Effect of high-energy electron-beam irradiation on the optical properties of ion-beam-sputtered silicon oxynitride thin films

Silicon oxynitride thin films are prepared by ion-beam sputtering, and the optical properties and surface chemical composition are studied by spectrophotometric and x-ray photoelectron spectroscopy, respectively. It is seen that the films sputtered by use of nitrogen alone as the sputtering species from a silicon nitride target are completely transparent (k < 0.005) and have a refractive-index dispersion from 1.85 to 1.71 over the visible and near-infrared spectral regions, and the films show distinct spectral lines that are due to silicon, Si(2s), nitrogen, N(1s), and oxygen, O(1s). Sputter deposition of argon and of argon and nitrogen produces silicon-rich silicon oxynitride films that are absorbent and have high refractive indices. These films have a direct electronic transition, with a threshold energy of 1.75 eV. Electron irradiation transforms optically transparent silicon oxynitride films into silicon-rich silicon oxynitride films that have higher refractive indices and are optically absorbing owing to the presence of nonsaturated silicon in the irradiated films. The degradation in current responsivity of silicon photodetectors, under electron irradiation, is within 3% over the wavelength region from 450 to 750 nm, which is entirely due to the degradation of optical properties of silicon oxynitride antireflection coatings.     

Characterization of silicon oxynitride films prepared by the simultaneous implantation of oxygen and nitrogen ions into silicon

Silicon oxynitride films about 5 nm in thickness were prepared by simultaneously implanting 5 keV oxygen and nitrogen ions into silicon at room temperature up to saturation. These films with concentrations ranging from pure silicon oxide to silicon nitride were characterized using Auger electron spectroscopy, electron energy loss spectroscopy and depth-concentration profiling. The different behaviour of the silicon oxynitride films compared with those of silicon oxide and silicon nitride with regard to thermal stability and hardness against electron and argon ion irradiation is pointed out.     

Optical properties of LPCVD silicon oxynitride

Low pressure chemical vapour deposition (LPCVD) silicon oxynitride films of various compositions (from pure SiO₂ to pure Si₃N₄) were deposited by changing the relative gas flow ratio. The effects of oxygen on the physical properties of the films were studied by spectroellipsometry (using Bruggeman approximation and Wemple Di Domenico model) and infrared spectroscopy. Refractive index measured by spectroellipsometry method is studied as a function of some deposition parameters: temperature of deposition, gases fluxes ratio. The high value of deposition temperature means low values in refractive index. More oxygen into films decreases the refractive index. The refractive index dispersion is studied by single-oscillator Wemple Di Domenico model. The optical band gap varies monotonically from 5 eV for silicon nitride, to 9eV for HTO LPCVD silicon dioxide and for the studied silicon oxynitride was found to be between 5 and 6 eV.     

Optimization of PECVD silicon oxynitride films for anti-reflection coating

In this work, amorphous silicon oxynitride films were deposited on silicon substrates by plasma-enhanced chemical vapor deposition (PECVD). The main purpose was to use silicon oxynitride film as a single-layer anti-reflection coating for Si-based optoelectronic devices. The chemical information was measured by infrared spectroscopy. Surface and cross-section morphology was determined by a scanning electron microscope. Spectroscopic ellipsometry (SE) was applied to measure the refractive index, extinction coefficient and thickness. The results of SE presented the refractive indices varied in the range of 1.83-1.92 by altering SiH₄/NH₃ ratio. One-side polished silicon substrate coated with silicon oxynitride film exhibited low reflectance, and two-side polished silicon substrate coated with silicon oxynitride film exhibited high transmittance. The results suggested that silicon oxynitride film was a very attractive single-layer anti-reflection coating.     

An examination of the reactive sputtering of silicon nitride on to gallium arsenide

The deposition of silicon nitride thin films by the reactive sputtering of elemental silicon in a nitrogen/argon plasma has been investigated. The composition of the thin films has been examined using infra-red reflectance, X-ray photoelectron and Auger electron spectroscopies and spark source mass spectrometry. Oxygen has been found to be a major contaminant in these sputter deposited films, the oxygen concentration depending on the ambient gas pressure. The use of the silicon oxy-nitride films as annealing encapsulants for the activation of silicon ion implanted semi-insulating gallium arsenide has also been investigated.     

Optical,structural and electrical characteristics of aluminum oxynitride thin films deposited in an Ar-N gas mixture RF-sputtering system

The optical, structural and electrical characteristics of aluminum oxynitride thin films deposited on silicon by rf-sputtering under a fixed oxygen flow and two different Ar and N gas flows are reported. The stoichiometry of the films was studied by EDS as a function of the deposition parameters. In general, the relative oxygen content within the films was higher for a high N/Ar (5/1) gas flow ratio, these films presented refractive indexes in the range of 1.5–2.0, with deposition rates close to 4.0 nm/min, and surface roughness of approximately 13 Å. Films deposited with a low N/Ar (1/5) flow ratio presented refractive indexes in the range of 1.7 to 2.0, deposition rates of 7 nm/min and surface roughness of 26 Å. IR spectroscopy measurements on these films presented an absorption band spreading from 500 to 900 cm^?1. The width and peak of this band depends on the rf power and correlates with the oxygen content in the films. Films with the best electrical characteristics present an average dielectric constant of 7.2 and 8.7 standing electric fields up to 4.5 and 2 MV/cm without observing destructive dielectric breakdown for high and low N/Ar gas ratios respectively.     

Influence of Relevant Gas Pressure on the Properties of Ionplated Ta2O5 Films. Einfluss relevanter Gasdrücke auf die Eigenschaften ionenplattierter Ta2O5 Schichten

Ta₂O₅ films were deposited onto unheated fused silica substrates (Suprasil®) by reactive low voltage ion plating (RLVIP). From these films of about 200 nm thickness the optical properties (refractive index n and the absorption coefficient k) and also the mechanical properties (density ρ and intrinsic stress σ) were investigated in dependence of the working gas pressure (Ar) and the reactive gas pressure (O₂). The experiments show a reasonable correlation between refractive index, density and intrinsic stress of the films. With low total pressure high refractive indices (up to n₅₅₀=2.25), high compressive film stress and high relative film density were found. However the film density, the refractive index and also the intrinsic stress decreased with films prepared under raising total gas pressure. The optical absorption depends on the amount of oxygen in the gas phase during deposition. By adding more oxygen to the Ar/O₂ gas mixture primarily the absorption could clearly be decreased.     

IR transmittance studies of hydrogen-free and hydrogenated silicon nitride and silicon oxynitride films deposited by reactive sputtering

Amorphous silicon nitride and silicon oxynitride films were deposited by reactive r.f. sputtering in various reactive ambients of nitrogen, oxygen and hydrogen of different compositions. The IR transmittance of the films was studied as a function of their hydrogen content and the oxygen:nitrogen ratio. The results were discussed in terms of compensation of gap states by hydrogenation. The microscopic structure of the silicon oxynitride films is believed to depend on the oxygen:nitrogen atomic ratio.     

Raman spectra and structural analysis in ZrOxNy thin films

Raman spectroscopy has been used as a local probe to characterize the structural evolution of magnetron-sputtered decorative zirconium oxynitride ZrO_xN_y films which result from an increase of reactive gas flow in the deposition. The lines shapes, the frequency position and widths of the Raman bands show a systematic change as a function of the reactive gas flow (a mixture of both oxygen and nitrogen). The as-deposited zirconium nitride film presents a Raman spectrum with the typical broadened bands, due to the disorder induced by N vacancies. The recorded Raman spectrum of the zirconium oxide film is typical of the monoclinic phase of ZrO₂, which is revealed also by X-ray diffraction. Raman spectra of zirconium oxynitride thin films present changes, which are found to be closely related with the oxygen content in films and the subsequent structural changes.     

Effect of the oxygen fraction on the structure and optical properties of HfOxNy thin films

The main purpose of this work was to prepare hafnium oxynitride (HfO_xN_y) thin films. HfO_xN_y thin films were deposited by radio frequency reactive magnetron sputtering from a pure Hf target onto Quartz and ZnS substrates at room temperature. The depositions were carried out under an oxygen-nitrogen-argon atmosphere by varying the flow rate of the reactive gases (oxygen/nitrogen ratio). The variation of the flow rate of the reactive gases changed the structure and properties of the films. Glancing incidence X-ray diffraction (GIXRD) was used to study the structural changes of as-deposited films; a new crystalline hafnium oxynitride phase was formed in a region of oxygen/nitrogen ratio. Cross-section of the films observed by SEM revealed that the films grew with a columnar-type structure, and surface observation with AFM showed values of surface roughness changed with the flow rate of the reactive gases, higher oxygen fraction had lower surface roughness than lower oxygen fraction. Visible spectra, infrared spectra, refractive index, absorption coefficient also changed with the variation of the oxygen fraction.     

Effect of argon pressure on the optical properties of sputtered solar selective surfaces

The influence of argon gas pressure (0.15-40 Pa) on the refractive indices n,k of dc planar-magnetron reactively sputtered cermet and amorphous semiconductor films has been investigated for a layer thickness of approximately 50 nm. Stainless steel-carbon and amorphous hydrogenated carbon layers with relatively low index n and stainless steel-silicon and amorphous hydrogenated silicon layers with relatively high index n are examined with a view to solar selective surface applications. The development of structural porosity with associated reduction in n for layers deposited at high argon pressure significantly improves the solar absorptance of surfaces incorporating stainless steel-silicon or amorphous hydrogenated silicon layers.     

Effects of argon and oxygen addition to the CH4-H2 feed gas on diamond synthesis by microwave plasma enhanced chemical vapor deposition

In order to investigate the effects of argon and oxygen on diamond synthesis, the behaviors of diamond deposition using microwave plasma chemical vapor deposition method have been studied by varying the concentrations of argon and oxygen in the methane-hydrogen gas mixture. Diamond films were deposited on silicon wafer under the conditions of substrate temperatures: 1073 1173 K, total reaction pressure: 5333 Pa (40 Torr), methane concentrations: 0.5 5.0%, and they were characterized by scanning electron microscopy, Raman spectroscopy and optical emission spectroscopy. The deposition rates of diamond films were enhanced by adding argon into the methane-hydrogen system, but nondiamond carbon phases in the films also increased. It resulted from the increase of hydrocarbon radicals in the plasma. As oxygen was added, the quality of deposited diamond films was improved due to the decrease of C₂ radicals and increase of OH radicals in the plasma. Simultaneous addition of 0.3% oxygen and 20% argon has been able to effectively suppress the formation of nondiamond carbon components and increase the deposition rate of diamond films. It appears that the ionized argon (Ar⁺) and excited argon atoms (Ar*) may activate the various chemical species and promote the reactions between the gas phase species and oxygen in the plasma.     

Dependency of oxygen partial pressure on the characteristics of ZnO films grown by radio frequency magnetron sputtering

The effects of oxygen and argon gas contents on the structural and optical properties of epitaxially grown ZnO thin films on sapphire substrates by radio frequency magnetron sputtering were investigated. The growth rate of ZnO thin film decreases with increase in oxygen gas contents in the gas mixture. The high-resolution x-ray diffraction $ {\left( {10\overline{1} 2} \right)} $ rocking curve and plane-view transmission electron microscopy investigations reveal the presence of a reduced dislocation density in the ZnO thin films with decrease in oxygen/argon flow ratio. However, large density of defects were observed in the boundaries and inside of the micro-hillocks formed on the surface of ZnO thin film grown with pure argon. The increase in oxygen gas ratio resulted in the improvement of optical properties with suppression and red-shift of the deep level emission.     

Electrical properties of AlNxOy thin films prepared by reactive magnetron sputtering

Direct current magnetron sputtering was used to produce AlN_xO_y thin films, using an aluminum target, argon and a mixture of N₂ + O₂ (17:3) as reactive gases. The partial pressure of the reactive gas mixture was increased, maintaining the discharge current constant. Within the two identified regimes of the target (metallic and compound), four different tendencies for the deposition rate were found and a morphological evolution from columnar towards cauliflower-type, ending up as dense and featureless-type films. The structure was found to be Al-type (face centered cubic) and the structural characterization carried out by X-ray diffraction and transmission electron microscopy suggested the formation of an aluminum-based polycrystalline phase dispersed in an amorphous aluminum oxide/nitride (or oxynitride) matrix. This type of structure, composition, morphology and grain size, were found to be strongly correlated with the electrical response of the films, which showed a gradual transition between metallic-like responses towards semiconducting and even insulating-type behaviors. A group of films with high aluminum content revealed a sharp decrease of the temperature coefficient of resistance (TCR) as the concentration ratio of non-metallic/aluminum atomic ratio increased. Another group of samples, where the non-metallic content became more important, revealed a smooth transition between positive and negative values of TCR. In order to test whether the oxynitride films have a unique behavior or simply a transition between the typical responses of aluminum and of those of the correspondent nitride and oxide, the electrical properties of the ternary oxynitride system were compared with AlN_x and AlO_y systems, prepared in similar conditions.     

Characterization of bi-phased Zr2ON2–ZrO2 coatings deposited by RF magnetron sputtering

The aim of this work is to develop zirconium oxynitride coatings by RF magnetron sputtering on silicon substrates. The film properties were analyzed as a function of oxygen flux percentage in two different inert gas atmospheres namely argon and helium. At low oxygen flux percentage, Zr₂ON₂ and ZrO₂ phases are observed from the structural characterization by X-ray diffraction. The atomic ratio of nonmetallic to metallic atoms (N + O)/Zr content varies from 1.22 to 2.03 for zirconium oxynitride films deposited in argon atmosphere and from 1.43 to 2.33 for films deposited in helium atmosphere. The thickness of the film was measured by surface profiler and the growth rate decreases from 11.33 to 5.1 nm/min for films deposited in argon atmosphere and from 7.01 to 3.75 nm/min for films deposited in helium atmosphere with increase in oxygen flux percentage. The films deposited are hydrophobic and the contact angle was measured by contact angle measuring system. Higher surface roughness and maximum contact angle values of 100° and 103° are observed for films deposited in argon and helium atmosphere respectively at low oxygen flux percentage (2.5%). The surface energy of films was calculated by two methods: Owens-Wendt's geometric mean and Wu's harmonic mean approach. The elevated surface energy values were observed with increase in oxygen flux percentage. The stress measurements of the deposited films were done by sin²ψ X-ray diffraction method which depends on the variation of Zr₂ON₂ and m-ZrO₂ phases.     

Deposition of nickel oxide by direct current reactive sputtering: Effect of oxygen partial pressure

Nickel oxide thin films were deposited by Direct Current magnetron reactive sputtering from Ni target onto SnO₂:F conductive glass substrates. The process was carried out without intentional heating, in an argon/oxygen gas mixture with various oxygen contents and discharge currents. The polycrystalline NiO thin films were deposited with controlled growth of the structure along [111] and [200] crystallographic directions for chosen conditions. Morphology of as-deposited films was found to depend on the preferentially oriented NiO crystals. Moreover, on the basis of discharge voltage as a function of the O₂ partial pressure for a constant discharge current, we present here the method to estimate the deposition conditions allowing us to achieve the desired preferential growth of transparent p-type semiconductor NiO, by Direct Current magnetron reactive sputtering.     

Thermally stable narrow-bandpass filter prepared by reactive ion-assisted sputtering

Thermal stabilities of three-cavity narrow-bandpass (NB) filters with high-index half-wave spacers and 78-102 layers of Ta(2)O(5) and SiO(2) prepared by reactive ion-assisted bipolar direct-current (dc) magnetron sputtering of tantalum and silicon targets, respectively, were investigated. Pure argon and pure oxygen were used as the sputtering gas and the reactant, respectively. The oxygen gas was introduced and ionized through the ion gun and toward the unheated BK7 glass substrate. The refractive indices of single-layer Ta(2)O(5) and SiO(2) films were 2.1 and 1.45, respectively, at 1550 nm, which were comparable with those of films prepared by other ion-assisted coating techniques. The moisture-resistant properties of the films were excellent as evidenced from the water-immersion test, implying that the packing density of the films was close to that of their bulk materials. The temperature-dependant wavelength shifts of the NB filters were <3 x 10(-3) nm/ degrees C at temperatures of <75 degrees C, indicating that the temperature-induced wavelength shift of the filter was <0.15 nm when the temperatures were raised from room temperature to 75 degrees C, which was compliant with Bellcore GR-1209-CORE generic requirements of NB filters used for optical-fiber communication systems.     

Elaboration and characterization of Fe1-xO thin films sputter deposited from magnetite target

Majority of the authors report elaboration of iron oxide thin films by reactive magnetron sputtering from an iron target with Ar-O₂ gas mixture. Instead of using the reactive sputtering of a metallic target we report here the preparation of Fe_1-xO thin films, directly sputtered from a magnetite target in a pure argon gas flow with a bias power applied. This oxide is generally obtained at very low partial oxygen pressure and high temperature. We showed that bias sputtering which can be controlled very easily can lead to reducing conditions during deposition of oxide thin film on simple glass substrates. The proportion of wustite was directly adjusted by modifying the power of the substrate polarization. Atomic force microscopy was used to observe these nanostructured layers. Mössbauer measurements and electrical properties versus bias polarization and annealing temperature are also reported.     

A study of silicon oxynitride film prepared by ion beam assisted deposition

A SOI-based optoelectronic device needs a high-quality antireflection coating on both faces of the device to minimize the optical reflectance from the face. In this work amorphous silicon oxynitride films were deposited on silicon substrates by ion beam assisted deposition (IBAD). The main purpose was to use silicon oxynitride film as single layer anti-reflection coating for SOI-based optoelectronic devices. This application is primarily based on the ability to tune the silicon oxynitride optical functions to the optimal values by changing deposition parameters. The chemical information was measured by X-ray photoelectron spectroscopy (XPS). Spectroscopic ellipsometry (SE) was applied to measure the refractive index and thickness. Single-side polished silicon substrate that was coated with silicon oxynitride film exhibited low reflectance. Double-side polished silicon substrate that was coated with silicon oxynitride film exhibited high transmittance. In addition, the Fresnel losses could be reduced to 0.08 dB by depositing silicon oxynitride films onto double-side polished silicon substrates. The results suggested silicon oxynitride film was a very attractive single layer anti-reflection coating for SOI-based optoelectronic device.     

Advanced key technologies for magnetron sputtering and PECVD of inorganic and hybrid transparent coatings

Besides classical multilayer systems with alternating low and high refractive indices, reactive pulse magnetron sputtering processes offer various possibilities of depositing gradient films with continuously varying refractive index. Using nanoscale film growth control it is possible to achieve optical filter systems with a defined dependency of refractive index on film thickness, e.g. by sputtering a silicon target in a time variant mixture of oxygen and nitrogen. Also reactive co-sputtering of different target materials such as silicon and tantalum in oxygen is suitable as well. Rugate filters made from SiO_xN_y or Si_xTa_yO_z gradient refractive index profiles find their application in spectroscopy, laser optics and solar concentrator systems.Furthermore polymer substrates are increasingly relevant for the application of optical coatings due to their mechanical and economical advantages. Magnetron PECVD (magPECVD) using HMDSO as precursor allows to deposit carbon containing films with polymer-like properties. Results show the suitability of these coatings as hard coatings or matching layers. Multifunctional coatings with antireflective and scratch-resistant properties were deposited on polymer substrates using a combined magPECVD and sputter deposition process.