Synthesis of carbon films containing diamond particles by electrolysis of methanol

Carbon films containing diamond particles were deposited onto a Si (100) substrate by electrolysis of methanol under a direct current potential of 1200 V, with a current density of about 52 mA/cm², at atmospheric pressure and in the temperature range of 50-55 °C. The surface morphology, microstructure and crystalline structure of the deposited films were characterized by scanning electron microscopy (SEM), Fourier transformation infrared (FTIR) spectroscopy, Raman spectroscopy and transmission electron microscopy (TEM) respectively. The SEM images show that the films are formed by particle clusters and a surrounding glassy phase. The Raman spectra of the films indicate that the particle clusters are composed of diamond and that the glassy phase is composed of amorphous carbon. The FTIR measurements suggest the existence of hydrogen which is mainly bonded to the sp³ carbon in the films. The transmission electron diffraction patterns further indicate that the particles in the films consist of single-crystalline diamond. Both TEM and Raman measurements have confirmed unambiguously the formation of diamond crystals in the deposit, although the particles are not uniformly distributed on the entire surface.     

Cyclic voltammetry and impedance studies of undoped diamond films

The undoped, polycrystalline diamond films were deposited on tungsten wire substrates by hot filament chemical vapor deposition (HF CVD), using a precursor gas mixture of methanol with excess of hydrogen. The morphology and quality of the as-deposited films were monitored by scanning electron microscopy (SEM) and Raman spectroscopy. The surface morphology analyzed by SEM resembles a continuous and well faceted diamond film. Raman results showed essential differences in qualities of diamond films grown at different hydrocarbon concentrations. The electrochemical properties of diamond electrodes were examined with cyclic voltammetry (CV) and the electrochemical impedance spectroscopy (EIS). The CV experiments revealed a large chemical window (>～4.3 V) of undoped diamond. Analysis of the ferrocyanide-ferricyanide couple at a diamond electrode suggests some extent of electrochemical quasi-reversibility, but the rates of charge transfer across the diamond substrate interface vary with diamond quality.     

Novel plasma treatment in linear antenna microwave PECVD system

This work reports on hydrogen termination of nano-crystalline diamond films and the behavior of polymer SU-8 as passivating layer after plasma treatment performed at low temperature in a novel linear antenna microwave plasma enhanced system. Nano-crystalline diamond films were grown by microwave plasma enhanced chemical vapor deposition and then hydrogen terminated at different substrate temperatures. The results indicate that a temperature as low as 200 °C is sufficient to reliably attain a diamond surface conductivity of the order of 10⁻⁷ (Ω/□)⁻¹. An increase in substrate temperature up to 400 °C results in an increase in surface conductivity up to 1.7 × 10⁻⁶ (Ω/□)⁻¹. The structural changes of the SU-8 passivating layer, before and after plasma treatment, were investigated by FTIR spectroscopy.     

Preparation of Cu2ZnSnS4 thin films by sulfurization of stacked metallic layers

Stacked precursors of Cu, Sn, and Zn were fabricated on glass/Mo substrates by electron beam evaporation. Six kinds of precursors with different stacking sequences were prepared by sequential evaporation of Cu, Sn, and Zn with substrate heating. The precursors were sulfurized at temperatures of 560 °C for 2 h in an atmosphere of N₂ + sulfur vapor to fabricate Cu₂ZnSnS₄ (CZTS) thin films for solar cells. The sulfurized films exhibited X-ray diffraction peaks attributable to CZTS. Solar cells using CZTS thin films prepared from six kinds of precursors were fabricated. As a result, the solar cell using a CZTS thin film produced by sulfurization of the Mo/Zn/Cu/Sn precursor exhibited an open-circuit voltage of 478 mV, a short-circuit current of 9.78 mA/cm², a fill factor of 0.38, and a conversion efficiency of 1.79%.     

Ferroelectric properties of Pb(Zr,Ti)O3 films fabricated using a modified sol-gel based process

Ferroelectric PZT(20/80) thick films were fabricated by the screen printing method. And the PZT precursor solution was spin-coated on the PZT thick films to obtain a densification. Electrical properties of the thick films as a function of the firing temperature of the PZT precursor solution were investigated. The thickness of all thick films was approximately 60-62 μm. The porosity increased with increasing the firing temperature of the sol, and the porous microstructure and some large pores were observed above 700 °C due to the PbO evaporation. The relative dielectric constant, remanent polarization and dielectric breakdown strength of the specimen fired at 650 °C were 222, 16.5 μC/cm² and 73 kV/cm, respectively.     

Field emission from diamond and diamond-like carbon films

Field emission from diamond and diamond-like carbon thin films deposited on silicon substrates has been studied. The diamond films were synthesized using hot filament chemical vapor deposition technique. The diamond-like carbon films were deposited using the radio frequency chemical vapor deposition method. Field emission studies were carried out using a sphere-to-plane electrode configuration. The results of field emission were analyzed using the Fowler-Nordheim model. It was found that the diamond nucleation density affected the field emission properties. The films were characterized using standard scanning electron microscopy, Raman spectroscopy, and electron spin resonance techniques. Raman spectra of both diamond and diamond-like films exhibit spectral features characteristic of these structures. Raman spectrum for diamond films exhibit a well-defined peak at 1333cm^?1. Asymmetric broad peak formed in diamond-like carbon films consists of D-band and G-band around 1550 cm^?1 showing the existence of both diamond (sp³ phase) and graphite (sp² phase) in diamond-like carbon films.     

Diamond nanocrystals and amorphous SiOx nanowires formed by rapid thermal annealing of carbon film

Rapid thermal annealing (RTA) has been performed on the carbon films prepared by radio frequency plasma-enhanced chemical vapor deposition on Si substrate. The RTA at 800 °C for 60 s leads to the formation of many diamond nanocrystallites agglomerating on the film surface. Higher temperature RTA at 1100 °C for 60 s induces the high-density amorphous SiO_x (x = 1.2) nanowires on the film surface without diamond nanocrystallites. At both the RTA temperatures, a well-oriented SiC interlayer is also formed simultaneously. The sp³ sites in the carbon film and the oxygen during the RTA treatment as well as the RTA temperature are considered to play important roles in determining the final reaction products.     

Effects of low temperatures, low pressures and seeding over the crystalline quality, yield and stress of diamond films grown by ECR-assisted chemical vapor deposition

We have studied diamond films grown by electron cyclotron resonance (ECR)-assisted chemical vapor deposition (CVD) on Si (100) substrates seeded with diamond, boron nitride and unseeded. Relatively low temperatures (550–710°C) and low pressures (1–2 Torr) were employed. Raman spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD) were used to characterize the crystalline quality, diamond yield, and stresses developed in these films. Most of the diamond films exhibit a Raman blue-shift with respect to natural diamond, indicating that the net stress is compressive. However, this net stress is significantly more compressive than the one estimated by taking into account the thermal interfacial stress and the stress developed at the grain boundaries. In addition, this net stress exhibits an inverse correlation with diamond yield, and a direct correlation with crystalline quality. These results were interpreted in terms of the critical interplay between the supply of precursor species to the growing surface and the surface mobility of adsorbed species. The excess (or intrinsic) compressive stress shows an inverse correlation with diamond crystalline quality, indicating that the creation of point defects serves as a stress-relieving mechanism. Seeding effects, in general, are deleterious to diamond quality, in this temperature and pressure regime studied. Seeding with boron nitride had the effect of reversing the net stress from compressive into tensile, but this effect was rapidly lost as the diamond yield increased.     

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.     

Microstructure of highly crystalline silicon carbide thin films grown by HWCVD technique

Highly crystalline silicon carbide films were synthesised by HWCVD technique. Raman spectroscopic studies show that the SiC films contain crystalline SiC and also carbon phases. Carbon is graphitic at higher chamber pressures (≥ 50 Pa) and resembles diamond-like carbon at low pressure (5 Pa). Cross-section TEM results show a columnar morphology of the crystallites with typical column diameters up to ∼ 50 nm. Transmission electron diffraction patterns reveal SiC in its cubic and hexagonal SiC phases and the C diamond phase at low pressure. Annealing at 1000 °C for 1 h results in enhancement of crystallite size without nucleation of new phases.     

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.     

Epitaxial growth and surface morphology of aluminum films deposited on mica studied by transmission electron microscopy and atomic force microscopy

The bulk structure and epitaxial growth of aluminum films deposited on mica substrates by thermal evaporation in a wide temperature range (16-550 °C) in high vacuum were investigated by transmission electron microscopy and transmission electron diffraction. The surface morphology of the films was observed and analyzed by atomic force microscopy. The films prepared at room temperature consist of single crystals having a diameter of 90 ± 40 nm with (111) planes. The surface of the films comprises spherical grains with morphology that is caused by self-shadowing during the deposition. The surface of the films becomes smoother as the temperature increases, and atomically-smooth surfaces with a root-mean-square roughness of about 0.45 nm over an area of 1 μm² are obtained at 250-350 °C. The crystals are oriented randomly along the [111] direction perpendicular to the substrate. The surface of the films consists of larger (> 300 nm) grains with terraces, and the surface becomes rough above 400 °C. Films with well-oriented single crystals along the [111] direction perpendicular to the substrate are obtained above 520 °C. The films grown epitaxially at 520-550 °C are characterized by the isolated grains with a diameter of 1220 ± 450 nm.     

Growth and characterization of diamond particles,diamond films,and CNT-diamond composite films deposited simultaneously by hot filament CVD

It is important to understand the growth of CNT-diamond composite films in order to improve the inter-link between two carbon allotropes, and, in turn, their physical properties for field emission and other applications. Isolated diamond particles, continuous diamond thin films, and thin films of carbon nanotubes (CNTs) having non-uniformly distributed diamond particles (CNT-diamond composite films) were simultaneously grown on unseeded, seeded, and catalyst pre-treated substrates, respectively, using a large-area multi-wafer-scale hot filament chemical vapor deposition. Films were deposited for four different growth durations at a given deposition condition. The changes in surface morphology and growth behavior of diamond particles with growth duration were investigated ex situ using field emission scanning electron microscopy and 2D confocal Raman depth spectral imaging, respectively. A surface morphological transition from faceted microcrystalline nature to nanocrystalline nature was observed as a function of growth duration in the case of isolated diamond particles grown on both unseeded and catalyst pre-treated substrates. However, such a morphological transition was not observed on the simultaneously grown continuous diamond thin films on seeded substrates. 2D confocal Raman depth spectral imaging of diamond particles showed that the local growth of CNTs did not affect the growth behavior of neighboring diamond particles on catalyst pre-treated substrates. These observations emphasize the importance of surface chemical reactions at the growth site in deciding sp² or sp³ carbon growth and the final grain size of the diamond films.     

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.     

Effects of precursor evaporation temperature on the properties of the yttrium oxide thin films deposited by microwave electron cyclotron resonance plasma assisted metal organic chemical vapor deposition

Yttrium oxide thin films are deposited using indigenously developed metal organic precursor (2,2,6,6-tetra methyl-3,5-hepitane dionate) yttrium, commonly known as Y(thd)₃ (synthesized by ultrasound method). Microwave electron cyclotron resonance plasma assisted metal organic chemical vapor deposition process was used for these depositions. Depositions were carried out at a substrate temperature of 350 °C with argon to oxygen gas flow rates fixed to 1 sccm and 10 sccm respectively throughout the experiments. The precursor evaporation temperature (precursor temperature) was varied over a range of 170-275 °C keeping all other parameters constant. The deposited coatings are characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and refractive index of the coatings are measured by the spectroscopic ellipsometry. Hardness and elastic modulus of the films are measured by load depth sensing nanoindentation technique.C-Y₂O₃ phase is deposited at lower precursor temperature (170 °C). At higher temperature (220 °C) cubic yttrium oxide is deposited with yttrium hydroxide carbonate as a minor phase. When the temperature of the precursor increased (275 °C) further, hexagonal Y₂O₃ with some multiphase structure including body centered cubic yttria and yttrium silicate is observed in the deposited film. The properties of the films drastically change with these structural transitions. These changes in the film properties are correlated here with the precursor evaporation characteristics obtained at low pressures.     

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.     

Nucleation and initial growth processes of diamond thin films for stripper foils

Carbon ion beam stripper foils were fabricated from diamond films synthesized on silicon via chemical vapor deposition. Fine-grained polycrystal diamond foils with decent surface flatness were obtained using a nucleation enhancement pretreatment process. Freestanding diamond foils were formed by etching a portion of the silicon substrate on which the diamond films well-adhered. In preliminary lifetime evaluations, the 1–3 μm-thick diamond foils lasted between 20 and 420 min for 3.2 MeV Ne⁺ion-beam charge stripping.     

Field emission characteristics of fast grown nanocrystalline diamond/amorphous carbon composite films by microwave plasma-enhanced chemical deposition method

This study synthesized the nanocrystalline diamond/amorphous carbon (NCD/a-C) composite films by the microwave plasma-enhanced chemical vapor deposition (MPCVD) system with Ar/CH₄/N₂ mixtures. A localized rectangular-type jet-electrode with high density plasma was used to enhance the formation of NCD/a-C films, and a maximum growth rate of 105.6 µm/h was achieved. The content variations of sp² and sp³ phases via varying nitrogen gas flow rates were investigated by using Raman spectroscopy. The NCD/a-C film which synthesized with 6% nitrogen concentration and no hydrogen plasma etching treatment possessed a low turn-on electric field of 3.1 V/µm at the emission current of 0.01 µA.     

Surface morphology of polycrystalline diamond films etched by Ar+ beam bombardment

Polycrystalline diamond films etched by Ar⁺ beam bombardment were investigated by scanning electron microscopy and Raman spectroscopy. In an ion sputtering apparatus, an etching rate of 14 m C^–1 was obtained when 10 kV-accelerated Ar⁺ ions penetrated with an angle of 15–30° from the normal. A number of cavities were created on the surface treated at low incidence angle. In contrast, micro-prominence was seen under the condition of high incidence angle. The degree of surface roughness on etched films was also changed with the incidence angle of the beam. A relatively smooth surface appeared after the treatment with an incidence angle of 15°. Raman spectroscopy revealed that the physical etching of diamond is effective in obtaining high quality surface of polycrystalline diamond films.     

Fabrication by electrostatic spray deposition and structural investigation of ultra thin and dense zirconia films

The aim of this work was to prepare ultra thin and dense zirconia films by electrostatic spray deposition to be applied in microelectronic devices. In this paper, the influence of the precursor solution was investigated on the morphology of zirconia films, in terms of salt concentration starting from zirconium acetylacetonate and solvent composition based on butyl carbitol and/or ethanol. The microstructure of zirconia films was studied by Scanning and Transmission Electron Microscopies. The as-deposited films, less than 20 nm in thickness, were found to be amorphous. A film densification, leading to its thickness decrease to 7 nm, occurred through a thermal treatment at 600 °C under helium. A partial crystallization was observed and the structure of the film was found to be mainly tetragonal, according to electron diffraction. An appearance of 6 mol% monoclinic phase was detected by Raman microspectrocopy.