Nanodiamond lateral comb array field emission diode for high current applications

Nanodiamond comb-shaped lateral field emitter arrays in diode configuration were fabricated and characterized for high current field emission. Nitrogen-incorporated nanocrystalline diamond with grain size of 5–10 nm was micropatterned using RIE to realize interconnected arrays of comb structures equipped with uniformly spaced high aspect ratio lateral emitter fingers. A 9000-fingered nanodiamond lateral comb array diode with an inter-electrode spacing of 8 μm demonstrated a high emission current of  25 mA at an anode voltage of 260 V (electric field  32 V/μm) in 10^− 7 Torr vacuum. The lateral emitter configuration shows potential for higher power with no emission current saturation observed. These vacuum micro/nanoelectronic devices comprised of nanodiamond lateral field emission diodes are attractive for low-voltage operating high current electron sources, high-power and high-speed switches, and other extreme demand/extreme environment electronics.     

High-Q optomechanical circuits made from polished nanocrystalline diamond thin films

We demonstrate integrated optomechanical circuits with high mechanical quality factors prepared from nanocrystalline diamond thin films. Using chemomechanical polishing, the RMS surface roughness of as grown polycrystalline diamond films is reduced below 3 nm to allow for the fabrication of high-quality nanophotonic circuits. By integrating free-standing nanomechanical resonators into integrated optical devices, efficient read-out of the thermomechanical motion of diamond resonators is achieved with on-chip Mach–Zehnder interferometers. Mechanical quality factors up to 28,800 are measured for four-fold clamped optomechanical resonators coupled to the evanescent near-field of nanophotonic waveguides. Our platform holds promise for large-scale integration of optomechanical circuits for on-chip metrology and sensing applications.     

Characterization of high-quality polycrystalline diamond and its high FET performance

We characterized high-quality polycrystalline diamond with large grains and fabricated polycrystalline diamond field effect transistors (FETs). The polycrystalline diamond had (110) preferred orientation, and its typical grain size was  100 μm. Well-resolved free exciton related emissions were observed at room temperature in cathodoluminescence. The FETs showed extremely high DC and RF performance. The cut-off frequency for current gain (f_T) and power gain (f_max) were 45 and 120 GHz, respectively. The maximum drain current (I_DS) was 550 mA/mm. These values are the highest among diamond FETs, including those fabricated from single-crystal diamond. These results suggest that high-quality polycrystalline diamond, whose maximum size is 4 in., is very promising for diamond electronic devices.     

Field penetration and its contribution to field enhanced thermionic electron emission from nanocrystalline diamond films

Field emission from sulfur doped nanocrystalline diamond films is characterized by intense emission sites with nm scale diameters. Field emission measurements were obtained at room temperature and analyzed in terms of the Fowler–Nordheim expression where electron emission is due to tunneling through a diminished barrier. The electron emission versus temperature was also recorded at a series of applied fields from 0.5 to 0.8 V/μm. These results were analyzed in terms of a modified Richardson–Dushman relation which describes field dependent thermionic emission. It was found that both sets of data could be fit with a work function of 2.0 eV and a field enhancement factor of  1750. The large field enhancement could not be correlated with specific structures on the relatively flat surfaces. The field and thermionic-field emission from the sulfur doped nanocrystalline diamond films is evaluated by a model which includes barrier lowering as a result of field penetration effects.     

Superconducting nano-mechanical diamond resonators

In this work we present the fabrication and characterization of superconducting nano-mechanical resonators made from nanocrystalline boron doped diamond (BDD). The oscillators can be driven and read out in their superconducting state and show quality factors as high as 40,000 at a resonance frequency of around 10 MHz. Mechanical damping is studied for magnetic fields up to 3 T where the resonators still show superconducting properties. Due to their simple fabrication procedure, the devices can easily be coupled to other superconducting circuits and their performance is comparable with state-of-the-art technology.     

Carbon nanotubes field emission integrated triode amplifier array

Because the high frequency operation of a field emission triode amplifier is dictated by the cutoff frequency and not the electron transit time, a high ratio of transconductance, g_m to the overlapping interelectrode capacitance, C_g is the desired outcome. Consequently, to achieve high frequency performance of the CNT amplifier array in this study, C_g was reduced by performing a dual-mask photolithography process to minimize the overlapping gate area, and, the insulating layer's thickness was increased. Moreover, wedge-shaped CNT emitter arrays are employed to increase emission sites, resulting in return higher g_m. Both dc and ac performance of the amplifier were characterized. The triode amplifier array exhibited a high current of  0.32 mA (74 mA/cm²), g_m of  63 μS and voltage gain of  18 dB. Frequency response of the triode amplifier up to 20 kHz was also investigated. A theoretical cutoff frequency of > 70 MHz could be achieved with proper shielding of the test setup.     

The application of polycrystalline diamond in a thin film packaging process for MEMS resonators

This paper reports the design, fabrication and testing of a polycrystalline diamond (poly-C) thin film packaging process for a MEMS cantilever type resonator using a 4-mask fabrication process, which integrates chemical vapor deposition (CVD) diamond thin film technology with an encapsulation packaging process. After poly-C cantilever beam resonators were fabricated using the first two masks, a sacrificial PECVD SiO₂ layer with a thickness in the range of 4–5 μm was deposited at 350 °C and patterned to create the package anchor. Then, a 4-μm-thick poly-C film was grown and patterned to create the thin film packaging structure containing fluidic access ports for the removal of the sacrificial layer. The fluidic access ports were finally sealed with an additional poly-C growth. To evaluate the efficacy of the poly-C encapsulation process, poly-C cantilever beam resonators were tested using a piezoelectric actuation and laser detection method before and after the poly-C packaging process. Resonance frequencies measured before and after are in the range of 240–320 kHz, which is consistent with predicted calculations. A modified fabrication process was designed to test the fluidic hermiticity of the thin film package.     

Pre-nucleation techniques for enhancing nucleation density and adhesion of low temperature deposited ultra-nanocrystalline diamond

Effect of pre-nucleation techniques on enhancing nucleation density and the adhesion of ultra-nanocrystalline diamond (UNCD) deposited on the Si substrates at low temperature were investigated. Four different pre-nucleation techniques were used for depositing UNCD films: (i) bias-enhanced nucleation (BEN); (ii) pre-carburized and then ultrasonicated with diamond powder solution (PC-U); (iii) ultrasonicated with diamond and Ti mixed powder solution (U-m); (iv) ultrasonicated with diamond powder solution (U). The nucleation density is lowest for UNCD/U-substrate films ( 10⁸ grains/cm²), which results in roughest surface and poorest film-to-substrate adhesion. The UNCD/PC-U-substrate films show largest nucleation density ( 1 × 10¹¹ grains/cm²) and most smooth surface (8.81 nm-rms), whereas the UNCD/BEN-substrate films exhibit the strongest adhesion to the Si substrates (critical loads =  67 mN). Such a phenomenon can be ascribed to the high kinetic energy of the carbon species, which easily form covalent bonding, Si–C, and bond strongly to both the Si and diamond.     

A novel “coral” carbon microprobe with and without N2 incorporation

“Coral”-type microstructure carbon films, with and without N₂ incorporation, were grown on sharpened tungsten microprobes by plasma enhanced chemical vapor deposition (PECVD) using H₂/CH₄/N₂ and H₂/CH₄ gas mixtures, respectively. The electrochemical behaviors of the coral-type carbon coated tungsten microprobe, characterized by various concentrations of ferrocyanide in a background of 0.1 M KCl, show excellent structural stability with similar microstructure before and after prolonged analysis without the need of surface pretreatment. The microprobes exhibit quasi-reversible kinetics with high signal-to-noise S/B ratio. The N₂ incorporated microprobe shows a slightly wider potential window, no surface adsorption of the analyte and higher sensitivity as compared to the sample without nitrogen incorporation. Furthermore, the wide potential window of  3 V is very good as compared to boron-doped diamond electrodes which are  3.5 V. This well behaved; broad electrochemical behavior and the simple fabrication method make the “coral” carbon film microprobe an excellent candidate for electrochemical sensing.     

UV Schottky photodiode on boron-doped CVD diamond films

We report on experimental study of photosensitivity and Q-DLTS spectra of polycrystalline CVD diamond UV photodetectors. The measured characteristics of Schottky photodiode on boron-doped diamond films are compared with those obtained for planar photoconductive structures (photoresistor type) based on undoped CVD diamond. The Schottky photodiode exhibited a sharp cut-off in photoresponse with spectral discrimination ratio (between wavelengths of 190 nm and 700 nm) as high as 5 · 10⁵ at zero bias voltage (at zero dark current). The photodiode showed the maximum of photoresponse at wavelength < 190 nm, and a low density of trapping and recombination centers as evaluated with the Q-DLTS technique. The devices demonstrated the photoresponsivity at 190 nm from 0.03 to 0.1 A/W with quantum yield of 0.20 to 0.67 in closed circuit, while the photovoltage ≥ 1.6 V was measured in open circuit regime. Another type of UV detector, the planar photoconductive structures with interdigitizing ohmic electrodes fabricated on undoped diamond film and operated under a bias voltage, revealed a higher density of (surface) defect centers and the maximum photoresponse at  210 nm wavelength. A strong influence of UV light illumination on the Q-DLTS spectra of the planar photoconductive structures was observed. This effect can be used for development of new UV detectors and dosimeters based on the Q-DLTS signal measurements.     

Homoepitaxial CVD diamond: Raman and time-resolved PL characterization

In this work, we report on the structural characterization of homoepitaxial Microwave Plasma Enhanced CVD diamond grown onto Ib diamond substrates by varying systematically the methane to hydrogen ratio in the gas mixture (1–7% CH₄). X-ray diffraction, Raman spectroscopy and photoluminescence (PL) have been used to characterize the diamond samples. Raman measurements pointed out the excellent crystalline quality and phase purity of the specimens. PL measurements in the 1.7–2.7 eV energy range have shown completely flat spectra, excluding the presence of nitrogen-related optical centers. Such results show that the homoepitaxial CVD diamond can be grown, at moderate microwave power (720 W), and at growth rates not too low ( 1 μm/h) preserving a good quality. Moreover, the homoepitaxial crystals exhibited a strong free-exciton recombination radiation at room temperature even at the highest methane concentration used (7%). Preliminary measurements of the lifetime of the free exciton at room temperature have been also performed. The excitation was produced by a 5 ns pulsed laser irradiation at energies above the diamond band gap. The results have been compared with the structural properties of the samples and correlated with the growth conditions.     

Enhanced performance of HFCVD nanocrystalline diamond self-mated tribosystems by plasma pretreatments on silicon nitride substrates

Nanocrystalline diamond (NCD) coatings were grown by the hot-filament chemical vapour deposition (HFCVD) method on hydrogen plasma pretreated silicon nitride (Si₃N₄) substrates. The friction and wear behaviour of self-mated NCD films, submitted to unlubricated sliding and high applied loads (up to 90 N), was assessed using an oscillating ball-on-flat configuration in ambient atmosphere. The reciprocating tests revealed an initially high friction coefficient peak, associated to the starting surface roughness of NCD coatings (R_q = 50 nm). Subsequently, a steady-state regime with low friction coefficient values (0.01–0.04) sets in, related to a smoother (R_q = 17 nm) tribologically modified surface. A polishing wear mechanism governing the material loss was responsible for mild wear coefficients (k  10^− 7 mm³ N^− 1 m^− 1). The hydrogen etching procedure notably increased the film adhesion with respect to untreated surfaces as demonstrated by the high threshold loads (60 N; 3.5 GPa) prior to film delamination.     

High-pressure and high-temperature annealing effects on CVD homoepitaxial diamond films

High-pressure and high-temperature (HPHT) annealing effects on the chemical vapor-deposited (CVD) homoepitaxial diamond films were investigated. By the HPHT annealing, the intensity of free-exciton (FE)-related emission was increased by  2 times and the luminescence bands from 270 to 320 nm, which originate from 5RL and 2BD bands, were almost completely eliminated in the cathodoluminescence (CL) spectrum. The CL intensity of band-A emission, which is related to crystal defects in diamond, was also decreased. The hole mobility at room temperature was increased from 826 to 1030 cm²/Vs by HPHT annealing. These results suggest that HPHT annealing decreases the crystalline defects and improves the optical and electronic properties of homoepitaxial diamond films.     

Thermal activation and alkali dissolution of silicon from illite

TGA, DTA, FTIR, XRD and 29Si MAS NMR were used to investigate the thermal activation of illite. Illite experiences a series of thermal solid-state phase transformations. Dehydroxylation at 400700 °C forms dehydrated illite, which remains the layered framework of illite. From 700 °C to 1093 °C, Si–O tetrahedral framework remains unchanged. When heated above 1093 °C, the layered structure is destroyed and an amorphous silica-rich glass phase is formed. The mullitization occurs when the temperature exceeds 1100 °C.XRD and FTIR studies show that the silica in silica-rich glass phase dissolves in soda liquor, which indicates that silicon can be removed from illite after thermochemical activation (TCA) followed by alkali leaching. The formation of sodium aluminosilicates of Na₉₆Al₉₆Si₉₆O₃₈₄ and 0.95Na₂O · Al₂O₃ · 3.25SiO₂ · 4.79H₂O during alkali leaching may reduce the desilication to a great extent.Desilication tests after TCA show that the suitable activation conditions for illite are 11001150°C and 9060 min. A desilication of 45% was obtained under the conditions for an ore sample bearing about 85% illite, 9% quartz and 5% muscovite.     

Electrically conductive properties of tungsten-containing diamond-like carbon films

Tungsten-containing diamond-like carbon films with different metal concentrations were investigated. The films of several hundred nanometers in thickness were deposited on the silicon wafer using RF-PECVD (radio frequency plasma enhanced chemical vapor deposition) method. During deposition, metal component was co-sputtered using DC magnetron of tungsten target. The six samples with the concentration of 3.8, 6.1, 8.0, 16.3, 24.3 and 41.4 at.% of tungsten were made. The structural analyses were performed by TEM (transmission electron microscope) and Raman spectroscopy. These results indicated that tungsten clusters were well dispersed in amorphous carbon host matrix in the case of tungsten concentration from 3.8 to 24.2 at.%. However, no such a structure can be observed in the sample with 41.4 at.%. The AC electrical resistance was measured in the temperature range of 2–300 K using four-probe method in vacuum condition. The observed temperature dependence of electrical conductivity can be expressed by σ=σ₀exp−2(C₀/kT)^1/2 and tungsten concentration from 3.8 at.% to 24.2 at.%. In addition, the sample with 41.4 at.% showed the resistive superconducting transition at T_c of around  5.5 K.     

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.     

Piezo-actuated nanodiamond cantilever technology for high-speed applications

Diamond cantilever actuators show high resonance frequencies but need also high actuation forces, pointing towards piezoelectric actuation by a PZT/diamond unimorph. In this study lead zirconate titanate (Pb(Zr,Ti)O₃, PZT) layers have been deposited onto nanocrystalline diamond films by sol–gel deposition, to realize high-speed MEMS actuators. The fabrication technology is based on self-aligned patterning and on optical lithography. A mechanical resonance frequency of 3.9 MHz has been obtained for 30 µm cantilever length dominated by the nanodiamond Young's modulus of approximately 1000 GPa.     

Noncatalytic synthesis of carbon nanotubes, graphene and graphite on SiC

Graphene and carbon nanotubes (CNT) can be produced by vacuum decomposition of SiC, but discrepancies and conflicting data in the literature limit the use of this method for CNT synthesis. A systematic study of the effects of SiC surface morphology and carbon transport through the gas phase leads to reproducible and controlled growth of arrays of small-diameter (1–4 walls) nanotubes, which show pronounced radial breathing modes in Raman spectra, on either carbon or silicon (0 0 0 1) face of 6H SiC wafers at 1400–1900 °C. These nanotube arrays have a very high density and are catalyst-free with no internal closures. They show a higher oxidation resistance compared to CNTs produced by catalytic chemical vapor deposition (CVD). Their integration with graphite/graphene or silica layers on SiC wafers is possible in a simple 2-step process and opens new horizons in nanoscale device fabrication.     

A quantitative electron-microscopic investigation of α-phase lamellae in isotactic polypropylene fractions

Lamellar thicknesses and cross-hatching frequencies in α-isotactic polypropylene have been measured for two series of fractions using linear nucleation to provide large arrays of oriented lamellae in row structures for sampling. One series is of high tacticity polymers differing in molecular mass from 6 × 10⁴ to 8 × 10⁵, the other has low and high tacticity materials for 9 × 10⁴ and 2 × 10⁵ masses. These have allowed the differing influences of both molecular mass and tacticity to be evaluated. Lamellar thicknesses increase with molecular mass to 5 × 10⁵ then level off. This is consistent with the fold surface increasing its free energy by 20% for longer molecules as its structure becomes progressively more complex. Except for the lowest fraction, the thickness of cross-hatching lamellae is less than that of its radial neighbours because of differential thickening. The frequency of cross-hatching is greatest for the least tactic fraction but decreases linearly with molecular length. This dependence suggests that chain ends play a key role in initiation probably by laying down the first segment in epitaxial orientation. This suggestion could also account for the reduced thermal stability of spherulite centres and regions of high cross-hatching density where there is competition for chain ends between thickening and cross-hatching. The curvature of lamellae at the very end of a row mirrors the dependence of lamellae thickness with molecular mass and allows cilia pressure, the factor strongly involved in causing the lamellar divergence underlying spherulitic growth, to be estimated as 100 Pa.     

Self-assembly hydrothermal assisted synthesis of mesoporous anatase in the presence of ethylene glycol

Mesoporous nanocrystalline anatase was prepared hydrothermally employing P123 as structure-directing agent. Ethylene glycol was used as a key synthesis parameter to fine tune the morphology, crystal size and pore size of the resultant mesophases. The incorporation of EG in the synthesis gel resulted in the formation of 1–2 μm sphere-like shapes and led to an increase in the specific surface area from 95 to 170 m²/g, decrease in the average pore size from 11 to 4.8 nm, and decrease in the average crystallite size from 17 to 12 nm. These mesophases were used as photocatalysts for the UV degradation of methylene blue and methyl orange. The mesoporous anatase phases photodegraded MB 1.5–3× faster than commercially available P25 and showed limited photocatalytic behavior for methyl orange.