An electron diffraction study of amorphous silicon oxide films

Amorphous silicon oxide films have been examined by high energy electron diffraction using the sector-microphotometer method of data collection common to gas phase electron diffraction. This data was analyzed with a least-squares procedure that is designed to minimize extraneous detail in the radial distribution function obtained by the Fourier sine transform of the interference function. The results of this analysis for thin film SiO₂ show that the overall bonding topology of the thin film agress well with that of bulk (vitreous) SiO₂ examined by X-ray diffraction. The experimental short distance parameters for the films whose composition was determined to be ～SiO_1.3, SiO, and SiO_0.8 are found to be consistent with those expected for a mixture of tetrahedrally bonded amorphous Si and SiO₂ phases in which the scale of the Si-like and SiO₂-like regions is of the order of a few basic tetrahedral units. This result is in agreement with previous examinations of SiO powder by X-rays and a previous examination of thin silicon oxide films by electron diffraction.     

Electron emission from excited states of E′ centers in SiO2

The applicability of the non-stationary optically stimulated electron emission (OSEE) to the spectroscopy of E′ centers in different SiO₂ modifications was demonstrated. Spectral dependences of the OSEE from E′ centers in samples of silica glass, crystalline α-quartz, SiO₂ films and nanoceramics exposed to fast electrons and ions were obtained. A model of the energy structure of E′ centers accounting for the absence of luminescence and taking into account the presence of two non-radiative relaxation channels (intracenter and ionization) is discussed. This model was used to substantiate the mechanism of the photothermal decay of E′ centers and to determine the quantum yields of OSEE for different types of E′ centers.     

Fluorinated nanoporous SiO2 films with ultra-low dielectric constant

Fluorinated nanoporous silica (denoted as SiO₂:F) thin films with low dielectric constant were prepared by a sol-gel method and spin coating technique. The leakage current densities of the SiO₂:F thin films were 10⁻⁸ and 3 × 10⁻⁶ A/cm² respectively for the as-deposited films and for those subjected to annealing at a temperature of 450 °C. These currents are more than one order of magnitude lower than those of the common SiO₂ films. Photoluminescent results showed strong blue-light emission and a small blue shift in the SiO₂:F films that were related to the increment of the porosity. The dielectric properties were also characterized and the k value of the annealed SiO₂:F film was found to be about 1.67. The hole size in the films is small and the size distribution is uniform for the annealed SiO₂:F samples due to the effects of fluorination. The underlying mechanism for fluorination is discussed in this paper.     

Ablation and compaction of amorphous SiO2 irradiated with ArF excimer laser

The structure of amorphous SiO₂ exposed to ArF excimer laser irradiation was examined. Threshold fluence for causing ablation with a single pulse depended on sample preparation: more specifically, 1 J/cm² for thermally grown SiO₂ films on silicon and 2.5 J/cm² for bulk SiO₂. It was found that the bond angle of Si-O-Si was reduced by irradiation near the interface of thermally grown SiO₂ films. In contrast, evolution of the bond angle by irradiation was absent in both the bulk SiO₂ and SiO₂ film-near the top surface, even though the concentration of puckered four-membered rings deduced from Raman spectra dramatically increased. It is assumed that planar three-membered rings were generated in the SiO₂ thin layer near the interface, and puckered four-membered rings were generated in the bulk SiO₂. The concentration of both the Si³⁺ and Si²⁺ structure was increased at a fluence of 800 mJ/cm² with an increasing number of pulses, although generation of both was absent at higher fluence for a single pulse. The author proposes that the structure of SiO₂ is created by flash heating and quenching by pulse laser irradiation. Structural similarities were found between the irradiated SiO₂ and SiO₂ at high temperatures.     

EXAFS study of the Er3+ ion coordination in SiO2–TiO2–HfO2 sol–gel films

The local order around ion-implanted Er³⁺ ions in SiO₂–TiO₂–HfO₂ thin films prepared by sol–gel, was studied by extended X-ray absorption fine structure at the Er-L_III edge. Both the first and second coordination shells of Er³⁺ were analyzed for different heat-treatments. While the first coordination shell always consisted of ～6–7 oxygen atoms at distances varying between 2.23 and 2.27 Å, the structure of the second shell was found to vary with the film composition and heat-treatment. Namely, whereas Si was found to be the only second neighbor of erbium in binary SiO₂–TiO₂ films, the addition of HfO₂ caused a preferential replacement of Si by Hf. The post-implantation thermal treatments also played a fundamental role in determining the final environment of the erbium ions.     

Structural inhomogeneities and magnetic properties of Co/Cu multilayer films

The polycrystalline Co/Cu multilayer films are prepared by magnetron sputtering onto Si/SiO₂ substrates. The static magnetization and the ferromagnetic resonance (FMR) spectra of these films are investigated. The microscopic cross-sectional structure of the films is examined using transmission electron microscopy. It is demonstrated that the differences in the magnetization curves and the ferromagnetic resonance spectra are associated with the specific structural features governed by the technological parameters of the film sputtering. The possible structural features that arise during the formation of layered structures and are responsible for the appearance of additional lines in the FMR spectra are discussed.     

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.     

SiOx films prepared using RF magnetron sputtering with a SiO target

In this study, SiO_x thin films were prepared using reactive radio frequency magnetron sputtering at room temperature with a SiO sintered target. The obtained SiO_x films were identified using X-ray diffraction, transmission electron microscopy, infrared absorption spectroscopy, X-ray photoelectron spectroscopy and ultraviolet-visible transmittance measurement. The x in SiO_x film was controlled from 0.98 to 1.70 by changing the oxygen flow ratio at deposition. Increasing the oxygen flow ratio increased the optical gap of the SiO_x films from 3.7 to greater than 6 eV.     

X-ray spectroscopic investigation of the structure of silica,silicates and oxides in the crystalline and vitreous state

The Si Kα_1,2 emission lines and their satellite lines α′, α₃ and α₄ were measured for several samples of vitreous silica (Suprasil W, Infrasil, Suprasil), sodium silicate glasses (8, 15, 20 and 25 wt% Na₂O), and crystalline Mg₂SiO₄ (Forsterite). The observed shifts of the peak positions indicate a systematic increase of the electron density on the silicon atoms with increasing break-up of the SiO₂ network by OH^? or alkali ions. These results are compared with information from the corresponding Si Kβ and O K emission bands and also with the O K emission bands from quartz, MgO and Al₂O₃. They are discussed on the basis of the MO theory and are compared with the characteristic physical properties and structure of silica and silicate glasses. Both the O K and Si Kβ emission bands are closely related to the electronegativities of the relevant metal atoms of the oxides and glasses.     

Effects of passivation and postannealing on the photoluminescence properties of MgO/SiO2 core‐shell nanorods

MgO nanorods were grown by the thermal evaporation of Mg₃N₂ powders on the Si (100) substrate coated with a gold thin film. The MgO nanorods grown on the Si (100) substrate were a few tens of nanometers in diameter and up to a few hundreds of micrometers in length. MgO/SiO₂ core‐shell nanorods were also fabricated by the sputter‐deposition of SiO₂onto the MgO nanorods. Transmission electron microscopy (TEM) and X–ray diffraction (XRD) analysis results indicated that the cores and shells of the annealed core‐shell nanorods were a face‐centered cubic‐type single crystal MgO and amorphous SiO₂, respectively. The photoluminescence (PL) spectroscopy analysis results showed that SiO₂ coating slightly decreased the PL emission intensity of the MgO nanorods. The PL emission of the MgO/SiO₂ core‐shell nanorods was, however, found to be considerably enhanced by thermal annealing and strongly depends on the annealing atmosphere. The PL emission of the MgO/SiO₂ core‐shell nanorods was substantially enhanced in intensity by annealing in a reducing atmosphere, whereas it was slightly enhanced by annealing in an oxidative atmosphere. The origin of the PL enhancement by annealing in a reducing atmosphere is discussed with the aid of energy‐dispersive X‐ray spectroscopy analyses. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Anomalous amorphous SiO2 films

Anomalous SiO₂ films have been prepared by sputtering Si in a mixture of Ar-10% O₂ at 77 K. The same sputtering conditions at room temperature yield normal SiO₂ which means that the anomaly is produced by the low temperature deposition. The anomaly reveals itself in several physical properties. The density of the anomalous SiO₂ is 1.72 as compared with 2.20 for bulk and the dielectric constant is about 50% larger than bulk and with a much stronger temperature dependence. The infrared (ir) spectrum of the anomalous SiO₂ is only slightly different from bulk SiO₂ but esr experiments reveal about 3 × 10¹⁸ spins cm which do not exist in bulk SiO₂. These anomalous films are extremely stable: upon heating only a small amount of oxygen (1 part in 10⁵) evolves at 440°C but the density and IR spectrum remain unchanged up to 1300°C. Annealing at 1500°C completely removes the ESR signal and returns the ir spectrum and the density to that of cristobalite. An electron diffraction and transmission electron microscopy study reveals that the anomalous SiO₂ films consist of essentially bulk like SiO₂ clusters about 250 Å in diameter separated by a low density network. The low density network undoubtedly contains unbound O atoms and the SiSi bonds which give rise to the esr signal. The structural model can account for all the anomalous properties.     

Preparation,structure and photoluminescence properties of SiO2–coated ZnS nanowires

It is essential to passivate one‐dimensional (1D) nanostructures with insulating materials to avoid crosstalking as well as to protect them from contamination and oxidation. The structure and influence of thermal annealing on the photoluminescence properties of ZnS‐core/SiO₂‐shell nanowires synthesized by the thermal evaporation of ZnS powders followed by the sputter deposition of SiO₂ were investigated. Transmission electron microscopy and X‐ray diffraction analyses revealed that the cores and shells of the core‐shell nanowires were single crystal zinc blende‐type ZnO and amorphous SiO₂, respectively. Photoluminescence (PL) measurement showed that the core‐shell nanowires had a green emission band centered at around 525 nm with a shoulder at around 385 nm. The PL emission of the core‐shell nanowires was enhanced in intensity by annealing in an oxidative atmosphere and further enhanced by subsequently annealing in a reducing atmosphere. Also the origin of the enhancement of the green emission by annealing is discussed based on the energy‐dispersive X‐ray spectroscopy analysis results. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural Properties of CuGaxIn1-xSe2 Thin Films Deposited by Spray Pyrolysis

Thin films of CuGa_xIn_1-xSe₂ (x=0.0-1.0) have been prepared by spray pyrolysis onto soda-lime glass substrates heated to a temperature of 325° C. The structure, crystal orientations, lattice parameters and grain size of the experimental films have been studied using the X-ray diffraction and scanning electron microscopy. All the deposited films were polycrystalline and showed single phase with an intense (112) orientation. The lattice parameters, a and c of the films vary linearly with the change of gallium composition. The grain size of the films decrease with the increase of gallium content.     

Application of D‐optimal experimental design in nano‐sized ZSM‐5 synthesis for obtaining higher crystallinity

D‐optimal experimental design with three levels of SiO₂/Al₂O₃, template/SiO₂, H₂O/SiO₂, SiO₂/Na₂O and TPABr/TPAOH ratio parameters was used to optimize the experimental parameters by the analysis of variance (ANOVA). The effects of above mentioned ratios in the initial synthetic mixture on the crystallinity of the ZSM‐5 zeolite were studied. The synthesized samples were characterized by XRD, FE‐SEM, and TEM analysis. Fischer test results showed that SiO₂/Al₂O₃ and H₂O/SiO₂ molar ratios are the most and least effective parameters, respectively, in the range studied. The most important two‐way interaction variable was that of template/SiO₂ and Na₂O/SiO₂ molar ratios. The optimum composition of the gel compound to achieve relative maximum crystallinity is SiO₂/Al₂O₃ = 99.96, template/SiO₂ = 0.16, H₂O/SiO₂ = 34.68, Na₂O/SiO₂ = 0.02 and TPABr/TPAOH = 1.44.     

RHEED Investigations on Low-temperature Thermal SiO2 Films

The structural changes in thermal SiO₂ films grown at 1123–1173 K in a double walled furnace tube with chlorine between the inner and the outer tube are studied. The layers have a higher degree of crystallinity in comparison with the layers grown by standard high temperature dry oxidation (1273 K). A difference between the crystalline type structures of SiO₂ films on p- and n-Si is observed. The increase of the growth temperature from 1123 to 1273 K increases the variety of crystalline structures in the layers but decreases strongly their quantity and makes the films predominantly amorphous.     

Influence of amorphous buffer layers on the crystallinity of sputter-deposited undoped ZnO films

Undoped ZnO films were deposited by radio frequency (RF) magnetron sputtering on amorphous buffer layers such as SiO_x, SiO_xN_y, and SiN_x prepared by plasma enhanced chemical vapor deposition (PECVD) for dielectric layer in thin film transistor (TFT) application. ZnO was also deposited directly on glass and quartz substrate for comparison. It was found that continuous films were formed in the thickness up to 10 nm on all buffer layers. The crystallinity of ZnO films was improved in the order on quartz>SiO_x >SiO_xN_y>glass>SiN_x according to the investigated intensities of (0 0 2) XRD peaks. The crystallite sizes of ZnO were in the order of SiO_x～glass >SiN_x. Stable XRD parameters of ZnO thin films were obtained to the thickness from 40 to 100 nm grown on SiO_x insulator for TFT application. Investigation of the ZnO thin films by atomic force microscope (AFM) revealed that grain size and roughness obtained on SiN_x were larger than those on SiO_x and glass. Hence, both nucleation and crystallinity of sputtered ZnO thin films remarkably depended on amorphous buffer layers.     

Influence of thermoannealing on crystallinity and optical properties of Sb2S3 thin films

Sb₂S₃ thin films are obtained by evaporating of Sb₂S₃ powder onto glass substrates maintained at room temperature under pressure of 2×10^‐5 torr. The composition of the thin films was determined by energy dispersive analysis of X‐ray (EDAX). The effect of thermal annealing in vacuum on the structural properties was studied using X‐ray diffraction (XRD) technique and scanning electron microscopy (SEM). The as‐deposition films were amorphous, while the annealed films have an orthorhombic polycrystalline structure. The optical constants of as‐deposited and annealed Sb₂S₃ thin films were obtained from the analysis of the experimental recorded transmission spectral data over the wavelength range 400‐1400 nm. The transmittance analysis allowed the determination of refractive index as function of wavelength. It was found that the refractive dispersion data obeyed the single oscillator model, from which the dispersion parameters (oscillator energy, E₀, dispersion energy, E_d) were determined. The static refractive index n(0), static dielectric constant, ε_∞, and optical band gap energy, E_g, were also calculated using the values of dispersion parameters. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Use of cadmium selenide thin films as a carbon dioxide gas sensor

Cadmium Selenide (CdSe) thin films were prepared in different growth conditions by thermal evaporation. The films were characterised using transmission electron microscopy and X-ray diffraction. The electrical parameters such as resistivity, carrier mobility, and concentration were determined. The sensitivity of carbon dioxide (CO₂) gas on CdSe thin films were studied. A tentative mechanism was proposed, in which the role of CO₂ gas in increasing the conductivity of CdSe thin films were explained by Molecular Orbital (MO) theory. CO₂ gas sensing alarm system was fabricated.     

Influence of temperature on the microcrystalline structure of thermally evaporated Sb2S3 thin films

Thin films of antimony trisulfide (Sb₂S₃) were prepared by thermal evaporation under vacuum (p=5×10^–5 torr) on glass substrates maintained at various temperatures between 293 K and 523 K. Their microstructural properties have obtained by transmission electron microscopy (TEM). The electron diffraction analysis showed the occurrence of amorphous to polycrystalline transition in the films deposited at higher temperature of substrates (523 K). The polycrystalline thin films were found to have an orthorhombic structure. The interplanar distances and unit‐cell parameters were determined by high‐resolution transmission electron microscopy (HRTEM) and compared with the standard values for Sb₂S₃. The surface morphology of Sb₂S₃ thin films was investigated by scanning electron microscopy (SEM). The optical transmission spectra at normal incidence of Sb₂S₃ thin films have been measured in the spectral range of 400–1400 nm. The analysis of the absorption spectra revealed indirect energy gaps, characterizing of amorphous films, while the polycrystalline films exhibited direct energy gap. From the photon energy dependence of absorption coefficient, the optical band gap energy, E_g, were calculated for each thin films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mesoporous materials from SiO2 and NiTiO3

In this work, we synthesized and characterized mesoporous thin films of SiO₂ and NiTiO₃ structured by a surfactant called Brij58. These films were fabricated by the method of dip coating and the best conditions for well-structured thin films were investigated as a function of surfactant concentration and different types of substrates. These films have been characterized by X-ray reflectivity which was calculated using the matrix formalism. We demonstrated that the silicon substrate had a great effect on the structure and porosity of the fabricated films for both SiO₂ and NiTiO₃. Furthermore, we found that mesoporosity has been increased as a function of the surfactant concentration in the solution. This experimental procedure allows also to produce NiTiO₃ powders which have been characterized by X-ray diffraction. The XRD coupled to the crystallographic software “Maud”shows that the samples are constituted by 98, 2% NiTiO₃ powders.