Kamatchi Jothiramalingam Sankaran

Origin of a needle-like granular structure for ultrananocrystalline diamond films grown in a N2/CH4 plasma

Microstructural evolution as a function of substrate temperature (TS) for conducting ultrananocrystalline diamond (UNCD) films is systematically studied. Variation of the sp2 graphitic and sp3 diamond content with TS in the films is analysed from the Raman and near-edge x-ray absorption fine structure spectra. Morphological and microstructural studies confirm that at TS = 700 °C well-defined acicular structures evolve. These nanowire structures comprise sp3 phased diamond, encased in a sheath of sp2 bonded graphitic phase. TS causes a change in morphology and thereby the various properties of the films. For TS = 800 °C the acicular grain growth ceases, while that for TS = 700 °C ceases only upon termination of the deposition process. The grain-growth process for the unique needle-like granular structure is proposed such that the CN species invariably occupy the tip of the nanowire, promoting an anisotropic grain-growth process and the formation of acicular structure of the grains. The electron field emission studies substantiate that the films grown at TS = 700 °C are the most conducting, with conduction mediated through the graphitic phase present in the films.

Enhancing electrical conductivity and electron field emission properties of ultrananocrystalline diamond films by copper ion implantation and annealing

Copper ion implantation and subsequent annealing at 600 °C achieved high electrical conductivity of 95.0 (Ωcm)−1 for ultrananocrystalline diamond (UNCD) films with carrier concentration of 2.8 × 1018 cm−2 and mobility of 6.8 × 102 cm2/V s. Transmission electron microscopy examinations reveal that the implanted Cu ions first formed Cu nanoclusters in UNCD films, which induced the formation of nanographitic grain boundary phases during annealing process. From current imaging tunneling spectroscopy and local current-voltage curves of scanning tunneling spectroscopic measurements, it is observed that the electrons are dominantly emitted from the grain boundaries. Consequently, the nanographitic phases presence in the grain boundaries formed conduction channels for efficient electron transport, ensuing in excellent electron field emission (EFE) properties for copper ion implanted/annealed UNCD films with low turn-on field of 4.80 V/μm and high EFE current density of 3.60 mA/cm2 at an applied field of 8.0 V/μm.

Humidity-dependent friction mechanism in an ultrananocrystalline diamond film

Friction behaviour of an ultrananocrystalline diamond film deposited by the microwave plasma-enhanced chemical vapour deposition technique is studied in a controlled humid atmosphere. The value of friction coefficient consistently decreases while increasing the humidity level during the tribology test. This value is 0.13 under 10% relative humidity conditions, which is significantly decreased to 0.004 under 80% relative humidity conditions. Such a reduction in friction coefficient is ascribed to passivation of dangling covalent bonds of carbon atoms, which occurs due to the formation of chemical species of hydroxyl and carboxylic groups such as C?COO, CH3COH and CH2?O bonding states.

Engineering the Interface Characteristics of Ultrananocrystalline Diamond Films Grown on Au-Coated Si Substrates

Enhanced electron field emission (EFE) properties have been observed for ultrananocrystalline diamond (UNCD) films grown on Au-coated Si (UNCD/Au-Si) substrates. The EFE properties of UNCD/Au-Si could be turned on at a low field of 8.9 V/μm, attaining EFE current density of 4.5 mA/cm(2) at an applied field of 10.5 V/μm, which is superior to that of UNCD films grown on Si (UNCD/Si) substrates with the same chemical vapor deposition process. Moreover, a significant difference in current-voltage curves from scanning tunneling spectroscopic measurements at the grain and the grain boundary has been observed. From the variation of normalized conductance (dI/dV)/(I/V) versus V, bandgap of UNCD/Au-Si is measured to be 2.8 eV at the grain and nearly metallic at the grain boundary. Current imaging tunneling spectroscopy measurements show that the grain boundaries have higher electron field emission capacity than the grains. The diffusion of Au into the interface layer that results in the induction of graphite and converts the metal-to-Si interface from Schottky to Ohmic contact is believed to be the authentic factors, resulting in marvelous EFE properties of UNCD/Au-Si.

Direct observation and mechanism for enhanced electron emission in hydrogen plasma-treated diamond nanowire films.

The effect of hydrogen plasma treatment on the electrical conductivity and electron field emission (EFE) properties for diamond nanowire (DNW) films were systematically investigated. The DNW films were deposited on silicon substrate by N2-based microwave plasma-enhanced chemical vapor deposition process. Transmission electron microscopy depicted that DNW films mainly consist of wirelike diamond nanocrystals encased in a nanographitic sheath, which formed conduction channels for efficient electron transport and hence lead to excellent electrical conductivity and EFE properties for these films. Hydrogen plasma treatment initially enhanced the electrical conductivity and EFE properties of DNW films and then degraded with an increase in treatment time. Scanning tunneling spectroscopy in current imaging tunneling spectroscopy mode clearly shows significant increase in local emission sites in 10 min hydrogen plasma treated diamond nanowire (DNW10) films as compared to the pristine films that is ascribed to the formation of graphitic phase around the DNWs due to the hydrogen plasma treatment process. The degradation in EFE properties of extended (15 min) hydrogen plasma-treated DNW films was explained by the removal of nanographitic phase surrounding the DNWs. The EFE process of DNW10 films can be turned on at a low field of 4.2 V/μm and achieved a high EFE current density of 5.1 mA/cm(2) at an applied field of 8.5 V/μm. Moreover, DNW10 films with high electrical conductivity of 216 (Ω cm)(-1) overwhelm that of other kinds of UNCD films and will create a remarkable impact to diamond-based electronics.

Structural and Electrical Properties of Conducting Diamond Nanowires

Conducting diamond nanowires (DNWs) films have been synthesized by N₂-based microwave plasma enhanced chemical vapor deposition. The incorporation of nitrogen into DNWs films is examined by C 1s X-ray photoemission spectroscopy and morphology of DNWs is discerned using field-emission scanning electron microscopy and transmission electron microscopy (TEM). The electron diffraction pattern, the visible-Raman spectroscopy, and the near-edge X-ray absorption fine structure spectroscopy display the coexistence of sp³ diamond and sp² graphitic phases in DNWs films. In addition, the microstructure investigation, carried out by high-resolution TEM with Fourier transformed pattern, indicates diamond grains and graphitic grain boundaries on surface of DNWs. The same result is confirmed by scanning tunneling microscopy and scanning tunneling spectroscopy (STS). Furthermore, the STS spectra of current-voltage curves discover a high tunneling current at the position near the graphitic grain boundaries. These highly conducting regimes of grain boundaries form effective electron paths and its transport mechanism is explained by the three-dimensional (3D) Motts variable range hopping in a wide temperature from 300 to 20 K. Interestingly, this specific feature of high conducting grain boundaries of DNWs demonstrates a high efficiency in field emission and pave a way to the next generation of high-definition flat panel displays or plasma devices.

Gold ion implantation induced high conductivity and enhanced electron field emission properties in ultrananocrystalline diamond films

We report high conductivity of 185 (Ω cm)−1 and superior electron field emission (EFE) properties, viz. low turn-on field of 4.88 V/μm with high EFE current density of 6.52 mA/cm2 at an applied field of 8.0 V/μm in ultrananocrystalline diamond (UNCD) films due to gold ion implantation. Transmission electron microscopy examinations reveal the presence of Au nanoparticles in films, which result in the induction of nanographitic phases in grain boundaries, forming conduction channels for electron transport. Highly conducting Au ion implanted UNCD films overwhelms that of nitrogen doped ones and will create a remarkable impact to diamond-based electronics.

Investigations on Diamond Nanostructuring of Different Morphologies by the Reactive-Ion Etching Process and Their Potential Applications

We report the systematic studies on the fabrication of aligned, uniform, and highly dense diamond nanostructures from diamond films of various granular structures. Self-assembled Au nanodots are used as a mask in the self-biased reactive-ion etching (RIE) process, using an O2/CF4 process plasma. The morphology of diamond nanostructures is a close function of the initial phase composition of diamond. Cone-shaped and tip-shaped diamond nanostructures result for microcrystalline diamond (MCD) and nanocrystalline diamond (NCD) films, whereas pillarlike and grasslike diamond nanostructures are obtained for Ar-plasma-based and N2-plasma-based ultrananocrystalline diamond (UNCD) films, respectively. While the nitrogen-incorporated UNCD (N-UNCD) nanograss shows the most-superior electron-field-emission properties, the NCD nanotips exhibit the best photoluminescence properties, viz, different applications need different morphology of diamond nanostructures to optimize the respective characteristics. The optimum diamond nanostructure can be achieved by proper choice of granular structure of the initial diamond film. The etching mechanism is explained by in situ observation of optical emission spectrum of RIE plasma. The preferential etching of sp(2)-bonded carbon contained in the diamond films is the prime factor, which forms the unique diamond nanostructures from each type of diamond films. However, the excited oxygen atoms (O*) are the main etching species of diamond film.

Improvement in Tribological Properties by Modification of Grain Boundary and Microstructure of Ultrananocrystalline Diamond Films

Grain boundaries and microstructures of ultrananocrystalline diamond (UNCD) films are engineered at nanoscale by controlling the substrate temperature (TS) and/or by introducing H2 in the commonly used Ar/CH4 deposition plasma in a microwave plasma enhanced chemical vapor deposition system. A model for the grain growth is proposed. The films deposited at low TS consist of random/spherical shaped UNCD grains with well-defined grain boundaries. On increasing TS, the adhering efficiency of CH radical onto diamond lattice drops and trans-polyacetylene (t-PA) encapsulating the nanosize diamond clusters break due to hydrogen abstraction activated, rendering the diamond phase less passivated. This leads to the C2 radical further attaching to the diamond lattice, resulting in the modification of grain boundaries and promoting larger sized clustered grains with a complicated defect structure. Introduction of H2 in the plasma at low TS gives rise to elongated clustered grains that is attributed to the presence of atomic hydrogen in the plasma, preferentially etching out the t-PA attached to nanosized diamond clusters. On the basis of this model a technologically important functional property, namely tribology of UNCD films, is studied. A low friction of 0.015 is measured for the film when ultranano grains are formed, which consist of large fractions of grain boundary components of sp(2)/a-C and t-PA phases. The grain boundary component consists of large amounts of hydroxylic and carboxylic functional groups which passivates the covalent carbon dangling bonds, hence low friction coefficient. The improved tribological properties of films can make it a promising candidate for various applications, mainly in micro/nanoelectro mechanical system (M/NEMS), where low friction is required for high efficiency operation of devices.

An amperometric urea bisosensor based on covalent immobilization of urease on N2 incorporated diamond nanowire electrode

N2 incorporated diamond nanowire (N-DNW) film electrochemical biosensor has utilized for the quantitative determination of urea in aqueous solution and urine sample. N-DNW electrode is wet-chemically cleaned (oxidation) by boiling in a mixture of H2SO4 and HNO3 (3:1) at 200°C for 2h to remove graphite. Urease (Urs) and glutamate dehydrogenase (GLDH) are covalently attached to the oxidized N-DNW electrode by activating the COOH group of N-DNW using ethyl(dimethylaminopropyl)carbodiimide as the coupling agent and N-hydroxysuccinimide as activator. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy data reveal that carboxylic and hydroxyl functionalized nature of N-DNW electrodes Urs-GLDH immobilized N-DNW (Urs-GLDH/N-DNW) has been successfully utilized in urea biosensor which exhibits good performance in sensitivity (6.18 μA/mg dL/cm(2)), stability (~1 month), reproducibility, lower detection limit (3.87 mg/dL) and fast response time (>10s). Urs-GLDH/N-DNW also exhibits electrochemical response when tested for different concentration of human urine in buffer solution (from 1:9 to 4:6). In addition, Urs-GLDH/N-DNW bioelectrode retains 80% of its initial enzyme activity for <1 month, when stored at 4-6°C in a refrigerator.