Raman investigation of rutile RuO2

We report the first Raman investigation of the rutile material RuO₂. The four allowed first-order Raman-active phonon modes have been observed and classified. Comparison is made with other rutile materials.     

Characterization of AgInS2 thin films prepared by vacuum evaporation

We characterized AgInS₂ thin films prepared by vacuum evaporation. In the case of thin films annealed at 400 °C, diffraction peaks were observed only for the chalcopyrite AgInS₂ phase. The chemical composition of the thin films annealed at 400 °C was 26.5 at% Ag, 23.8 at% In, and 49.7 at% S. PL spectra of the AgInS₂ thin films at 10.7 K showed peaks at 1.70, 1.80, and 1.83 eV. The PL peak at1.80 eV was attributed to sulfur deficiency.     

Investigation of structural phase transition in polycrystalline SrTiO3 thin films by Raman spectroscopy

Polycrystalline SrTiO₃ thin films were prepared by pulsed laser deposition technique. The phonon properties and structural phase transition were studied by Raman spectroscopy. The first-order Raman scattering, which is forbidden in SrTiO₃ single crystal, has been observed in the films, due to the structural distortion caused by strain effect and oxygen vacancies. The Fano-type line shape of TO₂ phonon reveals the existence of polar microregions in the STO thin films. The evolution of TO₂ and TO₃ phonons with temperature shows the occurrence of a structural phase transition at 120 K related to the formation of polar macroregions in the films.     

Raman study of WO3 thin films

The influence of substrates, thermal treatment and coloration-bleaching cycles on the structure of WO₃ thin films used in electrochromic devices has been investigated by Raman microscopy. Films (2000–8000 Å) were prepared by RF sputtering from a metallic tungsten target at a constant pressure (5 × 10^?3Torr) of pure oxygen or a mixture of Ar20% O₂. They are amorphous, transparent and electrochromic. Thermal treatment at 360°C produces crystallization. Modifications of the WO₃ framework are also induced by coloration-bleaching cycles.     

Characterization of electrodeposited Bi2S3 thin films by holographic interferometry

Optical non destructive evaluation methods, using lasers as the object illumination source, include holographic interferometry. It is widely used to measure stress, strain, and vibration in engineering structures. Double exposure holographic interferometry (DEHI) technique is used to determine thickness and stress of electrodeposited bismuth trisulphide (Bi₂S₃) thin films for various deposition times. The same is tested for other concentration of the precursors. It is observed that, increase in deposition time, increases thickness of thin film but decreases stress to the substrate. The structural, optical and surface wettability properties of the as deposited films have been studied using X-ray diffraction (XRD), optical absorption and contact angle measurement, respectively. The X-ray diffraction study reveals that the films are polycrystalline with orthorhombic crystal structure. Optical absorption study shows the presence of direct transition with band bap 1.78 eV. The water contact angle measurement shows hydrophobic nature of Bi₂S₃ thin film surface.     

Raman microprobe spectroscopy measurements of residual stress distribution along blisters in Cr2O3 thin films

Raman spectroscopy has been used to characterise the buckling phenomenon of Cr₂O₃ films obtained by oxidation in air at 900 °C of Ni33 at%Cr. The observed circular blisters are described by measuring the radius from the optical top view, the profile via an autofocus device and the residual stress in each point of the chromia film: far away from the centre of the blister, in the vicinity and across the blister. The subsequent spalls are related to the morphology of the blisters and to the stress.     

Electronic structure of CeAl2 thin films studied by X-ray absorption spectroscopy

We report X-ray absorption near edge structures (XANES) study of CeAl₂ thin films of various thicknesses, 40-120 nm, at Al K- and Ce L₃-edges. The threshold of the absorption features at the Al K-edge shifts to the higher photon energy side as film thickness decreases, implying a decreased in Al p-orbital charges. On the other hand, from Ce L₃-edge spectra, we observed a decrease in the 5d4f occupancy as the surface-to-bulk ratio increases. The valence of Ce in these thin films, as revealed by the Ce L₃-edge spectral results, is mainly trivalent. From a more detailed analysis we found a small amount of Ce⁴⁺ contribution, which increases with decreasing film thickness. Our results indicate that the surface-to-bulk ratio is the key factor which affects the electronic structure of CeAl₂ thin films. The above observations also suggest that charge transfer from Al to Ce is associated with the decrease of the film thickness.     

Chemical synthesis of nano-porous ruthenium oxide (RuO2) thin films for supercapacitor application

Ruthenium oxide (RuO₂) thin films have been prepared using single step chemical method containing Ru(III) Cl₃ solution in an aqueous medium at low temperature. The structural, morphological and optical properties have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and optical absorption technique. The XRD study revealed the formation of amorphous RuO₂ thin film. The surface examination by SEM showed formation of nano-porous material on the substrate. The TEM study revealed the formation of nanostructured material. The optical absorption studies showed the presence of direct band transition with band gap equal to 2.2 eV. The RuO₂ has proved its applicability in supercapacitor showing 50 F/g specific capacitance in 0.5 M H₂SO₄ at 20 mV/s scan rate.     

Surface composition of Fe-Al2O3 granular thin films by X-ray photoemission spectroscopy

X-ray photoemission Spectroscopy (XPS) results are presented which have given a direct insight into the surface composition of Fe-Al₂ O₃ “granular” thin films consisting of fine iron particles (φ ~ 40–150 Å) dispersed in an insulating alumina matrix. The data are mainly discussed in relation to: (i) the bulk iron content in the sample, (ii) the sample preparation procedure (e.g., by rotation of the sample target) and (iii) the mean iron particle size.At the surface, the iron is in a fully oxidized 3⁺ state within an alumina-rich partly hydrated region. Depth analysis, achieved by an Ar⁺ etching procedure, provides evidence of metallic iron and iron aluminate forms. In general, the metallic iron percentage increases with depth and with increasing iron bulk content.Good agreement is found between X-ray photoemission spectroscopy and Mössbauer Spectroscopy data. Fe²⁺ aluminate forms, which indicate an interaction between the metal particle and the alumina matrix, show increasing percentages with decreasing mean particle sizes.Particular attention is paid to evaluating the accuracy of XPS quantitative results, obtained by use of a first-principles model, and to assessing the importance of the artefacts associated with the Ar⁺ etching procedure.     

Single crystal RuO2/Ti and RuO2/TiO2 interface: LEED, Auger and XPS study

The interactions at the evolving RuO₂/titanium interface have been studied by LEED, AES and XPS. Titanium films of up to 5 monolayers were evaporated onto well ordered and ion sputtered ruthenium dioxide crystal surfaces of (110) and (100) orientation. Stabilization of the surface oxygen content under thermal treatment in UHV (up to 600°C) with increasing titanium coverage was established. After extended (up to 4 h) annealing in O₂ at 600°C an epitaxial ordering of TiO₂ on RuO₂(110) was observed. The (1 × 1) LEED patterns from the epitaxial layer exhibit a reduced background level when compared to the RuO₂ substrate itself. These findings are correlated with the XPS data and are interpreted in connection with the disappearance of the defect RuO₂ phase in the surface layer of the RuO₂. The appearance of the (1 × 2) surface reconstruction at the RuO₂(100)/Ti interface is discussed in the context of maximum cation coordination by oxygen atoms.     

Preparation of CuInS2 thin films by metal-organic decomposition

Metal-organic decomposition (MOD) technique has been developed as a low cost thin film CuInS₂ preparation method for solar cell application. XRD and Raman spectra measurement revealed that deposited films contain CuInS₂. Stoichiometric films with a bandgap of 1.53 eV and an FWHM of 0.45° were obtained from a solution with Cu/In=1.5.     

基于介孔TiO_2薄膜等离子体波导的拉曼光谱技术研究

利用溶胶-凝胶分子模板法在表面覆金的玻璃基底上制备275 nm厚的介孔二氧化钛(TiO_2)薄膜,形成等离子体波导(PW)传感芯片.利用菲涅耳公式拟合实验测得的导模共振波长,得出TiO_2薄膜的多孔度约为0.589.基于光学互易定理仿真分析了置于介孔导波层中的电偶极子的拉曼辐射角分布,结果表明:辐射到衬底中的拉曼光包含沿导模共振角辐射的定向信号和辐射角小于全反射角的非定向信号;前者需借助棱镜耦合器才能被探测到,后者可从芯片背面直接被探测到;从导波层直接辐射到空气中的拉曼光称为背向信号,它的角分布呈发散式,几乎不受棱镜耦合器影响;定向信号的最大功率值远大于非定向信号和背向信号的相应值.实验研究了吸附于介孔导波层中的结晶紫分子的拉曼光谱,采用体光束激发方式探测到了定向、非定向和背向拉曼信号,定向信号强度的最大值是非定向信号的2倍多,在使用棱镜耦合器前后测得的背向信号强度几乎不变.     

Dry etching of CuCrO2 thin films

Highly conducting films of p-type CuCrO₂ are attractive as hole-injectors in oxide-based light emitters. In this paper, we report on the development of dry etch patterning of CuCrO₂ thin films. The only plasma chemistry that provided some chemical enhancement was Cl₂/Ar under inductively coupled plasma conditions. Etch rates of ∼500 Å min⁻¹ were obtained at chuck voltages around −300 V and moderate source powers. In all cases, the etched surface morphologies were improved relative to un-etched control samples due to the smoothing effect of the physical component of the etching. The threshold ion energy for the onset of etching was determined to be 34 eV. Very low concentrations (≤1 at.%) of residual chlorine were detected on the etched surfaces but could be removed by simple water rinsing.     

Preparation of Cu2ZnSnS4 thin films by hybrid sputtering

In order to fabricate Cu₂ZnSnS₄ thin films, hybrid sputtering system with two sputter sources and two effusion cells is used. The Cu₂ZnSnS₄ films are fabricated by the sequential deposition of metal elements and annealing in S flux, varying the substrate temperature. The Cu₂ZnSnS₄ films with stoichiometric composition are obtained at the substrate temperature up to 400 °C, whereas the film composition becomes quite Zn-pool at the substrate temperature above 450 °C. The Cu₂ZnSnS₄ film shows p-type conductivity, and the optical absorption coefficient and the band gap of the Cu₂ZnSnS₄ film prepared in this experiment are suitable for fabricating a thin film solar cell.     

Nitridation of thin SiO2 films in N2 and NH3 plasmas

A low-temperature (700°C) plasma-enhanced nitridation process which improves the dielectric breakdown of thin silicon dioxide (SiO₂) layers is presented. It uses a new, production compatible, parallel plate plasma reactor working at low RF frequencies. Nitrided oxides produce less charge trapping under high field stress, higher breakdown charge and a tighter distribution of breakdown fields than pure SiO₂. More nitrogen is incorporated in films treated in a NH₃ plasma than in a N₂ plasma. However, the latter present better electrical properties.     

Laser spectroscopy of CaF2:Eu:Sm thin films grown by pulsed laser deposition

Thin films of CaF₂ co-doped with low concentrations of Eu and Sm ions were grown by pulsed laser deposition (PLD) using a KrF (λ=248 nm) as the ablation source. To the best of our knowledge, the work presented here is the first report of rare-earth-doped CaF₂ films grown by PLD with this source. Combined laser excitation-emission spectroscopy was used to map out electronic transitions of Eu³⁺ with ⁷F₀→⁵D₁ excitation and the ⁵D₀→⁷F₁ emission. At the low concentrations used here the crystal field center of cubic symmetry is dominant in the films that are same for laser targets. However, charge compensated centers are present in the bulk crystal precursor. The removal of the charge compensated centers in the films and the target is likely caused by the target preparation where high pressure and temperature were applied.     

Micro-structuring of TiO2 thin films by laser-assisted diffraction processing

Thin films of TiO₂ are deposited by magnetron sputtering on glass substrate and are irradiated by UV radiation using a KrF excimer laser (248 nm). These thin films are patterned with a razor blade placed on the way of the radiation just in front of the TiO₂ thin film. Just near the edge of the razor blade on the thin film, diffraction lines are observed, resulting in the ablation of the film. These patterns are characterized by optical microscopy, mechanical profilometry. Diffraction up to the 35th order is observed. The results are shown to be compatible with a model in which electronic excitation plays the major role.     

Optical properties and electronic transitions of SnO2 thin films by reflection electron energy loss spectroscopy

Optical properties of SnO₂ thin films in the 4–60 eV energy range are determined by reflection electron energy loss spectroscopy. Bulk and surface electron loss functions, real and imaginary parts of the dielectric function, refraction index, extinction and absorption coefficients are obtained from the analysis of the electron energy loss spectra. Electronic transitions are identified through the interpretation of the optical data. The samples (250–500 nm thick) were produced by ion beam-induced chemical vapor deposition. It is found that the compacity of the SnO₂ thin films affects their optical properties and therefore the relative intensity of the observed electronic transitions. The advantages of this method to determine optical properties of thin films are discussed. Inelastic mean free paths (6.2, 17 and 41 Å for electrons traveling in SnO₂ with kinetic energies of 300, 800 and 2000 eV, respectively) are obtained from the corresponding inelastic electron scattering cross-sections.     

Characterization of a thin CeO2-ZrO2-Y2O3 films electrochemical deposited on stainless steel

In this paper, we report for the first time formation of a thin CeO₂-ZrO₂-Y₂O₃ films electrodeposited on a stainless steel substrate. The samples have been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The XRD and XPS data indicate formation of a solid solution and additional existence of Ce³⁺ states near the surface. After annealing, SEM examination has shown a microstructure formed by dispersed spherical agglomerates having a size between 20 and 60 nm.