Effect of silane flow rate on structural,electrical and optical properties of silicon thin films grown by VHF PECVD technique

Hydrogenated silicon thin films deposited by VHF PECVD process for various silane flow rates have been investigated. The silane flow rate was varied from 5 sccm to 30 sccm, maintaining all other parameters constant. The electrical, structural and optical properties of these films were systematically studied as a function of silane flow rate. These films were characterized by Raman spectroscopy, Scanning Electron Microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy and UV–visible (UV–Vis) spectroscopy. Different crystalline volume fraction (22%–60%) and band gap (∼1.58 eV–∼1.96 eV) were achieved for silicon thin films by varying the silane concentration. A transition from amorphous to nanocrystalline silicon has been confirmed by Raman and FTIR analysis. The film grown at this transition region shows the high conductivity in the order of 10⁻⁴ Ω⁻¹ cm⁻¹.     

Electrochemical evaluation of the reliability of plasma-polymerized methylcyclohexane films

Plasma-polymerized thin films are developed for electronic devices to satisfy the important requirement of a low dielectric constant in the interlayer dielectrics. Three types of methylcyclohexane coatings are deposited on copper as interlayer dielectrics by plasma-enhanced chemical vapor deposition at three different deposition temperatures. The coating performance is evaluated by electrochemical impedance spectroscopy and potentiodynamic polarization testing in a 3.5 wt.% NaCl solution. The coatings are also analyzed by surface analyses, including atomic force microscopy, Fourier transform infrared spectroscopy, and contact angle measurements. The electrochemical behavior of the coatings is improved by increasing the deposition temperature. The methylcyclohexane films on the copper substrate show high protective efficiency, charge transfer resistance and low porosity, which indicate that the coating performance increased with increasing deposition temperature. Atomic force microscopy, Fourier transform infrared spectroscopy and contact angle measurements confirm the enhanced formation of C-H, C-C, and CC stretching configurations, improved surface roughness and wettability with increasing deposition temperature.     

Hydrogen peroxide vapor sensor using metal-phthalocyanine functionalized carbon nanotubes

We have developed a process for preparation of composites by blending and ultrasonification of multi-walled carbon nanotubes with metal-phthalocyanines and have used the same as very selective and sensitive sensor for detection of H₂O₂ vapors. A combination of sensors made from composites of cobalt-phthalocyanine and copper-phthalocyanine with multiwall carbon nanotubes has been found to show opposite conductivities to H₂O₂ vapors while the pair shows similar response to other chemical vapors. This unusual behavior makes this paired sensor as a reliable method to selectively identify the presence of H₂O₂ vapors with response and recovery times of few seconds. Our developed sensors work at room temperature and show resistivity in the range of 10⁴ to 10⁵ Ω cm. They can be employed for detection of H₂O₂ based explosives, to monitor levels of H₂O₂ in industrial units and other applications.     

Surface phonon polariton of wurtzite AlN thin film grown on sapphire

Polarized infrared attenuated total reflection (ATR) with Otto configuration was employed to access the surface phonon polariton (SPP) characteristics of wurtzite aluminium nitride (AlN) thin film grown on sapphire (Al₂O₃) substrate. The surface and guided wave polariton dispersion curves for the studied structure were derived by taking into account thin film and substrate anisotropy. From the p-polarized ATR spectrum, one prominent peak corresponds to the SPP mode of AlN thin film was clearly observed at 824 cm⁻¹. In addition, four guided wave modes were also detected at 467, 593.5, 633.5 and 668 cm⁻¹. For the s-polarized ATR spectrum, five pronounced dips associated to the guided wave modes were detected. The obtained results were in good agreement with the ATR spectra calculated based on the standard transfer matrix formulation. The origin of the observed ATR dips were verified from the dispersion curves simulated based on air/AlN epilayer/AlN buffer layer/Al₂O₃ model.     

Stability of plasma-deposited amorphous hydrogenated boron films

An investigation of radio-frequency plasma-deposited amorphous hydrogenated boron films was conducted in order to determine the influence of the substrate temperature T_S and d.c. self-bias U_SB on the physical properties and film stability. We found three different regions of stability depending on T_S and U_SB. Films prepared at high d.c. self-bias and substrate temperature are mechanically unstable due to internal stress. They peel off during the deposition process or on first contact with the ambient atmosphere. Films deposited at low self-bias and substrate temperature were found to be chemically unstable. Exposed to the ambient atmosphere, they undergo chemical changes and incorporate large amounts of oxygen and carbon. These two different regions of instability are separated by chemically and mechanically stable films. The chemical composition and the structural properties of chemically stable and unstable films were determined by Fourier transform infrared spectroscopy, X-ray induced photoelectron spectroscopy and ion beam analysis. These measurements show that chemical stability correlates with the boron density. Chemically stable films reveal densities of more than 68% up to 99% of the density of crystalline boron. In general, elevated substrate temperature and ion energy cause densification of the films and increasing internal stress. Densification leads to chemical stability, while internal stress is the reason for mechanical instability.     

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.     

Effects of oxygen percentage on the growth of copper oxide thin films by reactive radio frequency sputtering

Copper oxide thin films were deposited onto glass substrates by reactive radio frequency magnetron sputtering at various oxygen percentage flow rates R(O₂). X-ray diffraction analysis revealed that nanocrystallite copper oxide thin films with cubic, tetragonal, and monoclinic structure were formed at R(O₂) values of 10%, 20%, and ≥30%, respectively. Energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy were used to verify the copper oxides phases. With increased R(O₂), the root mean square surface roughness of the deposited films decreased from 4.82 nm to 1.78 nm. Moreover, both the band gap type and value changed with increased R(O₂). For R(O₂) at 20%, single phase tetragonal Cu₄O₃ thin film with a direct band gap of 2.20 eV was formed. For R(O₂) ≥ 30%, single phase monoclinic CuO thin films with an indirect band gap of 1.20 eV–1.25 eV were formed. In addition, conductive copper oxide thin films tended to form for R(O₂) < 30%, whereas insulator oxide thin films tended to form for R(O₂) ≥ 30%. Through this study, the crystallization behavior, the band gap, and the resistivity properties of the deposited copper oxide thin films as a function of the R(O₂) were obtained.     

The formation of a SiOx interfacial layer on low-k SiOCH materials fabricated in ULSI application

The characterizations of SiOCH films using oxygen plasma treatment depends linearly on the O₂/CO flow rate ratio. According to the results of Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses, it was found that the carbon composition decreases with increasing O₂/CO flow rate ratio, because more carbon in the Si–O–C and Si–CH₃ bonds on the film surface would be converted by oxygen radicals. It was believed that the oxygen plasma could oxidize the SiOCH films and form a SiO_x interfacial capping layer without much porosity. Moreover, the result of FTIR analysis revealed that there was no water absorbed on the film. A SiO₂-like capping layer formed at the SiOCH film by the O₂/CO flow rate ratio of 0.75 had nearly the same dielectric properties from the result of capacitance–voltage (C–V) measurement in our research.     

Composite Ag/C:H:N films prepared by planar magnetron deposition

Composite Ag/C:H:N films were deposited by means of an unbalanced magnetron operated in a gas mixture of nitrogen and n-hexane. Composition of the films was controlled by electric power delivered to the magnetron and by ratio of nitrogen and n-hexane in the working gas mixture. The films were characterized using transmission electron microscopy, by the absorption spectra in visible and near infrared regions and by Fourier transform infrared spectroscopy. Immediately after film deposition and without breaking vacuum (in situ) corresponding vibration infrared spectra were scanned and their evolution during ageing of the films was monitored. Wettability as determined from water contact angle was improved with raising nitrogen contents, i.e. with increasing the electric power and the ratio of nitrogen/n-hexane in the working gas mixture. The increased wettability is likely caused by presence of NH_x groups in Ag/C:H:N films. The incorporation of nitrogen effectively prevents the formation of carboxylate groups on the silver inclusions surfaces during the aging in the open air. In addition, the oxidation mechanism of the polymer matrix is modified.     

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.     

The effect of the presence of Ag nanoparticles on the photocatalytic degradation of oxalic acid adsorbed on TiO2 nanoparticles monitored by ATR-FTIR

Photocatalytic degradation of oxalic acid adsorbed on the Ag/P25 TiO₂ composite nanoparticle films were investigated using ATR-FTIR technique under UV irradiation. Ag/P25 TiO₂ composite nanoparticle films with various Ag content were tested. Topography and chemical structure/composition of the composite nanoparticle films were analyzed by AFM and XPS respectively. It was found that in the degradation reaction of the oxalic acid, the presence of only 2% Ag nanoparticles leads to six times more oxalic acid degradation compared to that degraded in the presence of pure P25 TiO₂ nanoparticles. The degradation rate of the oxalic acid is three times higher in the case of Ag/TiO₂ composite nanoparticle film than in the case of pure TiO₂ nanoparticles. It was observed that both the rate of oxalic acid degradation and the degraded amount of the oxalic acid were significantly affected by Ag incorporation.     

Optical spectroscopic characterization of plasma-polymerized thin films

We report optical spectroscopic measurements of plasma-polymerized thin films coated on aluminum (Al) substrates over a spectral range from 0.01 to 6 eV. While the reflectance spectra, R(ω), remain almost unchanged in the infrared range as compared with the bare Al, R(ω) starts to decrease significantly in the higher energy above 2.5 eV. This decrease in R(ω) arises from electronic absorptions characteristic of the polymer films. Moreover, the details of R(ω) in the energy above 3 eV depend on the fabrication conditions of the polymer films. Our results, therefore, demonstrate that this optical measurement can be an excellent method to characterize the quality of polymer films deposited by the plasma polymerization process.     

Effect of high-frequency on etching of SiCOH films in CHF3 dual-frequency capacitively coupled plasmas

The effect of high-frequency (HF) frequency on etching characteristics of SiCOH films in a CHF₃ dual-frequency capacitively couple plasma driven by 13.56 MHz/2 MHz, 27.12 MHz/2 MHz or 60 MHz/2 MHz sources was investigated in this work. The surface structure of the films after etching and the CHF₃ discharge plasma were characterized. The increase of HF frequency reduced the critical HF power for the etching, suppressed the C:F deposition at the surface of etched films, and improved the etching of SiCOH films. The improvement of etching was attributed to the increase of ions energy and F concentration at high HF frequency.     

High deposition rate of amorphous silicon thick layers using a gas mixture of 10% silane in hydrogen

The deposition rate of amorphous silicon of the order of 0.9 μm/h, has been obtained using a gas mixture of 10% silane (SiH₄) in hydrogen (H₂), with a RF source of 13.56 MHz. Best films were deposited at a total flow rate of 100–200 sccm, 300°C substrate temperature, 66.7 Pa, and RF power density of 150 mW/cm². The geometrical configuration of the reaction chamber included a gas injector that was specially designed for this purpose. Films were characterized by Fourier transform infrared (FTIR), secondary ion mass spectrometry (SIMS), and profilometer. In addition, thick p-i-n diodes were prepared and characterized, obtaining reverse current densities lower than 5×10⁻⁶ A/cm² at full depletion.     

Optical properties change in amorphous (As2S3)0.87Sb0.13 thin films by photo and thermal induced process

Exposure with above band gap light and thermal annealing at a temperature near to glass transition temperature, of thermally evaporated amorphous (As₂S₃)_0.87Sb_0.13 thin films of 1 μm thickness, were found to be accompanied by structural effects, which in turn, lead to changes in the optical properties. The optical properties of thin films induced by illumination and annealing were studied by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Photo darkening or photo bleaching was observed in the film depending upon the conditions of the light exposure or annealing. These changes of the optical properties are assigned to the change of homopolar bond densities.     

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.     

Polycrystalline AlN films with preferential orientation by plasma enhanced chemical vapor deposition

AlN thin films for acoustic wave devices were prepared by Microwave Plasma Enhanced Chemical Vapor Deposition under different process conditions, employing Si (100) and Pt (111)/SiO₂/Si (100) substrates. The films were characterized by X-ray diffraction, Fourier transform infrared transmission spectroscopy, atomic force microscopy, scanning electron microscopy, and transmission electron microscopy. The values of the distance between the plasma and the tri-methyl-aluminum precursor injector, the radiofrequency bias potential, and the substrate temperature were central in the development of polycrystalline films. The choice of the chamber total pressure during deposition allowed for the development of two different crystallographic orientations, i.e., <0001> or <1010>. The film microstructures exhibited in general a column-like growth with rounded tops, an average grain size of about 40 nm, and a surface roughness lower than 20 nm under the best conditions.     

Gas pressure dependence of composition in Ta–Ti–N films prepared by pulsed high energy density plasma

Tantalum titanium nitride (Ta–Ti–N) films were deposited on silicon wafer substrates by pulsed high energy density plasma (PHEDP), under different intake gas pressures, ranging from 0.1 to 0.4 MPa. The films were investigated by X-ray photoelectron spectroscopy. Results were analyzed in detail, which reveals that the contents of the metallic elements (Ta and Ti) tend to decrease with pressure, while that of nitrogen increases as expected. With increasing pressure, the films can be denoted as TaTi_3.9N_2.8, TaTi_4.7N_6.0, TaTi_2.2N_8.4 and TaTi_3.1N1_3.5, respectively. The bonding state of tantalum, titanium, as well as nitrogen was fitted and discussed. Our results demonstrate that almost all the titanium bonded with nitrogen. The Ta–N and Ti–N bonds have equal shares under low gas intake pressure, while the Ti–N bonds prevail under high pressure. The preferential sputtering between the coaxial electrodes should be responsible for this phenomenon. Under low nitrogen pressure, the preferential sputtering is quite significant; while it could be neglected under high pressure.     

Linked influence of pH and cations on fatty-acid monolayer integrity related to high-quality Langmuir-Blodgett films

This study shows the connection between the morphological structure of transferred films and the chemical composition of the monolayer before transfer. The stability of a behenic acid monolayer depends on the linked influence of the type of cation and of the pH value in the aqueous subphase. The stability of the monolayer is assessed by the expansion of the solid-packed state and by the relaxation time. Its integrity is characterized by the number of crystal defects which appear in transferred Langmuir-Blodgett (LB) films as seen through Nomarski microscope observations. Both stability and integrity are greatly improved when Cd²⁺ or Mn²⁺are added to the subphase at pH 5.75 and 6 respectively. In these conditions, the transfer is very efficient and the LB films thus obtained are of very high quality. The pH values of the subphase at which the molecules of behenic acid are transformed into bivalent salts differ significantly according to the nature of the cation involved. Comparing infrared spectra of the LB films, it appeared that the relative amount of acid/salt found in the monolayer was practically the same with a subphase containing either Cd²⁺ at pH 5.75 or Mn²⁺ at pH 6. This suggests that the ratio of acidic and salt forms would be a key parameter for obtaining high-quality LB films.     

Silicon-carbon-oxynitrides grown by plasma-enhanced chemical vapor deposition technique

In this paper we report some preliminary results about the growth at low temperature (493 K) of hydrogenated silicon-carbon-oxygen-nitrogen amorphous thin-film alloys (a-SiC_xO_yN_z:H) by means of capacitively-coupled radio-frequency (13.56 MHz) plasma-enhanced chemical vapor deposition using a mixtures of silane (SiH₄), propane (C₃H₈), nitrous oxide (N₂O) and ammonia (NH₃) precursor gases. Thin films of a-SiC_xO_yN_z:H were grown at different deposition conditions, obtaining growth speeds varying from 0.22 to 0.44 nm/s. The films were characterized by means of Fourier transform infra-red spectroscopy in order to investigate the internal bonding structure, by UV-VIS transmittance spectroscopy to check the optical properties and by mechanical profilometry to measure the film thickness and estimate the growth rate. The comparison of structural and optical properties of samples grown with and without NH₃ presence in the gas mixture showed that the ammonia addition allows a better control of nitrogen incorporation in the film structure, while increasing film transparency and reducing the growth rate.