Microstructural change and interfacial reactions of Pt/Ti thin films on SiNx/Si during annealing in various ambients

The microstructural changes and interfacial reactions of Pt/Ti/SiN_x/Si during annealing were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), and Auger electron spectroscopy (AES). Pt/Ti thin films were deposited on SiN_x/Si substrates by a d.c. magnetron sputtering system. Pt/Ti/SiN_x/Si specimens were annealed at 600°C in an oxygen ambient or a vacuum. Annealing ambients strongly influenced the microstructural change in the Pt/Ti thin films. When the specimens were annealed in oxygen, the oxygen diffused into metal layers from the ambient and reacted with Ti to form the rutile phase. When the specimens were annealed in vacuum, Ti reacted with nitrogen which was dissociated from SiN_x to form TiN and reacted with Pt to form Pt₃Ti.     

Pulsed laser deposition of crystalline ZrC thin films

ZrC thin films were grown on Si substrates by the pulsed laser deposition (PLD) technique under various conditions. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), X-ray diffraction and reflectivity, spectroscopic ellipsometry, and four point probe measurements were used to characterize the properties of the deposited films. It has been found that crystalline films could be grown only by using laser fluences higher than 5 J/cm² and substrate temperatures in excess of 500 °C. For a fluence of 10 J/cm² and a substrate temperature of 700 °C, cubic ZrC films (a = 0.469 nm) exhibiting a (200)-texture were deposited under vacuum or low pressure C₂H₂ atmosphere. These films were smooth, with surface roughness values below 1.0 nm and mass densities around the tabulated value of 6.7 g/cm³. AES depth profiling investigations showed oxygen contamination around 7% in the bulk region. Despite the relatively high levels of oxygen contamination, the deposited ZrC films were very conductive. The use of a low C₂H₂ pressure atmosphere during deposition had a small beneficial effect on crystallinity and stoichiometry of the films.     

Microwave annealing for preparation of crystalline hydroxyapatite thin films

A sol was spun on single crystal silicon substrates at a spin-rate of 3000–5000 rpm followed by a low temperature cure to form a stable sol–gel/silicon structure. Good quality crystalline HA films of thickness ∼300–400 nm were obtained by annealing the sol–gel/Si structure in a conventional cavity applicator microwave system with a magnetron power of 1300 W, frequency of 2.45 GHz, and at a low processing temperature of 425 °C for annealing times ranging from 2–60 min. X-ray Diffraction and FTIR analysis confirmed that the crystalline quality of the thin films were comparable or better than those heat-treated under the same processing conditions (temperature and time) in a Rapid Thermal Annealing (RTA) system. The RBS data suggests a composition corresponding to stoichiometric hydroxyapatite Ca₁₀(PO₄)₆(OH)₂, the major inorganic component of bone. The results showed that the HA film thickness decreases with increasing sol spin-rate. The HA films showed good biocompatibility because little monocyte adhesion occurred and hence no inflammatory response was activated in vitro. The potential of microwave annealing for rapid and low temperature processing of good crystalline quality HA thin films derived from sol–gel is demonstrated.     

Effect of gas enhanced metal-semiconductor-metal UV photodetectors based on thermal annealing tungsten oxide thin film prepared by sol–gel method

Metal-semiconductor-metal ultraviolet photodetectors were fabricated on annealed tungsten oxide thin films which were synthesized by the sol–gel reaction. Surface morphology, microstructure, opto-electrical properties and crystal structure tests of the W₁₈O₄₉ thin films were examined by scanning electron microscopy, transmission, photoluminescence, and X-ray diffraction, respectively. The photo-responsivity of the photodetector shows a dependence on atmosphere environments. The photocurrent measured in a vacuum is about ~2 times higher than the illuminated photocurrent in air. The illumination conductance in a vacuum and in air increase by a factor of 100 compared to that in oxygen ambient. Furthermore, the obtained photoresponse curves showed significant changes in dark, under illumination, and during recovery for gas switching experiment. The solid-state process of electron-hole generation/recombination and surface effects of oxygen was discussed to explain the changes in the observed photoresponse.     

Ni2+掺杂ZnO薄膜及粉体的结构和发光性能研究

采用激光脉冲沉积法,用XeCl准分子激光器在Si (100)基片、真空和5Pa氧气气氛下制备了Ni2+(0.8％(原子分数))掺杂的呈六角纤锌矿结构的ZnO薄膜.氧气气氛下制备的薄膜沿(002)取向生长,表面比较平整,平均颗粒尺寸为80nm.真空条件下制备的薄膜出现Zn2SiO4杂相,平均颗粒尺寸为150nm.和真空条件下制备的薄膜相比,氧气气氛下制备的薄膜具有较强的ZnO本征发光,在425nm附近出现由于填隙Zn缺陷引起的较宽的蓝光发光带,并且在482nm处出现了由于氧空位和氧间隙间的转换引起的较强的蓝光发光峰,同时由于氧缺陷引起的449nm附近的蓝光发光峰强度明显降低.     

Auger electron spectroscopy and electron energy loss spectroscopy studies of the formation of silicon nitride by implanting low energy nitrogen ions into silicon

Thin (d ? 10 nm) films of almost stoichiometric silicon nitride were prepared by implanting nitrogen ions with energies below 5 keV into silicon with subsequent thermal annealing. A combination of Auger electron spectroscopy (AES) and electron energy loss spectroscopy (ELS) was used to determine the chemical composition and to investigate the chemical bonding states of the thin films. The spectra are in good agreement with those obtained for Si₃N₄ produced by chemical vapour deposition. The use of AES and electron ELS allowed the stepwise formation of the SiN bonds to be investigated for the first time, and hence further information about the electronic structure of Si₃N₄ was obtained. Depth-concentration profiles for nitrogen are presented.     

Benefits of carbon addition on the hydrogen absorption properties of Mg-based thin films grown by Pulsed Laser Deposition

Mg-Ni thin films were grown using Pulsed Laser Deposition. In situ optical changes from shiny metallic to transparent states were observed for films deposited in vacuum and under an Ar/H₂ gas mixture (93/7%), respectively. Optical changes were also achieved by ex situ hydrogenation under hydrogen gas pressure of 15 bars at 200 °C. However, after ex situ hydrogenation, the optical transmittance of the Mg-based hydrogenated thin films did not exceed 25%. Such limitation was attributed to oxygen contamination, as deduced by High Resolution Transmission Electron Microscopy observations, showing the co-existence of both Mg-based and MgO phases for as-deposited films. A significant decrease in oxygen contamination was successfully achieved with the addition of carbon, leading to the preparation of (Mg-based)-C_x (x < 20%) thin films showing a faster and easier hydrogenation.     

Growth and physicochemical characterization of CuAlTe2 films obtained by reaction, induced by annealing, between Cu/Al/Te/Al/Cu... Al/Cu/Al/Te layers sequentially deposited

CuAlTe₂ thin films have been synthesized by annealing under an argon flow a multilayer structure of thin Cu, Al and Te layers sequentially deposited by evaporation under vacuum. The films have been characterized by X-ray diffraction, microprobe analysis, photoelectron spectroscopy and Raman scattering. At the end of the process, the XRD spectra demonstrate that textured CuAlTe₂ films have been obtained with preferential orientation of the crystallites along the (112) direction. The Raman patterns are in good accordance with the reference. The XPS spectra show that the binding energies of the elements are in good agreement with bonds of CuAlTe₂. Even after a decrease of the oxygen contamination by improvement of the depositing process the oxygen present in the films is found to be about 12 at %. This revised version was published online in September 2006 with corrections to the Cover Date.     

Crystallization of amorphous Si thin films by the reaction of MoO3/Al nanoengineered thermite

In this work, we investigated a new crystallization method for amorphous silicon (a-Si) using a mixture of nano-energetic materials: molybdenum oxide and aluminum (MoO₃/Al). The purpose of using nano-energetic materials is to improve the performance of a-Si films with a self-propagating exothermic reaction over a period of microseconds without any substrate damage. The mixture of MoO₃/Al nanopowders was used for a thermite reaction for crystallization of a-Si thin films.Characterization results showed that a-Si thin films were successfully crystallized to poly-Si as evidenced by a Raman peak near 519 cm^− 1. The crystalline volume fraction of poly-Si after the nanoengineered thermite reaction was about 94.7% and poly-Si grains was uniformly distributed with an average grain size of around 40-50 nm. These results indicate that high quality poly-Si thin films were successfully prepared on the substrate.     

Effect of vacuum annealing on the phase composition of In/SnO/Si, In/SnO2/Si, and Sn/In2O3/Si heterostructures

The chemical interaction between indium and thin SnO and SnO₂ films and between tin and thin In₂O₃ films during vacuum annealing was studied. The metallic films were deposited onto single-crystal silicon substrates by magnetron sputtering, the SnO and SnO₂ films were produced by heat-treating the Sn film in flowing oxygen at 673 and 873 K, respectively, and the In₂O₃ film was produced by heat-treating the In film at 573 K. The results indicate that annealing of the In/SnO/Si and In/SnO₂/Si heterostructures in vacuum (residual pressure of 0.33 × 10^?2 Pa) at 773 K gives rise to the reduction of Sn and oxidation of In, whereas annealing of Sn/In₂O₃/Si causes partial tin substitution for indium in the cubic indium oxide lattice.     

Characterization of low pressure chemically vapour- deposited thin silicon nitride films

Silicon nitride films prepared on silicon by low pressure chemical vapour deposition (LPCVD) were characterized by electrical measurements (current-voltage and capacitance-voltage), Auger electron spectroscopy (AES) and reflection high energy electron diffraction (RHEED). The contact current versus contact field characteristics were interpreted in terms of the Fowler-Nordheim tunnelling of holes from silicon into silicon nitride, with the field of charged traps and the effect of changing the triangular shape of the barrier under steady state conditions taken into account and on the assumption of a Poole-Frenkel detrapping mechanism. AES data show that the LPCVD process yields stoichiometric Si₃N₄ films. RHEED data shows that films of thickness more than 10 nm are amorphous. Some crystalline structures of Si₃N₄ and SiO₂ are observed for thicknesses of less than 10 nm.     

Growth of zinc peroxide (ZnO2) and zinc oxide (ZnO) thin films by the successive ionic layer adsorption and reaction – SILAR – technique

Zinc peroxide, ZnO₂, thin films were grown by successive ionic layer adsorption and reaction (SILAR) technique at room temperature and normal pressure. The thin films were grown on glass, quartz, silicon, on poly(vinyl chloride) and polycarbonate substrates. The precursors used for ZnO₂ films were diluted aqueous solutions of ZnCl₂ complexed with ethylenediamine for cation and H₂O₂ for anion constituent of the film. The zinc peroxide film could be decomposed to zinc oxide by annealing in air or in vacuum. The as-grown films were polycrystalline, or amorphous and the annealed films were amorphous on all substrate materials. According to scanning electron microscopy images the films were uniform and homogeneous. The films were also characterized by UV spectroscopy.     

铝诱导晶化真空蒸镀多晶硅薄膜的研究

采用真空蒸镀的方法在玻璃衬底上沉积1层非晶硅薄膜,再通过铝诱导晶化的方法制备出晶粒分布较均匀、晶粒尺寸0.5～5μm、晶化率达到89%的多晶硅薄膜。研究了衬底距离、衬底温度、退火温度对薄膜表面形貌、晶粒尺寸和分布及晶化率的影响。结果表明适中的衬底距离下得到的薄膜晶粒分布均匀,表面平整度好,薄膜厚度较大。薄膜的晶化率随着衬底温度和退火温度的提高而增大;随着退火温度的进一步提高,薄膜的晶化率达到最大值然后降低。     

Formation of a silicate layer between lead oxide and a silicon-wafer surface during heat treatment

PbO thin films were deposited on a silicon substrate by plasma-enhanced chemical vapour deposition (PECVD) using Pb(C₂H₅)₄ and oxygen at 250°C. The interdiffusion reaction phenomena between the PbO thin film and the silicon substrate during heat treatments were investigated in a horizontal furnace in the temperature range between 350 and 650°C under a nitrogen ambient for 1 h. The PECVD PbO film deposited on the silicon substrate at 250°C, was amorphous and contained carbon-related contaminants which could almost be removed by heat treatment at 350°C. The PbO on the silicon substrate initially participated in the interdiffusion reaction in the temperature range between 400 and 450°C. This produced a silicate layer containing lead components. The lead content in the film varied with the depth of film and heat-treatment temperature. Metallic lead was observed as a cluster in the specimen heated at 550°C. This cluster was produced by the agglomeration of metallic lead originating from PbO decomposition. The oxygen source for silicate formation was not ambient oxygen coming from the decomposition of Pb–O bonding. The metallic lead clusters dissolved as weakly bound metallic lead or as an unbound nanosized metal particle in the silicate layer at 650°C. This revised version was published online in November 2006 with corrections to the Cover Date.     

Confined palladium colloids in mesoporous frameworks for carbon nanotube growth

Palladium colloidal nanoparticles with an average size of approximately 2.4 nm have been incorporated into mesoporous inorganic thin films following a multistep approach. This involves the deposition of mesoporous titania thin films with a thickness of 200 nm by spin-coating on titanium plates with a superhydrophilic titania outer layer and activation by calcination in a vacuum furnace at 573 K. Nanoparticles have been confined within the porous titania network by dip-coating noble metal suspensions onto these mesoporous thin films. Finally, the resulting nanoconfined systems were used as substrates for the growth of oriented carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition at 923 K in order to enhance their surface area. These CNTs were tested in the hydrogenation of phenylacetylene by hydrogen in a batch reactor. The initial reaction rate observed on a CNT/TiO₂ structured catalyst was considerably higher than that on 1 wt% Pd/TiO₂ thin films.     

Effect of oxygen on the surface morphology of CuGaS2 thin films

Since the effect of oxygen is very significant during the heat treatment of the thin films, we study the effect of this during the annealing of CuGaS₂ thin films by two different types. In this study, CuGaS₂ thin films were deposited by vacuum thermal evaporation of CuGaS₂ powder on heated glass substrates at 200 °C submitted to a thermal gradient. The films are annealed in air and under nitrogen atmosphere at 400 °C for 2 h. In order to improve our understanding of the influence of oxygen during two annealing types on device performance, we have investigated our CuGaS₂ material by X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX) and spectrophotometry. A correlation was established between the surface roughness, growth morphology and optical properties, of the annealed CuGaS₂ thin films. It was found that annealing of CuGaS₂ film in nitrogen atmosphere leads to a decrease of the mean grain size and to an evolution of a (112) preferred film orientation. Annealing in air results in the growth of oxide phases such as CuO and modifies the films structure and their surface morphology.     

Structural changes in tungsten wire and their effect on the properties of hydrogenated nanocrystalline cubic silicon carbide thin films

We investigated the structural changes in tungsten wire heated to 1800 °C in SiH₄/CH₄/H₂/N₂ atmosphere and the effect of the aging tungsten wire on the properties of N-doped hydrogenated nanocrystalline cubic silicon carbide (nc-3C-SiC:H) thin films. The aged tungsten wire had two parts: hot parts of the middle of the wire and relatively cold parts connected to clamps. Tungsten carbide (W₂C) layer formed in the wire of the hot parts, while crystalline silicon and cubic silicon carbide (c-Si/3C-SiC) layer deposited on the wire of the cold parts. N-doped nc-3C-SiC:H thin films were deposited for 5 min (thickness: ~ 30 nm) after the tungsten wire was heated under the same condition as during the film deposition for given times (exposure time). No changes in the structural, electrical and optical properties of the nc-3C-SiC:H thin films were observed for the exposure time up to 450 min.     

Growth parameter effect in superconducting YBa2Cu4O8 thin films by d.c. magnetron sputtering

High- T _c YBa₂Cu₄O₈ (124) thin films have been made by d.c. magnetron sputtering deposition on (100) MgO substrates. The effect of several processing variables, including the ratio of oxygen to argon, total pressure, and substrate temperature, on the superconducting properties of the thin films, were systematically investigated. The as-prepared films annealed in flowing oxygen at 800°C for 4 h under ambient pressure obtained nearly phase-pure 124 and exhibited superconducting onset transition at 75 K.     

FT-IR and UV-Vis-NIR characterisation of pure and mixed MoO3 and WO3 thin films

We report a spectroscopic characterisation of MoO₃, WO₃ and a MoO₃-WO₃ mixed oxide thin films deposited on alumina and silicon substrates. Absorbance FT-IR and diffuse reflectance UV-Vis-NIR spectra were recorded after treatments in vacuum and after interaction with O₂, NO₂/O₂, CO/O₂ or pure CO at increasing temperatures up to 673 K. For all the films, reducing treatments (vacuum, CO or CO/O₂) cause the increase of a variety of broad absorptions both in the Vis-NIR and medium IR regions. These absorptions decrease in intensity after contact with oxidising atmospheres (O₂ or NO₂/O₂), so that they are all assignable to electronic transitions due to the presence of a variety of donor levels related to oxygen defects.     

Real-time investigation on photocatalytic oxidation of gaseous methanol with nanocrystalline WO3-TiO2 composite films

Here we report on our investigation on photocatalytic oxidation (PCO) of gaseous methanol with WO₃-TiO₂ composite films. WO₃ and WO₃-TiO₂ composite thin films were prepared by drop casting method. PCO of gaseous methanol and hydrogen generation process on platinum loaded WO₃-TiO₂ composite thin films in high vacuum were investigated using a home-made reactor with a six-channel quadrupole mass spectrometer at real-time scale under UVA (300-400 nm) light illumination.In the case of Pt loaded WO₃ thin films, PCO of gaseous methanol proceeds through intermediates viz. formaldehyde, CO and finally to CO₂ and H₂. PCO of gaseous methanol occurs via direct hole transfer over Pt loaded WO₃ thin films. On the other hand, PCO of gaseous methanol over Pt loaded WO₃-TiO₂ composite thin films proceeds with competitive direct and indirect hole transfer reactions. Our real-time analysis of gas phase photocatalysis realized the identification of direct and indirect hole transfer processes and the reaction intermediates thereof.