Suppression of hydrogen-ion drift into underlying layers using plasma deposited silicon oxynitride film during high-density plasma chemical vapor deposition

Hydrogen ions drifting into underlying layers during HDP-CVD were successfully suppressed by the insertion of plasma deposited silicon oxynitride (p-SiO_xN_yH_z) film, and the hydrogen-trapping mechanism was clarified. The hydrogen ions are trapped in bonding states, not in interstitial ones. After HDP-CVD undoped silicate glass (HDP-USG) film deposition on the p-SiO_xN_yH_z film, the decrease of the dangling bonds in the p-SiO_xN_yH_z film measured by ESR was much lower than the increase of the desorbed hydrogen concentration measured by TDS. These results suggest that new hydrogen-trapping sites are mainly generated from ESR-inactive bonds by drifted hydrogen ions and atomic hydrogen during HDP-CVD.     

Fabrication of nanocrystalline silicon carbide thin film by helicon wave plasma enhanced chemical vapour deposition

Nanocrystalline cubic silicon carbide thin films have been fabricated by helicon wave plasma enhanced chemical vapour deposition on Si substrates using the mixture of SiH₄, CH₄, and H₂ at a low substrate temperature of 300 °C. The infrared absorption spectroscopy analyses and microstructural characteristics of the samples deposited at various magnetic fields indicate that the high plasma intensity in helicon wave mode is a key factor to the success of growing nanocrystalline silicon carbide thin films at a relative low substrate temperature. Transmission electron microscopy measurements reveal that the films consist of silicon carbide nanoparticles with an average grain size of several nanometers, and the light emission measurements show a strong blue photoluminescence at room temperature, which is considered to be caused by the quantum confine effect of small size silicon carbide nanoparticles.     

Study of plasma enhanced chemical vapor deposition of ZnO films by non-thermal plasma jet at atmospheric pressure

Plasma enhanced chemical vapor deposition using a non-thermal plasma jet was applied to deposition of ZnO films. Using vaporized bis(octane-2,4-dionato)zinc flow crossed by the plasma jet, the deposition rate was as high as several tens of nm/s. From the results of infrared spectra, the films deposited at the substrate temperature T_sub = 100 °C contained a significant amount of carbon residue, while the films prepared at T_sub = 250 °C showed less carbon fraction. The experimental results confirmed that the plasma jet decomposed bis(octane-2,4-dionato)zinc in the gaseous phase and on the substrate, and that there should be the critical T_sub to form high-quality ZnO films in the range from 100 to 250 °C.     

Tunnelling through diamond-like carbon nanofilms deposited by electron-beam-induced deposition

The tunnelling properties in metal/diamond-like carbon (DLC)/semiconductor junctions and structural characteristics of thin DLC films produced using different electron beam conditions were studied. We show that under the same electron dose conditions, thicker DLC films were obtained using lower accelerating voltages (2 kV) than when using higher accelerating voltage (20 kV). However, under the settings used the thicker films showed worse insulating performance than the thinner films. We attribute this effect to the variation of tunnelling barrier height in DLC deposited using different accelerating voltages. DLC films with a tunnelling barrier height of up to 3.12 eV were obtained using a 20 kV electron-beam, while only 0.73 eV was achieved for 2 kV DLC films. The X-ray photoemission spectra of the C 1s core level in these films reveal components at 284.4 ± 0.1 eV and 285 ± 0.1 eV, which were identified as the sp² and sp³ hybrid forms of carbon. The sp³/sp² concentration ratio increased with increasing electron beam accelerating voltage. We show how this effect is responsible for the barrier height variation.     

Localized high-rate deposition of zinc oxide films at atmospheric pressure using inductively coupled microplasma

Linear transparent zinc oxide films were fabricated using an inductively coupled microplasma jet generated in argon under atmospheric conditions. The films were formed by the sputtering and melting of a zinc filament placed inside the plasma. Film growth rates varied between 10 to 30 nm/s for input powers between 20 and 30 W. Film roughness below 20 nm and optical transmittances up to 90% in the visible were obtained while the sheet resistances ranged between 2 × 10⁴ and 1 × 10⁵Ω/□. The presented technique may allow high-rate, localized, fabrication of functional ZnO films for optoelectronic applications.     

Thin cobalt oxide films for catalysis deposited by plasma-enhanced metal-organic chemical vapor deposition

The plasma-enhanced metal-organic chemical vapor deposition was used to prepare thin films of cobalt oxide starting with cyclopentadienyldicarbonyl-cobalt(I) (CpCo(CO)₂) mixed with argon and oxygen. The films were characterized by Raman and Fourier transform infrared spectroscopies, electron diffraction, and energy dispersive X-ray microanalysis. Their thickness was estimated by ellipsometric measurements. Catalytic properties of the films were tested in oxidation of n-hexane. It has been found that spinel-type Co₃O₄ nanoclusters with a crystallite size of 4-6 nm are formed in the deposits. Amorphous carbon and amorphous CoO_x phases are also observed in the films. The content of these phases depends on the molar fraction of oxygen in the gas mixture. Preliminary catalytic tests have shown that precalcined Cr-Al steel carrier covered by the plasma-deposited films reveals much higher catalytic effect then the non-deposited substrate.     

ITO thin films deposited by advanced pulsed laser deposition

Indium tin oxide thin films were deposited by computer assisted advanced PLD method in order to obtain transparent, conductive and homogeneous films on a large area. The films were deposited on glass substrates. We studied the influence of the temperature (room temperature (RT)-180 °C), pressure (1-6 × 10^− 2 Torr), laser fluence (1-4 J/cm²) and wavelength (266-355 nm) on the film properties. The deposition rate, roughness, film structure, optical transmission, electrical conductivity measurements were done. We deposited uniform ITO thin films (thickness 100-600 nm, roughness 5-10 nm) between RT and 180 °C on a large area (5 × 5 cm²). The films have electrical resistivity of 8 × 10^− 4 Ω cm at RT, 5 × 10^− 4 Ω cm at 180 °C and an optical transmission in the visible range, around 89%.     

Effect of impinging ion energy on the substrates during deposition of SiOx films by radiofrequency plasma enhanced chemical vapor deposition process

Radiofrequency (13.56 MHz) plasma enhanced chemical vapor deposition process is used for deposition of SiO_x films on bell metal substrates using Ar/hexamethyldisiloxane/O₂ glow discharge. The DC self-bias voltage developed on the substrates is observed to be varied from − 35 V to − 115 V depending on the RF power applied to the plasma. Plasma potential measurements during film deposition process are carried out by self-compensated emissive probe. The deposited films are characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), nanoindentation, nano-scratch test and thermogravimetric analysis. The characterization results show strong dependency of the SiO_x films properties on the energy of the ions impinging on the substrates during deposition. Analysis of Raman spectra indicates an increase in vitreous silica content and reduction in defective Si-O-Si chemical structure in the deposited SiO_x films with increasing ion energy impinging on the substrates. The increase in inorganic (Si and O) content in the SiO_x films is further confirmed from XPS analysis. The growth of SiO_x films with more inorganic content and defect free chemical structure apparently contribute to the increase in their hardness and scratch resistance behavior. The films show higher thermal stability as the energy of the ions arriving at substrates increases with DC self-bias voltage. The possibility of using SiO_x films for surface protection of bell metal is also explored.     

ZnO nanostructured film deposition using the separated pulsed laser deposition (SPLD) assisted by electric and magnetic drift motion

We have developed the separated pulsed laser deposition (SPLD) technique to prepare high quality ZnO based films exhibiting uniform and droplet-free properties. This SPLD consists of an ablation chamber and a deposition chamber which can be independently evacuated under different ambient gases.The gas species and the pressures in both chambers can be arbitrarily chosen for the specific deposition such as nanostructured films and nanoparticles. The ablation chamber is a stainless steel globe and the deposition chamber is a quartz tube connected to a metallic conic wall with an orifice. We used a KrF excimer laser with λ = 248 nm and 25 ns pulse duration. The different gas conditions in two chambers allow us to realize optimal control of the plasma plume, the gas phase reaction and the film growth by applying the bias voltage between the conic wall and the substrate under the magnetic field. We can expect that at appropriate pressures the electric and magnetic field motion (E × B azimuthal drift velocity) gives significant influences on film growth.We have deposited ZnO thin films at various pressures of ablation chamber (Pab) and deposition chamber (Pd). The deposition conditions used here were laser fluence of 3 J/cm², laser shot number of 30,000, Pab of 0.67-2.67 Pa (O₂ or Ar), Pd of 0.399-2.67 Pa (O₂), and substrate temperature of 400 °C. Particle-free and uniform ZnO films were obtained at Pab of 0.67 Pa (Ar) and Pd of 1.33 Pa (O₂). The ZnO film showed high preferential orientation of (002) plane, optical band gap of 2.7 eV, grain size of 42 nm and surface roughness of 1.2 nm.     

Aging of silicon-based dielectric coatings deposited by plasma polymerization

Silicon-based dielectric coatings were deposited from tetravinylsilane or a mixture of tetravinylsilane with oxygen gas by pulsed plasma. The coatings in the form of a-SiC:H or a-SiOC:H alloy were stored at ambient conditions for 800 h to investigate aging effects. The SiH, SiC, and CH_x species in the plasma polymer film were identified as responsible for strong oxidation of the deposited material. The increased oxygen concentration up to 19 at.% in the dielectric coatings resulted in a decrease of the refractive index. Oxygen concentrations > 10 at.% resulted in reduction of mechanical properties of dielectric coatings deposited at powers ≥ 2.5 W. Suitable deposition conditions were deduced to reduce aging effects.     

Dual comb-type electrodes as a plasma source for very high frequency plasma enhanced chemical vapor deposition

Dual comb-type electrodes were developed as a plasma source in very high frequency (VHF) plasma enhanced chemical vapor deposition system for uniform deposition of silicon films. Two VHF powers introduced to each electrode produced parallel plasma bands, and their positions could be changed by manipulating the phase difference between the supplied VHF waves. Excitation frequency was 80 MHz. The maximum plasma density using this plasma source was 1.5 × 10¹⁰/cm³ and the electron temperature was around 2 eV with input power of 2.5 kW, which were measured by double tip Langmuir probe. The uniformity of deposition rate under ± 13% was achieved on 1 m² area with optimal plasma conditions.     

Properties of aluminum oxide thin films deposited by pulsed laser deposition and plasma enhanced chemical vapor deposition

The chemical, structural, mechanical and optical properties of thin aluminum oxide films deposited at room temperature (RT) and 800 °C on (100) Si and Si-SiO₂ substrates by pulsed laser deposition and plasma enhanced chemical vapor deposition are investigated and compared. All films are smooth and near stoichiometric aluminum oxide. RT films are amorphous, whereas γ type nano-crystallized structures are pointed out for films deposited at 800 °C. A dielectric constant of ∼ 9 is obtained for films deposited at room temperature and 11-13 for films deposited at 800 °C. Young modulus and hardness are in the range 116-254 GPa and 6.4-28.8 GPa respectively. In both cases, the results show that the deposited films have very interesting properties opening applications in mechanical, dielectric and optical fields.     

The effect of argon dilution on deposition of microcrystalline silicon by microwave plasma enhanced chemical vapor deposition

Microwave plasma-enhanced chemical vapor deposition (PECVD) is a very promising method for industrial scale fabrication of microcrystalline silicon solar cells since the technique is well applicable for large areas, and high deposition rates can be obtained. We have investigated the effect of Ar dilution on the growth process and the material properties of microcrystalline silicon. The major benefit of Ar addition in the MWPECVD process, using H₂ and SiH₄ as reactant gases, is an improved stabilization of the plasma, in particular at low pressure and MW power. We show, however, that material properties of the microcrystalline silicon layers deteriorate if we partly substitute H₂ by Ar during the deposition. The density of the layers - as expressed by the refractive index - decreases, and the defect density (measured by Fourier transform photocurrent spectroscopy) increases with increasing Ar flow. Investigation of the plasma by optical emission study shows that Ar atoms play a very active role in the dissociation processes of H₂ and SiH₄. Substitution of H₂ by Ar decreases the SiH^? emission and increases the Si^? emission. On the other hand, the H_α/H_β ratio increases upon substitution of H₂ by Ar. The latter effect shows that Ar addition does not lead to higher electron temperatures and we conclude that the changes of SiH^? and Si^? emissions are due to dissociation of SiH₄ by Ar^? (quenching reactions). The precise role of Ar in MWPECVD of microcrystalline silicon needs further investigation, but we conclude that the usage of this gas should be minimized in order to maximize the quality of the silicon layers.     

Thin molybdenum oxide films produced by molybdenum pentacarbonyl 1-methylbutylisonitrile with plasma-assisted chemical vapor deposition

Molybdenum oxide thin films were prepared by plasma-enhanced chemical vapor deposition of molybdenum pentacarbonyl 1-methylbutylisonitrile. This precursor is an interesting alternative for the commonly used molybdenum hexacarbonyl, because the substance is liquid at room temperature, offers sufficient volatility and stability to air and water. The film growth was monitored in situ by a soft X-ray reflectivity measurement. The films were deposited with different plasma gases (hydrogen and oxygen) under different conditions and analysed by Auger electron spectroscopy, X-ray diffraction and spectral ellipsometry.     

SiO2 thin film deposition on the inner surface of a poly(tetra-fluoroethylene) narrow tube by atmospheric-pressure glow microplasma

SiO₂ thin films were deposited on the inner surfaces of a commercial poly(tetrafluoroethylene) narrow tube with an inner diameter of 0.5 mm using tetraethoxysilane/O₂ feedstock gases and He carrier gas by atmospheric-pressure microplasma-enhanced chemical vapor deposition. A glow microplasma was generated inside the tube by radio frequency (RF) capacitively coupled discharge. X-ray photoelectron spectroscopy spectra showed that the tube inner surface was covered by a SiO₂ thin film. Transparent SiO₂ thin films were obtained with a deposition rate of 230 nm/min at an RF power of 6 W and substrate temperature of 100 °C. The wettability of the SiO₂-coated tube was about 3 times as large as that of an untreated sample tube.     

Mechanical properties of carbon-modified silicon oxide barrier films deposited by plasma enhanced chemical vapor deposition on polymer substrates

Cohesive and adhesive properties of silicon oxide barrier coatings deposited from an oxygen/hexamethyldisiloxane gas mixture by plasma enhanced chemical vapor deposition, with controlled incorporation of carbon on 12 μm thick polyethylene terephtalate films were investigated. The reactor was equipped with a 2.45 GHz slot antenna plasma source and a 13.56 MHz-biased substrate holder. The two plasma sources were operated separately or in a dual mode. It was found that no or negligible internal stresses were introduced in the silicon oxide coatings as long as the increase of energy experienced by the film was compensated by the densification of the oxide. For a range of process parameters and carbon content on the changes of the crack onset strain, adhesion, and cohesion were found to be similar. Generally a high crack onset strain or good adhesion and cohesion were measured for films with an increased carbon content, although this was obtained at the expense of the gas barrier performance. Promising approaches towards high-barrier thin films with good mechanical integrity are proposed, based on coatings with a gradient in the carbon content and in the mechanical properties, on nano-composite laminates, and on organo-silane treatments.     

In situ Fourier transform P-polarized infrared reflection absorption spectroscopic investigation of an interface properties of SiO2/Si(100) deposited using electron cyclotron resonance microwave plasma at room temperature

Amorphous SiO₂ films have been deposited onto the Si substrate, without heating, using sputtering-type electron cyclotron resonance (ECR) microwave plasma. In situ Fourier transform P-polarized infrared reflection absorption spectroscopy (ISFT-PIRRAS) has been used to study the properties of a-SiO₂/Si interface. The results from ISFT-PIRRAS monitoring indicated that the interface stress led to significant distortion in the local structure, which resulted in the broadening of a transverse optical mode (TO₃) located at 1050 cm⁻¹. The interface stress decreased with increased film thickness. In addition, the longitudinal optical phonon mode (LO₃, located at 1223 cm⁻¹) related to TO₃ mode was observed due to Berreman effect [B. Harbecke, Appl. Phys. A: Solids Surf. 38 (1985) 263]. This phonon mode is very sensitive to SiO₂ film thickness, which enables it to be used to detect and characterize ultra thin SiO₂ film. When the film thickness is over 30 nm, a non-linear dependence of the intensity of LO₃ mode on film thickness was observed. However, the TO₃ mode has a near linear dependence on film thickness. Thus, it is more accurate and suitable to detect thick film by monitoring TO₃ mode intensity.     

Influences of deposition and crystallization kinetics on the properties of silicon films deposited by low-pressure chemical vapour deposition from silane and disilane

The paper deals with the properties of silicon films obtained by low-pressure chemical vapour deposition (LPCVD). Two gaseous sources characterized by different deposition temperatures, i.e. disilane Si₂H₆ (420-520 °C) and silane SiH₄ (520-750 °C), was studied in order to understand the influences of deposition and crystallization kinetics on silicon film properties. Thus, the deposition of amorphous, semi-crystallized and polycrystalline silicon films was related to “volume random” and “surface columnar” crystallization phenomena, highlighting a linear relationship between the refractive index and the polysilicon volume fraction and, showing complex residual stress dependency with process conditions. Finally, by introducing the ratio V_d/V_c between the deposition and crystallization rates as a major parameter, different deposition behaviours and related semi-empirical relationships were defined in order to characterize fully the various properties of LPCVD silicon films (microstructure, polysilicon volume fraction, refractive index and residual stress) according to the chosen gaseous source, silane or disilane.     

Visible electroluminescence from silicon nanoclusters embedded in chlorinated silicon nitride thin films

Visible electroluminescence (EL) has been obtained from devices with active layers of silicon nanocrystals embedded in chlorinated silicon nitride (Si-nc/SiN_x:Cl) thin films, deposited by remote plasma enhanced chemical vapour deposition, using SiCl₄/NH₃/H₂/Ar. The active nc-Si/SiN_x:Cl film was sandwiched between Al contacts and a transparent conductive contact of ZnO_x:Al deposited by the pyrosol process. White EL centred at around 600 nm was observed, with a turn-on voltage of 5 V, and the intensity increasing as a function of voltage. Recombination between electron-hole pairs generated in the Si-nc by electron impact ionization is proposed as the EL mechanism.     

Effect of deposition process parameters on resistivity of metal and alloy films deposited using anodic vacuum arc technique

Thin solid films of copper, aluminum and nichrome have been deposited on glass substrates with thickness ranging from 20 nm to 200 nm, using the anodic vacuum arc deposition technique. Electrical resistivity and average grain size of deposited thin films have been measured and their dependence on the deposition process parameters has been investigated. Thickness dependence of resistivity has also been compared with numerically generated results using Fuchs-Sondheimer theory and Mayadas-Shatzkes theory which has been found to be in good agreement for film thickness greater than 80 nm. The resistivity values of Cu, Al and NiCr has been found to take a minimum value (approaching that of corresponding bulk material) of 80 A arc current and a substrate bias of around − 50 V.