Oxygen plasma treatment of SiOxCy(− H) films polymerized by atmospheric pressure dielectric barrier discharge using hexamethylcyclrotrisiloxane

The SiO₂-like layers were obtained by plasma-oxidation of the SiO_xC_y(− H) films deposited from hexamethylcyclotrisiloxane (HMCTSO) with helium and oxygen. The SiO₂-like layers were formed on as-deposited SiO_xC_y(− H) films within a second by oxidation using the He/O₂ atmospheric pressure dielectric barrier discharge (APDBD). The elemental ratio of oxygen to silicon in the layer was increased up to 1.95 which is closed to stoichiometry of SiO₂. The elemental composition and surface morphology were studied by means of x-ray photoelectron spectroscopy and atomic force microscopy. Wettability of the oxidized thin films was investigated by water droplet contact angle measurement. The contact angle of SiO_xC_y(− H) films are decreased from 63° to below 10° within a second by oxidation. Correlation between the elemental composition and the contact angle were discussed. The effects of oxidation duration and discharge generation voltage on the composition and surface morphology of the film were investigated.     

Room temperature plasma oxidation in DCSBD: A new method for preparation of silicon dioxide films at atmospheric pressure

In this paper a new process for the preparation of thin silicon dioxide (SiO₂) film is presented: the oxidation of c-Si (1 1 1) surface in atmospheric pressure plasma at room temperature. Diffuse coplanar surface barrier discharge (DCSBD) at atmospheric pressure in air and oxygen atmosphere has been used. The oxidation rate and the thickness of oxidized layers were estimated by ellipsometry. The structure and the chemical composition of oxidized layers were investigated by infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray (EDX) analysis. Scanning electron microscopy (SEM) was used to observe the morphology of the layer surface. It was found that stoichiometric SiO₂ layers were obtained with oxidation rates comparable to thermal oxidation.     

Atomic layer deposition of SiO2 from Tris(dimethylamino)silane and ozone by using temperature-controlled water vapor treatment

Atomic layer deposition of SiO₂ from tris(dimethylamino)silane (TDMAS) and ozone as precursors on Si(100) surfaces at near-room temperatures was studied by infrared absorption spectroscopy with a multiple internal reflection geometry. TDMAS can be adsorbed at OH sites on hydroxylated Si surfaces at room temperature. Ozone oxidation of the TDMAS-treated Si surface is effective in removing hydroaminocarbon adsorbates introduced during TDMAS adsorption at room temperature. After oxidation by ozone, treatment with H₂O vapor at a substrate temperature of around 160 °C causes regeneration of OH sites for TDMAS adsorption. Cycles involving TDMAS adsorption and ozonization at room temperature followed by H₂O treatment at 160 °C permit the buildup of layers of SiO₂. The amount of residual hydroaminocarbon at the interface between the growing SiO₂ film and the substrate can be reduced with the ozone treated Si surface as a starting surface.     

High-temperature oxidation of silicon nitride-based ceramics by water vapour

Hot-pressed Si₃N₄, sintered Si₃N₄ and three kinds of sialon with different compositions were oxidized in dry air and wet nitrogen gas atmospheres at 1100 to 1350° C and 1.5 to 20 kPa water vapour pressure. All samples were oxidized by both dry air and water vapour at high temperature, and formed oxide films consisting of SiO₂, Y₂Si₂O₇ and Y4A1209. The oxidation rate was in the order sialon > sintered Si₃N₄ > hot-pressed Si3N4. The oxidation rate of sialon increased with increasing Y₂O₃ content, and oxidation kinetics obeyed the usual parabolic law. The oxidation rates in dry air and wet nitrogen were almost the same: the rate in wet nitrogen was unaffected by water vapour pressure above 1.5 kPa. The activation energy was about 800 kJ mol^–1.     

Room temperature plasma oxidation: A new process for preparation of ultrathin layers of silicon oxide, and high dielectric constant materials

In this paper we present basic features and oxidation law of the room temperature plasma oxidation, (RTPO), as a new process for preparation of less than 2 nm thick layers of SiO₂, and high-k layers of TiO₂. We show that oxidation rate follows a potential law dependence on oxidation time. The proportionality constant is function of pressure, plasma power, reagent gas and plasma density, while the exponent depends only on the reactive gas. These parameters are related to the physical phenomena occurring inside the plasma, during oxidation. Metal-Oxide-Semiconductor (MOS) capacitors fabricated with these layers are characterized by capacitance-voltage, current-voltage and current-voltage-temperature measurements. Less than 2.5 nm SiO₂ layers with surface roughness similar to thermal oxide films, surface state density below 3 × 10¹¹ cm^− 2 and current density in the expected range for each corresponding thickness, were obtained by RTPO in a parallel-plate reactor, at 180 mW/cm² and pressure range between 9.33 and 66.5 Pa (0.07 and 0.5 Torr) using O₂ and N₂O as reactive gases. MOS capacitors with TiO₂ layers formed by RTPO of sputtered Ti layers are also characterized. Finally, MOS capacitors with stacked layers of TiO₂ over SiO₂, both layers obtained by RTPO, were prepared and evaluated to determine the feasibility of the use of TiO₂ as a candidate for next technology nodes.     

Transparent, amorphous and organics-free ZnO thin films produced by chemical solution deposition at 150 °C

We have studied the low-temperature processing of ZnO by chemical solution deposition. A transparent, stable precursor solution prepared from zinc acetate dihydrate dissolved in 2-methoxyethanol was spin-coated on SiO_x/Si, soda-lime glass and polymer substrates and heated at 150 °C. Selected thin films deposited on SiO_x/Si were additionally heated at 450 °C.Microstructural and chemical analyses showed that the thin films heated at 150 °C in air were amorphous, contained no organic residues and had a root mean square roughness of 0.7 nm. The films deposited on SiO_x/Si and heated at 450 °C were crystallised and consisted of randomly oriented grains with a diameter of about 20 nm. All thin films were transparent, exhibiting a transmission of over 80% in the visible range. The resistivity of the 120-nm thick ZnO films processed at 150 °C was 57 MΩ cm and upon heating at 450 °C it decreased to 1.9 kΩ cm.     

Simulations of Si and SiO2 etching in SF6 + O2 plasma

Chemical etching of Si and SiO₂ in SF₆ + O₂ plasma is considered. The concentrations of plasma components are calculated using values extrapolated from experimental data. Resulting calculations of plasma components are used for the calculation of Si and SiO₂ etching rates. It is found that the reaction constants for reactions of F atoms with Si atoms and SiO₂ molecules are equal to (3.5 ± 0.1) × 10⁻² and (3.0 ± 0.1) × 10⁻⁴, respectively. The influence of O₂ addition to SF₆ plasma on the etching rate of Si is quantified.     

Investigation of electronic structure of Si nanocrystals and their interface with host matrix in P-doped SiO2:Si and Al2O3:Si nanocomposites

The system of the nanoinclusions of Si in the SiO₂ and Al₂O₃ matrix (SiO₂:Si, Al₂O₃:Si) attracts great attention due to its ability of the luminescence in visible and near-IR range of spectrum. The influence of the P ion alloying on the electronic structure of nanocomposites was investigated. The P ion doping and post-annealed at T = 1000 °C (2 h) results in the enhancement of the photoluminescence (PL) peak connected with the Si nanocrystals. The electronic structure was investigated by X-ray photoelectron spectroscopy (XPS) and high-resolution electron energy losses spectroscopy (HREELS) methods. Ion surface modification and annealing forms the special nanostructure with Si nanocrystals in SiO₂ and Al₂O₃ matrix having high density of interfaces with special atomic structure and various degree of oxidation of Si atoms on the boundaries. HREELS investigations show that the P ion doping increases the probability of interband transitions in SiO₂:Si and Al₂O₃:Si composites.     

Oxide and interface charges in thin SiO2 films thermally grown on RF plasma hydrogenated silicon

A study of the defect centres, related to oxide charge and interface traps, induced in thin SiO₂ layer by technological procedures has been made. Thermal oxidation of Si was performed in dry O₂ at a temperature of 850°C. The Si cleaning procedures included dry hydrogen plasma treatment at different substrate temperatures and standard RCA wet cleaning. Characterization of defects was performed by analyzing the frequency dispersion of the capacitance-voltage characteristics. The origin of the defects was assessed by analysis of the IR spectra through computer simulation of the oxide structure and AFM images.     

Metal-induced negative oxide charge detected by an alternating current surface photovoltage in thermally oxidized Fe-contaminated n-type Si (001) wafers

The atomic-bridging type negative oxide charge in SiO₂ is investigated using the Fe-contaminated (001) surface of n-type Si wafers. The investigation is done on the basis of a chemical analysis and a method in which the frequency-dependent alternating current (AC) surface photovoltage (SPV) is measured. At room temperature, an AC SPV appears and gradually increases, saturating after approximately one day (with an Fe concentration on the Si surface of 4.0 × 10¹³ atoms/cm²). The AC SPV eventually becomes inversely proportional to frequency except at very low frequencies (< 10 Hz) corresponding to weak or strong inversion, indicating that the negative Fe induced oxide charge appears in the form of a (FeOSi)⁻ network. Also, in Fe-contaminated n-type Si(001) surfaces thermally oxidized at between 550 and 650 °C for 60 min, strong inversion is unquestionably observed, proving that the (FeOSi)⁻ network survives and that most of the added Fe has segregated into the region closest to the surface of the thin SiO₂ film. At 850 °C and/or for long oxidation times, the AC SPV decreases and ultimately disappears, implying that the (FeOSi)⁻ network has collapsed and may have changed into Fe₂O₃. A model for the metal-induced negative oxide charge in the conventional oxide charge diagram is proposed.     

Plasma oxidation of Al thin films on Si substrates

In this study, Al thin films deposited on silicon wafers by direct current magnetron sputtering were oxidized under radio frequency 13.56 MHz O₂ plasma at temperatures up to 550 °C. During oxidation, plasma powers as well as oxidation temperature and time were varied to investigate the oxidation behavior of the Al films. X-ray photoelectron spectroscopy and Auger electron spectroscopy results show that the apparent alumina could be observed after O₂ plasma treatment with powers above 200 W as well as at temperatures above 250 °C. However, no alumina increment could be discerned after individual either heat treatment at 550 °C or plasma treatment at room temperature. The thickness of alumina layers increased remarkably with plasma power and could reach about 60 nm when undergone 400 W O₂ plasma treatment at 550 °C for 2 h. Moreover, the thickness of alumina increased parabolically with time during plasma oxidation aided by thermal treatment. The deduced activation energy of such plasma oxidation was 19.1 ± 0.5 kJ/mol.     

Effect of N2O/SiH4 flow ratios on properties of amorphous silicon oxide thin films deposited by inductively-coupled plasma chemical vapor deposition with application to silicon surface passivation

Silicon oxide (SiO_x) thin films have been deposited at a substrate temperature of 300 °C by inductively-coupled plasma chemical vapor deposition (ICP-CVD) using N₂O/SiH₄ plasma. The effect of N₂O/SiH₄ flow ratios on SiO_x film properties and silicon surface passivation were investigated. Initially, the deposition rate increased up to the N₂O/SiH₄ flow ratio of 2/1, and then decreased with the further increase in N₂O/SiH₄ flow ratio. Silicon oxide films with refractive indices of 1.47-2.64 and high optical band-gap values (>3.3 eV) were obtained by varying the nitrous oxide to silane gas ratios. The measured density of the interface states for films was found to have minimum value of 4.3 × 10¹¹ eV⁻¹ cm⁻². The simultaneous highest τ_eff and lowest density of interface states indicated that the formation of hydrogen bonds at the SiO_x/c-Si interface played an important role in surface passivation of p-type silicon.     

Low refractive index silicon oxide coatings at room temperature using atmospheric-pressure very high-frequency plasma

Low refractive index silicon oxide films were deposited using atmospheric-pressure He/SiH₄/CO₂ plasma excited by a 150-MHz very high-frequency power. Significant increase in deposition rate at room temperature could prevent the formation of dense SiO₂ network, decreasing refractive index of the resulting film effectively. As a result, a silicon oxide film with the lowest refractive index, n = 1.24 at 632.8 nm, was obtained with a very high deposition rate of 235 nm/s. The reflectance and transmittance spectra showed that the low refractive index film functioned as a quarter-wave anti-reflection coating of a glass substrate.     

Characterization of SiO2 and TiO2 films prepared using rf magnetron sputtering and their application to anti-reflection coating

Preparation of TiO₂ and SiO₂ films for optical applications was attempted using conventional rf magnetron sputtering in the sputtering ambient with various O₂/Ar+O₂ ratios and at substrate temperatures between room temperature and 400 °C. X-ray photoelectron spectroscopy (XPS) and optical spectroscopy investigations indicated that oxygen addition in the sputtering ambient was essential for growing TiO₂ films with stoichiometric compositions and good transmittance, while SiO₂ films had a stoichiometric composition of O/Si ratio=2.1-2.2 and were highly transparent in the visible wavelength region, independent of gas composition in the growing ambient. It was also identified from scanning electron microscope (SEM), atomic force microscope (AFM) and Fourier transform infrared spectroscopy (FTIR) measurements that the structural characteristics of both TiO₂ and SiO₂ films were significantly improved with O₂ addition in the sputtering ambient, showing smoother surface morphologies and higher resistances to water absorption when compared with films grown without O₂ addition. Heating of the substrate between 200 and 400 °C considerably increased the refractive index of TiO₂ layers, resulting in dense structures along with an improvement of crystallinity. For optical applications, AR coatings composed of 2-4 multi-layers on glass were designed and manufactured by stacking in turn the SiO₂ and TiO₂ films at room temperature and O₂/Ar+O₂=10%, and the performance of the produced coatings was compared with simulation results.     

SiO2 film deposition on the inner wall of a narrow polymer tube by a capacitively coupled μplasma

SiO₂ thin films were deposited on the inner wall of a narrow commercial poly(propylene) tube with inner/outer diameters of 1.0 mm/3.0 mm by plasma-enhanced chemical vapor deposition using He or Ar carrier gases and tetraethoxysilane (TEOS)/O₂ feedstock gases at high pressures from 30 kPa to atmospheric pressure and at room temperature. A glow μplasma was generated inside the tube by a radio frequency (RF 13.56 MHz) capacitively coupled discharge. X-ray photoelectron spectra and infrared spectra revealed that the inner surface of the plasma-treated tube was covered by a SiO₂ film. Scanning electron microscopy images indicated that the film produced by He/TEOS/O₂ μplasma had a smooth surface whereas the surface of the film produced by Ar/TEOS/O₂ μplasma appeared granulated. Typical deposition rates of approximately 300 nm/min were obtained by He/TEOS/O₂ μplasma at atmospheric pressure and a RF power of 11 W.     

Nucleation study of hydrogenated microcrystalline silicon (μc-Si:H) films deposited by VHF-ICP

Nucleation in the initial stage of hydrogenated microcrystalline silicon (μc-Si:H) film deposition by VHF inductivity-coupled plasma (ICP) has been investigated. When the SiH₄ concentration (R_SiH4 = [SiH₄] / ([SiH₄] + [H₂])) is 6%, the crystallization in the initial 1.1-2.4 nm film deposition is observed at the substrate temperature of 320 °C, while it is decreased to 150 °C by reducing the R_SiH4 to 3%. Furthermore, the nucleation is significantly promoted by H₂ plasma pretreatment as long as 90 s prior to μc-Si:H film deposition. The crystallinity was improved from 33 to 54% and the grain density was increased from 8.0 × 10¹⁰ to 1.7 × 10¹¹ cm^− 2 by the pretreatment. We confirmed no significant change in SiO₂ surface micro roughness after the H₂ plasma pretreatment. The chemical bond states at the SiO₂ surface before film deposition play an important role in nucleation.     

Thermal treatment effects on interfacial layer formation between ZrO2 thin films and Si substrates

This paper describes the growth condition of stoichiometric ZrO₂ thin films on Si substrates and the interfacial structure of ZrO₂ and Si substrates. The ZrO₂ thin films were prepared by rf-magnetron sputtering from Zr target with mixed gas of O₂ and Ar at room temperature followed by post-annealing in O₂ ambient. The stoichiometric ZrO₂ thin films with smooth surface were grown at high oxygen partial pressure. The thick Zr-free SiO₂ layer was formed with both Zr silicide and Zr silicate at the interface between ZrO₂ and Si substrate during the post-annealing process due to rapid diffusion of oxygen atoms through the ZrO₂ thin films. After post annealing at 650-750 °C, the multi-interfacial layer shows small leakage current of less than 10⁻⁸ A/cm² that is corresponding to the high-temperature processed thermal oxidized SiO₂.     

Atmospheric pressure PECVD of SiO2 thin film at a low temperature using HMDS/O2/He/Ar

SiO₂-like thin films were deposited at a low temperature (< 50 °C) by a remote-type, atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) using a pin-to-plate-type, dielectric barrier discharge with gas mixtures containing hexamethyldisilazane (HMDS)/O₂/He/Ar. The film characteristics were investigated according to the HMDS and O₂ flow rates. To obtain a more SiO₂-like thin film, an adequate combination of HMDS and oxygen flow rates was required to remove the -(CH₃)_x bonding in the HMDS and to oxidize the Si in HMDS effectively. At the optimized flow rates, the surface roughness of the SiO₂-like thin film was also the lowest. By using HMDS (50 sccm) and O₂ (500 sccm) flow rates in the gas mixture of HMDS/O₂/He (2 slm)/Ar (600 sccm), SiO₂-like thin films with a low impurity (< 6.35% C) were obtained at a deposition rate of approximately 10.7 nm/min.     

Sol-gel preparation of near-infrared broadband emitting Er-doped SiO2-Ta2O5 nanocomposite films

This article reports a study on the preparation, densification process, and structural and optical properties of SiO₂-Ta₂O₅ nanocomposite films obtained by the sol-gel process. The films were doped with Er³⁺, and the Si:Ta molar ratio was 90:10. Values of refractive index, thickness and vibrational modes in terms of the number of layers and thermal annealing time are described for the films. The densification process is accompanied by OH group elimination, increase in the refractive index, and changes in film thickness. Full densification of the film is acquired after 90 min of annealing at 900 °C. The onset of crystallization and devitrification, with the growth of Ta₂O₅ nanocrystals occurs with film densification, evidenced by high-resolution transmission electron microscopy. The Er³⁺-doped nanocomposite annealed at 900 °C consists of Ta₂O₅ nanoparticles, with sizes around 2 nm, dispersed in the SiO₂ amorphous phase. The main emission peak of the film is detected at around 1532 nm, which can be assigned to the ⁴I_13/2 → ⁴I_15/2 transition of the Er³⁺ ions present in the nanocomposites. This band has a full width at half medium of 64 nm, and the lifetime measured for the ⁴I_13/2 levels is 5.4 ms, which is broader compared to those of other silicate systems. In conclusion, the films obtained in this work are excellent candidates for use as active planar waveguide.     

Ellipsometric characterization of SiOx films with embedded Si nanoparticles

In this work we present results on the ellipsometric study of SiO_x films in the spectral range of 280-820 nm. The films were deposited by vacuum thermal evaporation of SiO onto Si substrates heated at 150 °C. To stimulate the formation of silicon clusters in the oxide matrix the films were annealed at temperatures 700, 1000 and 1100 °C in argon for 5, 15 and 30 min. By applying the Bruggeman effective-medium approximation theory and using multiple-layer optical models, from the ellipsometric data analysis the thickness, complex refractive index and composition of the films, as well as the size of the embedded Si nanocrystallites have been determined. Atomic-force microscopy imaging showed a very smooth surface, the roughness value of which correlated well with the top-layer thickness, determined from the ellipsometric data analysis.