Bias enhanced nucleation of diamond thin films in a modified HFCVD reactor

In this study we investigated the nucleation of synthetic diamond thin films on Si substrates by double bias enhanced Hot Filament Chemical Vapour Deposition (HFCVD) method. First, we investigated the influence of the bias voltage and secondly the influence of the nucleation time under different bias voltages. The bias voltage was varied from −120 V up to −220 V as well as the nucleation time was changed from 30 up to 120 min in order to obtain the optimized nucleation conditions for following growth of continuous diamond layer. Samples were analyzed by Scanning Electron Microscopy (SEM) and Raman Spectroscopy. SEM was used for determination of cluster sizes and their distribution on the Si surface, while Raman Spectroscopy for determination and analysis of carbon phases.     

Comparative study on dry etching of polycrystalline diamond thin films

The reactive ion etching (RIE) technique was used to etch polycrystalline diamond thin films. In this study we investigate the influence of process parameters (total pressure, rf power, gas composition) of standard capacitively coupled plasma RIE system on the etching rate of diamond films. The surface morphology of etched diamond films was characterized by Scanning Electron Microscopy and the chemical composition of the etched film part was investigated by Raman Spectroscopy.We found that the gas composition had a crucial effect on the diamond film morphology. The use of CF₄ gas resulted in flatter surfaces and lateral-like etching, while the use of pure O₂ gas resulted in needle-like structures. Addition of argon to the reactant precursors increased the ion bombardment, which in turn increased the formation of non-diamond phases. Next, increasing the rf power from 100 to 500 W increased the etching rate from 5.4 to 8.6 μm/h. In contrast to this observation, the rise of process pressure from 80 to 150 mTorr lowered the etching rate from 5.6 down to 3.6 μm/h.     

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.     

Preparation of high quality polycrystalline silicon thin films by aluminum-induced crystallization

High quality polycrystalline silicon (poly-Si) thin films without Si islands were prepared by using aluminum-induced crystallization on glass substrates. Al and amorphous silicon films were deposited by vacuum thermal evaporation and radio frequency magnetron sputtering, respectively. The samples were annealed at 500 °C for 7 h and then Al was removed by wet etching. Scanning electron microscopy shows that there are two layers in the thin films. After the upper layer was peeled off, the lower poly-Si thin film was found to be of high crystalline quality. It presented a Raman peak at 521 cm^− 1 with full width at a half maximum of 5.23 cm^− 1, which is similar to c-Si wafer.     

Broad band photoluminescence studies of diamond layers grown by hot-filament CVD

Photoluminescence and Raman spectroscopy were employed to investigate the broad band luminescence in thin diamond films grown on a silicon substrate by the HF CVD technique. The broad band luminescence with a maximum emission at 1.8–2 eV observed for CVD diamonds is characteristic for amorphous carbon with sp²-hybridized carbon bonds. As was shown by the Raman spectroscopy our diamond layer contained certain amounts of amorphous carbon phase and diamond nanocrystals which were the source of an additional energy state within the diamond energy gap. The experimental results precluded the possibility of broad band luminescence being due to the electron–lattice interaction. The amorphous carbon and diamond nanocrystals admixture in polycrystalline diamond layer introduced a defect state in the energy gap not in the form of point defects but rather in the form of a line or extended defects. In consequence these extended defects were responsible for the broad PL spectrum in the CVD diamond films.     

Structural and optical characterization of thick and thin polycrystalline diamond films deposited by microwave plasma activated CVD

Preliminary results of growth of thin diamond film in a recently installed 3 kW capacity microwave plasma activated CVD (MW-PACVD) system are being reported. The films were deposited on Si (100) substrate at 850°C using methane and hydrogen mixture at 1·5 kW MW power. The grown polycrystalline films were characterized by micro-Raman, transmission electron microscope (TEM), spectrophotometer and atomic force microscope (AFM). The results were compared with that of a thicker diamond film grown elsewhere in a same make MW-PACVD system at relatively higher power densities. The presence of a sharp Raman peak at 1332 cm^− 1 confirmed the growth of diamond, and transmission spectra showed typical diamond film characteristics in both the samples. Typical twin bands and also a quintuplet twinned crystal were observed in TEM, further it was found that the twinned region in thin sample composed of very fine platelet like structure.     

Low-temperature epitaxy of silicon by electron beam evaporation

In this paper we report on homoepitaxial growth of thin Si films at substrate temperatures T_s = 500-650 °C under non-ultra-high vacuum conditions by using electron beam evaporation. Si films were grown at high deposition rates on monocrystalline Si wafers with (100), (110) and (111) orientations. The ultra-violet visible reflectance spectra of the films show a dependence on T_s and on the substrate orientation. To determine the structural quality of the films in more detail Secco etch experiments were carried out. No etch pits were found on the films grown on (100) oriented wafers. However, on films grown on (110) and (111) oriented wafers different types of etch pits could be detected. Films were also grown on polycrystalline silicon (poly-Si) seed layers prepared by an Aluminum-Induced Crystallisation (AIC) process on glass substrates. Electron Backscattering Diffraction (EBSD) shows that the film growth proceeds epitaxially on the grains of the seed layer. But a considerably higher density of extended defects is revealed by Secco etch experiments.     

Nanocrystalline diamond/amorphous carbon composite films for applications in tribology,optics and biomedicine

Nanocrystalline diamond/amorphous carbon (NCD/a-C) composite thin films have been deposited by microwave plasma chemical vapour deposition from methane-rich CH₄/N₂ mixtures. The films have been thoroughly characterized with respect to basic properties such as growth rates, morphology and structure, composition, crystallinity, and bonding environment. They consist of diamond nanocrystals with diameters of 3–5 nm, which are embedded in an amorphous carbon matrix. Further studies are aimed at application relevant properties. I/V and Hall measurements showed that the films are p-type conductive with a resistitivity of 0.14 Ω cm, a carrier concentration of 1.9 × 10¹⁷ cm^− 3, and a carrier mobility of 250 cm²/Vs. Reflection, scattering and ellipsometric measurements revealed a refractive index of 1.95–2.1 in the visible region and an rather high extinction coefficient of about 0.14 at 400 nm. The films possess a hardness of ca. 40 GPa and a Young's modulus of ca. 390 GPa. Nano tribo test and nano scratch tests proved a low friction coefficient, and a strong protective effect and good adhesion on silicon substrates. First biomedical tests showed that the films are not cytotoxic but bioinert. Finally, the deposition of multilayers nano/polycrystalline diamond with improved properties is demonstrated.     

Effect of argon and substrate bias on diamond thin film surface morphology

Nanocrystalline materials are of high interest, because mechanical and physical properties of such materials are different from those or coarse-grained type. Continuous and smooth nanocrystalline diamond (NCD) thin films were successfully grown on mirror polished silicon substrates, using double bias plasma-enhanced hot filament chemical vapour deposition technique. A gas mixture of Ar:CH₄:H₂ and CH₄:H₂ was used as the precursor gas. The effect of the gas composition, flow rate and substrate bias during deposition on diamond crystallite size was investigated. Changing the growth parameters facilitates control of grain size of polycrystalline diamond thin films from microcrystalline to nanocrystalline. The structure of fine-grained NCD films has been studied with scanning electron microscopy and Raman spectroscopy.     

Characterization of hypervelocity impact craters on chemical vapour-deposited diamond and diamond-like carbon films

Microwave plasma chemical vapour-deposited (CVD) process has been used to grow polycrystalline diamond films over silicon substrates. Diamond-like carbon (DLC) thin films were grown over silicon substrates using a microwave plasma disc reactor. Reactant gases of CH4 and H2 were used in both CVD processes. Some preliminary feasibility tests were performed on the possible applicability of diamond and diamond-like carbon thin films for space-protective applications against artificially simulated electrically actuated plasma drag hypervelocity impact of olivine particles. As-deposited films were analysed by Raman for their chemical nature. The morphology and dimensions of hypervelocity impact craters in diamond and DLC films was also studied by scanning electron microscopy (SEM) and optical microscopy. The velocity of debris particles was determined by high-speed photography using a streak camera. The size of the impact particles was determined by measuring the size of the holes formed in the mylar sheet mounted just above the target diamond and DLC film/silicon and coordinates of the impact sites were determined using the same apparatus. This revised version was published online in November 2006 with corrections to the Cover Date.     

Surface nano-structured silicon carbide thin film produced using hot filament decomposition of ethylene at low temperature on silicon wafer

The structure and spectroscopic properties of nano-structured silicon carbide (SiC) thin films were studied for films obtained through deposition of decomposed ethylene (C₂H₄) on silicon wafers via hot filament chemical vapor deposition method at low temperature followed by annealing at various temperatures in the range 300-700 °C. The prepared films were analyzed with focus on the early deposition stage and the initial growth layers. The analysis of the film's physics and structural characteristics was performed with Fourier transform infrared spectroscopy and Raman spectroscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, and X-ray diffraction. The conditions for forming thin layer of cubic SiC phase (3C-SiC) are found. X-ray diffraction and Raman spectroscopy confirmed the presence of 3C-SiC phase in the sample. The formation conditions and structure of intermediate SiC layer, which reduces the crystal lattice mismatch between Si and diamond, are essential for the alignment of diamond growth. This finding provides an easy way of forming SiC intermediate layer using the Si from the substrate.     

Optical and microstructural properties of p-type SrCu2O2: First principles modeling and experimental studies

In this paper, we report first principles calculations and experimental studies of the optical and microstructural properties of both bulk and thin films of SrCu₂O₂. Polycrystalline SrCu₂O₂ films were grown by a conventional Pulsed Laser Deposition method in a flowing oxygen environment on corning glass 7059 and silicon substrates. Several characterization techniques, including X-ray diffraction (XRD), Fourier Transform IR (FTIR), Raman, spectroscopic ellipsometry, reflectance/transmission spectrophotometry and Atomic Force Microscopy have been used for the investigation of the microstructural and vibrational properties of both bulk and thin films of SrCu₂O₂.XRD shows that bulk SrCu₂O₂ is polycrystalline and assumes the pure tetragonal phase of SrCu₂O₂. The vibrational properties of the tetragonal phase of SrCu₂O₂ have been inferred from Raman and FTIR spectroscopies and for the first time both Raman and IR active modes have been assigned. The bulk polycrystalline SrCu₂O₂ optical band gap determined from spectroscopic ellipsometry was 3.34 ± 0.01 eV. XRD results confirmed that pure non-textured polycrystalline phase SrCu₂O₂ thin films with a smooth surface can be grown by PLD at low temperature (300 °C).     

Effect of B/C ratio on the physical properties of highly boron-doped diamond films

Highly boron-doped diamond films were deposited on silicon substrate by hot filament chemical vapor deposition in a gas mixture of hydrogen and methane. The chemical bonding states, surface texture, and electrical resistivity of these films were analyzed by X-ray photoelectron spectroscopy, scan electron microscope, and four-point probe method. It was found that boron dopants play an important role in the texture and chemical bonding states of the diamond films. An appropriate concentration of boron dopants (B/C ratio of 10 000 ppm) can simultaneously improve crystal quality and reduce resistivity of the diamond films. The minimum resistivity of diamond films reaches 1.12 × 10⁻² Ω cm, which is applicable as electrodes.     

Selective Oxidation of Graphite on Diamond Films Induced by UV Exposure

A selective oxidation technique for diamond films based on the extended exposure to UV light in air at room temperature was developed and studied by Raman Spectroscopy and Scanning Electron Microscopy. The diamond films were synthesized by the combustion flame technique in open atmosphere by using an oxy-acetylene gas mixture as the carbon source. A 125 W UV lamp was used to irradiate the films in the wavelength range of 180–250 nm, from 2 to 10 days. The Raman spectrum from the as-deposited diamond films shows the typical band at 1333 cm^–1, characteristic of the sp ³diamond structure, with a certain nondiamond or graphite content. After UV irradiation, graphite was selectively oxidized and partially removed without oxidation of diamond, indicating that the strong reaction of ozone (O₃) and atomic oxygen (O·) produced by the UV irradiation oxidized the graphite, even at room temperature, without the need of an additional heating source. The oxidation of graphite was best observed after 2 days of UV treatment. A sensible improvement in the diamond film quality was obtained after 2 days of irradiation, as revealed by the sharpening of the corresponding Raman band.     

Bioactive glass–ceramic coatings prepared by pulsed laser deposition from RKKP targets (sol–gel vs melt-processing route)

The deposition of innovative glass–ceramic composition (i.e. RKKP) coatings by Pulsed Lased Deposition (PLD) technique is reported. RKKP was synthesised following two methodologies: melt-processing and sol–gel, the latter being particularly suitable to tailor the compositional range. The PLD advantage with respect to other deposition techniques is the congruent transfer of the target composition to the coating. The physico-chemical properties of films were investigated by Scanning Electron and Atomic Force Microscopies, Fourier Transform Infrared Spectroscopy, Angular and Energy Dispersive X-ray Diffraction, and Vickers microhardness. The deposition performed at 12 J/cm² and 500 °C allows to prepare crystalline films with the composition that replicates rather well that of the initial targets. The 0.6 μm thin melt-processing RKKP films, possessing the hardness of 25 GPa, and the 4.3 μm thick sol–gel films with the hardness of 17 GPa were obtained.     

Electrical properties of diamond films prepared from carbon disulfide and ethanol in hydrogen

Sulfur doping of diamond samples produced by the hot-filament chemical vapor deposition (CVD) process using carbon disulfide highly diluted in ethanol and hydrogen has been investigated. The polycrystalline morphology observed by Scanning Electron Microscopy (SEM) and the characteristic diamond Raman peak were practically not affected by addition of CS₂ in the range of 0.8-2.0% by volume. The electrical resistivity dependence due to CS₂ addition showed a “down-and-up” curve with minimum resistivity of about 3.6 × 10⁻⁴ Ωcm. Hall mobility as high as 325.9 cm²V⁻¹s⁻¹ have been achieved. PIXE and XRF measurements showed that sulfur (100-400 ppm) was incorporated during the deposition independent of the CS₂ added. Unintentional contaminations with Si, W, Cu and Cr have been detected. All the samples, measured by hot-point method and Hall effect, showed p-type characteristics.     

Enhanced field emission from ZnO nanoneedles on chemical vapour deposited diamond films

ZnO nanoneedles were coated on hot filament chemical vapour deposited diamond thin films to enhance the field emission properties of ZnO nanoneedles. The virgin diamond films and ZnO nanoneedles on diamond films were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. The field emission studies reveal that the ZnO nanoneedles coated on diamond film exhibit better emission characteristics, with minimum threshold field (required to draw a current density ~ 1 μA/cm²) as compared to ZnO needles on silicon and virgin diamond films. The better emission characteristic of ZnO nanoneedles on diamond film is attributed to the high field-enhancement factor resulting due to the combined effect of the ZnO nanoneedles and diamond film.     

Carbon coatings with low secondary electron yield

Carbon thin films for electron cloud mitigation and anti-multipacting applications have been prepared by dc magnetron sputtering in both neon and argon discharge gases and by plasma enhanced chemical vapour deposition (PECVD) using acetylene. The thin films have been characterized using Secondary Electron Yield (SEY) measurements, Scanning Electron Microscopy (SEM), Nuclear Reaction Analysis (NRA) and X-ray Photoemission Spectroscopy (XPS). For more than 100 carbon thin films prepared by sputtering the average maximum SEY is 0.98 ± 0.07 after air transfer. The density of the films is lower than the density of Highly Oriented Pyrolytic Graphite (HOPG), a fact which partially explains their lower SEY. XPS shows that magnetron sputtered samples exhibit mainly sp² type bonds. The intensity on the high binding energy side of C1s is found to be related to the value of the SEY. In addition the initial surface concentration of oxygen has no influence on the resulting SEY, when it is below 16%. The thin films produced by PECVD have a much higher maximum SEY of 1.49 ± 0.07.Storage conditions in air, namely wrapping in aluminium foil, preserves the low SEY by more than one year. Such coatings have already been applied successfully in accelerators and multipacting test benches.     

Field emission studies of CVD diamond thin films: effect of acid treatment

Field emission from CVD diamond thin films deposited on silicon substrate has been studied. The diamond films were synthesized using hot filament chemical vapor deposition technique. Field emission studies of as-deposited and acid-treated films were carried out using ‘diode’ configuration in an all metal UHV chamber. Upon acid treatment, the field emission current is found to decrease by two orders of magnitude with increase in the turn-on voltage by 30%. This has been attributed to the removal of sp² content present in the film due to acid etching. Raman spectra of both the as-deposited and acid-treated films exhibit identical spectral features, a well-defined peak at 1333 cm⁻¹ and a broad hump around 1550 cm⁻¹, signatures of diamond (sp³ phase) and graphite (sp² phase), respectively. However upon acid treatment, the ratio (I_d/I_g) is observed to decrease which supports the speculation of removal of sp² content from the film. The surface roughness was studied using atomic force microscopy (AFM). The AFM images indicate increase in the number of protrusions with slight enhancement in overall surface roughness after acid etching. The degradation of field emission current despite an increase in film surface roughness upon acid treatment implies that the sp² content plays significant role in field emission characteristics of CVD diamond films.     

Effect of open air annealing on spin coated aluminum doped ZnO nanostructure

Aluminum doped ZnO thin film nanostructures were prepared by spin coating deposition on glass and silicon substrates. Electrical, optical and structural properties of these films were analyzed in order to investigate their dependence on post annealing temperature and number of coating cycles. Ultraviolet–Visible spectrophotometry and X-Ray diffraction (XRD) analysis confirmed that the films are optically transparent and polycrystalline in nature. Scanning electron microscopy (SEM) reveals worm like homogeneous morphology. Chemical analysis was carried out by Fourier transform infrared spectroscopy (FTIR). Atomic force microscopy (AFM) showed mountain and valley like nanostructure. Optimized films with a low resistivity of 2.11 × 10⁻¹ Ω cm were obtained at open air annealing temperature of 375 °C.