical and optical properties of the AZO films was systematically investigated by X-ray diffractometry, scanning electron microscope, four-point probe measurement and UV–vis spectrophotometer. As the sputtering pressures decrease, the crystallite sizes of the films became larger, while their deposition rate turns higher. Under the condition of lower sputtering pressures, a decrease in the resistivity was observed due to an increase in carrier concentration. The AZO film deposited at 0·5 Pa in the dynamic mode has shown the lowest resistivity of 9·5×10^?4 Ω cm. This work was performed in a dynamic deposition system in order to produce a large area of AZO films, which is more important in practical fields to improve productivity.     

Enhancement of cell performance using a gadolinium strontium cobaltite coated cathode in molten carbonate fuel cells

To enhance cathode performance, gadolinium strontium cobaltite (Gd_0.6Sr_0.4CoO₃, GSC) is coated onto a porous Ni plate by a vacuum suction method, for use as the cathode in molten carbonate fuel cells (MCFCs). GSC is a mixed ionic and electronic conductor (MIEC) material, and thus has high electronic conductivity and catalytic activity at low temperatures. The electrode performance of the GSC-coated cathode is examined by various methods, such as single cell operation and electrochemical impedance spectroscopy (EIS). At 600 °C, the performance of a single cell using a GSC-coated cathode is 0.813 V. This result is very surprising given that the performance of an uncoated conventional cathode is 0.69 V. Impedance analysis confirms that a dramatic decrease in the charge transfer resistance after GSC coating is primarily responsible for the cell enhancement at low temperature. The reaction orders for O₂ and CO₂ at uncoated and GSC-coated cathodes are also examined via a symmetric cell test, to identify the reaction mechanism of oxygen reduction. The peroxide mechanism, which is known to be a fast reaction, is predominant for the GSC-coated cathode at low temperatures, whereas the superoxide mechanism is predominant for the uncoated cathode.     

Electrochemical characterizations of multi-layer and composite silicon-germanium anodes for Li-ion batteries using magnetron sputtering

To improve the electrochemical performance of Si film, we investigate the addition of two film forms of Ge. Si/Ge multi-layered and Si-Ge composite electrodes that are fabricated by magnetron sputtering onto Cu current collector substrates are investigated. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and extended X-ray absorption fine structure (EXAFS) are employed to analyze the structures of the Si-Ge electrodes. When used as an anode electrode for a lithium ion battery, the first discharge capacity of a Si/Ge 150 multi-layer cell with a ratio of Si 15 nm/Ge 3 nm is 2099 mAh g⁻¹ between 1.1 and 0.01 V. A stable reversible capacity of 1559 mAh g⁻¹ is maintained after 100 cycles with a capacity retention rate of 74.25%. Additionally, the Si_0.84Ge_0.16 composite has an initial discharge capacity of 1915 mAh g⁻¹ and a capacity retention of 74.25%. In full cell tests of Si-Ge electrodes, the Si_0.84Ge_0.16/LiCoO₂ cell delivers a specific capacity of approximatly 160 mAh g⁻¹ and a capacity retention of 52.4% after 100 cycles. The results reveal that these two systems of sputtered Si-Ge electrodes can be used as anodes in lithium ion batteries with higher energy densities.     

Raman and XPS characterization of vanadium oxide thin films deposited by reactive RF sputtering

In this paper we report on Raman and XPS characterization of vanadium oxide thin films deposited by RF-sputtering. The samples were deposited by using a vanadium target in different oxygen fluxes, so that the stoichiometry (O/V ratio) of the oxide was varied. Several physical parameters of the films indicate a strong structural difference between the sample deposited at lower oxygen flux (1 scc m) and those obtained with higher flux (from 1.25 to 9 scc m). The increase of O/V ratio corresponds to a lower crystallinity of the thin films as indicated by the initial lowering and the final disappearance of the characteristic Raman mode of V₂O₅ (crystal) at about 140 cm⁻¹. For the highest flux samples new broad bands develop, typical of amorphous materials, both in polarized as well as in depolarized Raman spectra.     

High utilization of Pt nanocatalysts fabricated using a high-pressure sputtering technique

Pt nanocatalysts formed on a gas diffusion layer substrate for use in proton exchange membrane fuel cells were fabricated by using a high-pressure sputtering technique in a gaseous mixture of Ar and He. Rather than the dense film deposited by conventional sputtering techniques, the resulting structure was comprised of a porous Pt nanocatalyst layer with an average particle size of 8.9 nm. The porous Pt nanocatalysts were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray absorption near edge spectroscopy. Compared with the dense Pt catalyst layer, the electrochemical activated surface of the porous Pt nanocatalyst layer, measured using cyclic voltammetry, was enhanced about 250%. Polarization characteristics of the membrane electrode assembly, which utilized the porous Pt nanocatalyst layer in the proton exchange membrane fuel cells, showed that the maximum power density per unit area increased with an increase in the sputtering pressure. The high performance of Pt nanocatalysts fabricated at a sputtering pressure of 200 mTorr (Ar/He = 1) was due to miniaturization of the Pt particles and formation of the porous catalyst layer.     

Structural and optical properties of hot wall deposited CdSe thin films

Cadmium selenide (CdSe) films were prepared by hot wall deposition technique using optimized tube length under a vacuum of 6 mPa on to well-cleaned glass and ITO substrates. The X-ray diffraction analysis revealed that the films are polycrystalline in nature for lower thickness and at lower substrate temperatures, but with increasing thickness and increasing substrate temperature a more preferred orientation along (0 0 2) direction was observed. The crystallite size (D), dislocation density (δ) and strain () were calculated. An analysis of optical measurements revealed a sharp absorption around 700 nm and a direct allowed transition. The band gap was found to be around 1.7 eV. The effect of thickness and substrate temperature on the fundamental optical parameters like band gap, refractive index and extinction coefficient are studied.