Anisotropic dry etching of boron doped single crystal CVD diamond

Semiconducting boron doped single-crystal CVD diamond has been patterned using aluminum masks and an inductively coupled plasma (ICP) etch system. For comparison insulating HPHT diamond samples were also patterned using the same process. Diamond etch rates above 200 nm/min were obtained with an O₂/Ar discharge for a gas pressure of 2.5 mTorr using 600 W RF power. We have accomplished the fabrication of structures with a minimum feature size of 1 μm with vertical sidewalls in both CVD and HPHT diamond. The ICP etching produced smooth surfaces with a typical root-mean-square surface roughness of 3 nm. The dependence of etch rate on bias voltage was somewhat different for the two types of diamond. However, for all samples both the etch rate and anisotropy were found to improve with increasing bias voltage.     

Highly oriented growth of n-type ZnO films on p-type single crystalline diamond films and fabrication of high-quality transparent ZnO/diamond heterojunction

We present the results on the fabrication and characterization of high-quality transparent heterojunction between n-type ZnO film and p-type diamond single crystalline film on the substrate of diamond bulk single crystal. The results indicated that the current density of the fabricated p-n junction reaches 110 A/m² when the forward bias voltage is 2.5 V, and the turn-on voltage value is about 0.75 V and agreement with the expected value. Moreover, a good rectification characteristic and transparent in the visible light range was obtained in the device.     

Synthesis of carbon nanotubes on metallic substrates by a sequential combination of PECVD and thermal CVD

Carbon nanotubes were synthesized from acetylene and hydrogen gas mixture directly on stainless steel plates by sequential combination of rf PECVD and thermal CVD. PECVD was used for nucleation and initial growth of carbon nanotubes while thermal CVD was utilized for further growth of them. In this way decoupling of nucleation and growth of carbon nanotubes was realized, and growth of carbon nanotubes was enhanced compared to growth by PECVD. Synthesized carbon nanotubes were curly in shape, and proper pretreatment of the substrate surface was required for the satisfactory growth of carbon nanotubes. Carbon nanotubes could be fabricated into electrodes for electric double layer capacitors without any further treatment. With an electrolyte composed of lithium hexafluorophosphate, ethylene carbonate and diethyl carbonate, charge/discharge test showed specific capacitance in the range of 33-82 F/g.     

Synthesis of large single crystal diamond using combustion-flame method

A combustion flame method is used to synthesize large single crystal diamond in ambient atmosphere. The basic of this technique was originally described by Hirose and Kondo in 1988 [Hirose H, Komaki K. Eur Pat Appl 1988:EP324538]. The advantage of this method is the high growth rate of diamond films, which is about 60 μm/h [Alers P, Hanni W, Hintermann HE. A comparative study of laminar and turbulent oxygen-acetylene flames for diamond deposition. Diam Relat Mat 1992;2:393-6]. The diamond can grow on itself to achieve large single-crystal. Negative substrate-bias effects on diamond growth have been investigated. Diamonds films were characterized by scanning electron microscopy, Raman spectroscopy, and atomic force microscopy in tapping mode. For given conditions, diamond coatings with highly oriented {1 0 0} crystal facets were produced. Large singles crystals diamonds were obtained. The sizes of these crystals vary between 80 and 90 μm. These results are discussed with respect to the competing events occurring during the heteroepitaxial growth of diamond.     

UV Raman characteristics of nanocrystalline diamond films with different grain size

Nanocrystalline diamond films with different size were characterized by ultraviolet (UV) (244 nm) Raman spectroscopy. It was found that a diamond peak at 1333 cm⁻¹ was enhanced, while the D and G peak of graphite as well as photoluminescence was suppressed, compared with that measured by visible (514.5 nm) Raman. With decreasing the particle size from 120 to 28 nm, the diamond peak shifts from 1332.8 to 1329.6 cm⁻¹, the line width of the peak becomes broader, the intensity ratio of diamond and G peak decreases. The down shift and broadening of the diamond peak depending on the particle size by UV Raman measurements are consistent with the phonon confinement model.     

Prevention of Si-contaminated nanocone formation during plasma enhanced CVD growth of carbon nanotubes

We investigated the growth behavior and morphology of vertically aligned carbon nanotubes (CNTs) on silicon (Si) substrates by direct current (DC) plasma enhanced chemical vapor deposition (PECVD). We found that plasma etching and precipitation of the Si substrate material significantly modified the morphology and chemistry of the synthesized CNTs, often resulting in the formation of tapered-diameter nanocones containing Si. Either low bias voltage (∼500 V) or deposition of a protective layer (tungsten or titanium film with 10-200 nm thickness) on the Si surface suppressed the unwanted Si etching during growth and enabled us to obtain cylindrical CNTs with minimal Si-related defects. We also demonstrated that a gate electrode, surrounding a CNT in a traditional field emitter structure, could be utilized as a protection layer to allow growth of a CNT with desirable high aspect ratio by preventing the nanocone formation.     

Morphologies and microstructures of tree-like carbon produced at different reaction conditions in a CVD process

Centimeter-size multi-branched tree-like carbon structures have been generated by the catalytic chemical vapor deposition of toluene using ferrocene as the catalyst precursor and investigated by means of SEM, TEM, and EDX. It is found that a temperature of 1000-1200 °C and a carrier gas flow rate of 1000-2500 ml/min are necessary for the generation of the carbon trees. Their morphologies and microstructures change greatly with the changing reaction conditions. The fractal dimensions of the trees are calculated to quantitatively investigate the influence of different reaction temperatures on the morphologies.     

CVD growth of carbon nanotube bundle arrays

Recent discovery of enhanced field emission current intensity from arrays of bundles of carbon nanotubes (CNT) has prompted this investigation of the growth of CNT bundle arrays by metal-catalyzed chemical vapor deposition (CVD), in order to understand and control the growth of these arrays. CNT bundle array growth has been characterized as a function of array geometric parameters: the CNT bundle diameter and inter-bundle spacing. We find that CNT bundle array growth varies significantly with bundle size and spacing, which we suggest is due to the formation of a volatile molecular byproduct of ethylene decomposition that enhances CNT growth in areas with high concentrations of metal catalyst. We have also studied and optimized CNT growth with respect to a variety of CVD process parameters, in order to control the length of the resultant CNT bundles. We find that the length of the CNT can be reliably controlled by varying either the reaction time or the gas pressure. Such control over CNT bundle length will be crucial in the incorporation of these bundle arrays into high-intensity electron field emission devices.     

Field emission of polycrystalline diamond films grown by microwave-plasma chemical vapor deposition. I. Effects of surface morphology of diamond

The effects of surface morphology on the field emission of non-doped polycrystalline diamond films with thicknesses ranging from 5 to 55 μm were studied. Diamond films grown by a microwave-plasma chemical vapor deposition technique had both the diamond and non-diamond components with pyramidal and angular crystalline structures. Although the average crystallite size increased with increasing the film thickness (d), the volume fraction of the non-diamond components in the films was insensitive to the film thickness. However, the turn-on electric field, F_T, (defined as the low-end electric field to emit electrons) showed a U-shape dependence on the film thickness. This U-shape dependence was explained by a model in which the emission current was controlled by Fowler–Norheim tunneling of electrons at surface of the pyramids when d was thinner than 20 μm and by carrier transport in the polycrystalline diamond film when d was thicker than 20 μm. The lowest field of 4 V/μm was obtained in the film with 20 μm thick.     

Enhanced thermionic energy conversion and thermionic emission from doped diamond films through methane exposure

Thermionic electron emitters are a crucial component in applications ranging from high power telecommunication, electron guns, space thrusters and direct thermal to electrical energy converters. One key characteristic of diamond based electron sources is the negative electron affinity (NEA) properties of hydrogen terminated surfaces which can significantly reduce the emission barrier. Nitrogen and phosphorus doped diamond films have been prepared by plasma assisted chemical vapor deposition on metallic substrates for thermionic emitter application. Electron emission current versus temperature was measured and analyzed with respect to the Richardson-Dushman relation, with work function and Richardson constant deduced from the results. Initial emission measurements up to 500 °C in vacuum were followed by emitter characterization while the sample was exposed to methane. Vacuum measurements indicated a work function of 1.18 eV and 1.44 eV for phosphorus and nitrogen doped diamond films, respectively. Introduction of methane resulted in a significant increase of the emission current which was ascribed to contribution from ionization processes which increase charge transfer from the emitter surface. This phenomenon was utilized in a thermionic energy conversion structure by introduction of methane in the inter electrode gap where a two-fold increase in output power was observed upon introduction of the gaseous species.     

High-quality homoepitaxial diamond (100) films grown under high-rate growth condition

We present advantages of high-power microwave plasma chemical vapor deposition (MPCVD) in homoepitaxial diamond film deposition. Diamond films grown at comparatively high growth rate of 3.5 μm/h showed intense free-exciton recombination emission at room temperature. The free-exciton decay time of the diamond film at room temperature, 22 ns, was much longer than that of type-IIa single crystal, indicating electronically high quality of the homoepitaxial films. Dislocation-related emissions were locally observed, a part of which created by mechanical polishing process was successfully removed by surface etching process using oxygen plasma. Another advantage of the high-power MPCVD is effective impurity doping; boron-doped diamond films with high carrier mobility and high carrier concentration were reproducibly deposited. An ultraviolet photodetector fabricated using the high-quality undoped diamond film showed lower noise equivalent power as well as higher photoresponsivity for ultraviolet light with better visible-blind property, compared to those of standard Si-based photodetectors. The high-power MPCVD is, thus, indispensable technique for depositing high quality diamond films for electronic devices.     

Alpha particle transient response of a polycrystalline diamond detector

We report the transient response of room temperature pulses generated from alpha particles from a chemical vapor deposition (CVD) polycrystalline diamond detector. For transient signals dominated by electron transport only prompt pulse shapes were observed with an average rise time of 160 ns limited by the preamplifier rise time. For transient signals dominated by hole transport significant slow components were observed in the majority of pulses due to thermal emission of charge from shallow hole traps. These slow pulses were observed from the device when in its as-grown state, without any previous ‘priming’. Two separate slow components were identified from the hole pulses, with average rise times of 600 ns and 1–10 μs, respectively. These data suggest that room temperature electron transport in polycrystalline CVD diamond is prompt, with no evidence for thermal de-trapping. In contrast hole transport in our sample at room temperature contains a significant delayed component due to thermal emission of holes from at least two bands of shallow defects.     

Microstructural and biological properties of nanocrystalline diamond coatings

In this study, the microstructural, mechanical, adhesion, and hemocompatibility properties of nanocrystalline diamond coatings were examined. Microwave plasma chemical vapor deposition (MPCVD) was used to deposit nanocrystalline diamond coatings on silicon (100) substrates. The coating surface consisted of faceted nodules, which exhibited a relatively wide size distribution and an average size of 60 nm. High-resolution transmission electron microscopy demonstrated that these crystals were made up of 2–4 nm rectangular crystallites. Raman spectroscopy and electron diffraction revealed that the coating contained both crystalline and amorphous phases. The microscratch adhesion study demonstrated good adhesion between the coating and the underlying substrate. Scanning electron microscopy and energy dispersive X-ray analysis revealed no crystal, fibrin, protein, or platelet aggregation on the surface of the platelet rich plasma-exposed nanocrystalline diamond coating. This study suggests that nanocrystalline diamond is a promising coating for use in cardiovascular medical devices.     

Synthesis of diamond films and nanotips through graphite etching

A hot filament CVD process based on hydrogen etching of graphite has been developed to synthesize diamond films and nanotips. The graphite sheet was placed close to the substrate and only hydrogen was supplied during deposition. No hydrocarbon feed gases are required for this process. High quality diamond films were synthesized with high growth rate on P-type (1 0 0)-oriented silicon wafers without discharge or bias. The diamond growth rate is approximately five times higher than that through conventional hot filament chemical vapor deposition using a gas mixture of methane and hydrogen (1 vol.% methane) under similar deposition conditions. The diamond films synthesized in this process exhibit smaller crystallites and contain smaller amount of non-diamond carbon phases. Synthesis of well-aligned diamond nanotips with various orientation angles was achieved on the CVD diamond-coated Si substrate when the substrate holder was negatively biased in a DC glow discharge. The nanotips grown at locations far enough from the sample edges are aligned vertically, while those around the sample edges are tilted and point away from the sample center. The alignment orientation of the nanotips appears to be determined by the direction of the local electric field lines on the sample surfaces.