Plasma-enhanced chemical vapor deposition of nanocrystalline diamond

Nanocrystalline diamond films have attracted considerable attention because they have a low coefficient of friction and a low electron emission threshold voltage. In this paper, the author reviews the plasma-enhanced chemical vapor deposition (PE-CVD) of nanocrystalline diamond and mainly focuses on the growth of nanocrystalline diamond by low-pressure PE-CVD. Nanocrystalline diamond particles of 200–700 nm diameter have been prepared in a 13.56 MHz low-pressure inductively coupled CH₄/CO/H₂ plasma. The bonding state of carbon atoms was investigated by ultraviolet-excited Raman spectroscopy. Electron energy loss spectroscopy identified sp²-bonded carbons around the 20–50 nm subgrains of nanocrystalline diamond particles. Plasma diagnostics using a Langmuir probe and the comparison with plasma simulation are also reviewed. The electron energy distribution functions are discussed by considering different inelastic interaction channels between electrons and heavy particles in a molecular CH₄/H₂ plasma.     

Plasma-enhanced chemical vapor deposition of nanocrystalline diamond

Nanocrystalline diamond films have attracted considerable attention because they have a low coefficient of friction and a low electron emission threshold voltage. In this paper, the author reviews the plasma-enhanced chemical vapor deposition (PE-CVD) of nanocrystalline diamond and mainly focuses on the growth of nanocrystalline diamond by low-pressure PE-CVD. Nanocrystalline diamond particles of 200–700 nm diameter have been prepared in a 13.56 MHz low-pressure inductively coupled CH₄/CO/H₂ plasma. The bonding state of carbon atoms was investigated by ultraviolet-excited Raman spectroscopy. Electron energy loss spectroscopy identified sp²-bonded carbons around the 20–50 nm subgrains of nanocrystalline diamond particles. Plasma diagnostics using a Langmuir probe and the comparison with plasma simulation are also reviewed. The electron energy distribution functions are discussed by considering different inelastic interaction channels between electrons and heavy particles in a molecular CH₄/H₂ plasma.     

Spectroellipsometric and ion beam analytical investigation of nanocrystalline diamond layers

Optical properties of nanocrystalline and ultrananocrystalline diamond films were studied by ex situ variable angle spectroscopic ellipsometry. The films were prepared by Microwave Plasma Enhanced Chemical Vapor Deposition method. In the experiments Ar, CH₄, and H₂ gases were used as source gases. Elastic recoil detection analysis was applied to measure the hydrogen content of the deposited layers. Three-layer optical models were constructed for the evaluation of the measured ellipsometric spectra. Besides the Cauchy relation, the effective medium approximation and the Tauc-Lorentz dispersion relation were also used for the modeling of the optical properties of the diamond films. Atomic force microscopy was applied to investigate the surface roughness in function of the deposition conditions.     

Tuning the conditions for the deposition of nanocrystalline diamond by hot filament chemical vapour deposition

Although large focus has been placed into the deposition of nanocrystalline and ultra-nanocrystalline diamond films, most of this research uses microwave plasma assisted CVD systems. However, the growth conditions used in microwave systems cannot be directly used in hot-filament CVD systems. This paper, aims to enlarge the knowledge of the diamond film depositing process. H2/CH4/Ar gas mixtures have been used to deposit micro, nano and ultra-nanocrystalline diamond films by hot-filament CVD systems. Additionally, the distance between the filaments array and the substrate was varied, in order to observe its effect and consequently the effect of a lower substrate temperature in the nucleation density and deposition. All the samples were characterized for microstructure and quality, using scanning electron microscopy and Raman spectroscopy.     

沉积参数对化学气相沉积纳米金刚石薄膜的影响

用强电流直流伸展电弧化学气相沉积金刚石薄膜装置,在CH4-Ar和CH4-H2-Ar气氛中沉积了纳米金刚石薄膜,研究了沉积气氛中H2加入量和沉积压力对金刚石薄膜显微组织和生长机制的影响.沉积气氛中H2含量对金刚石薄膜的表面形貌、晶粒尺寸和生长速度有显著影响,随着H2含量增加,金刚石晶粒尺寸增大,薄膜生长速度提高.在1%CH4-Ar气氛中沉积的纳米金刚石薄膜,晶粒尺寸细小,薄膜表面形貌光滑平整.在1%CH4-少量H2-Ar气氛中沉积的金刚石薄膜,晶粒尺寸小于100nm,薄膜表面形貌较平整.随着沉积压力提高,金刚石薄膜的生长速度增大.用激光Ram an对金刚石薄膜进行了表征.     

Design and fabrication of piezoresistive strain gauges based on nanocrystalline diamond layers

The paper reports on design, fabrication and characterization of piezoresistive sensors based on boron doped nanocrystalline diamond (NCD) layers. The shape and position of the piezoresistive element was optimized using finite element 3D modeling. Mechanical and piezoresistive simulations were performed. The piezoresistive sensing boron doped diamond thin films were realized on SiO₂/Si₃N₄/Si substrates by microwave plasma enhanced chemical vapor deposition (CVD) and the piezoresistive structures were formed by reactive ion etching. The extensive study of sensor parameters e.g. deformation sensitivity, edge and contact resistances, temperature dependences gauge factor, temperature coefficient of resistance and bridge output voltage was performed. The highest gauge factor at higher temperatures (GF = 7.2 at 250 °C) was observed for moderate doping level (boron to carbon ratio of 3000 ppm). One of the aims was the extraction of piezoresistive coefficients of fabricated diamond layers for utilization in a finite element piezoresistive solver.     

CVD diamond layers for electrochemistry

Diamond electrodes of different morphologies and qualities were manufactured by hot filament chemical deposition (HF CVD) techniques by changing the parameters of diamond growth process. The estimation of diamond quality and identification of different carbon phases was performed by Raman spectroscopy measurements. The effect of diamond quality and amorphous carbon phase content on the electrochemical response of an obtained diamond electrode in 0.5 M H₂SO₄ as supporting electrolyte was investigated by cyclic voltammetry with [Fe(CN)₆]^4?/3? as a redox probe. The kinetic parameters such as catalytic reaction rate constant k₀ and electron transfer coefficient α were determined. The obtained results show that the analytical performance of undoped diamond electrodes can be implemented just by the change of diamond layers quality.     

Sputtered platinum-iridium layers as electrode material for functional electrostimulation

In this study co-sputtered layers of platinum-iridium (PtIr) are investigated as stimulation electrode material. The effects of different sputter parameters on the morphology and the electrochemical behavior are examined. It is shown that films sputtered at the lowest incident energy possess the highest charge storage capacity (CSC). At a Pt:Ir atomic-ratio of 55:45 the obtained CSC of 22 mC/cm² is enhanced compared to the standard stimulation material platinum (16 mC/cm²) but inferior to iridium which has a CSC of 35 mC/cm². Long term cyclic voltammetry measurements show that PtIr can be activated which increases the CSC to 29 mC/cm². Also a change in the film morphology is observed. Sputtered platinum-iridium films promise to combine high mechanical strength and increased charge storage capacity.     

Direct deposition of patterned nanocrystalline CVD diamond using an electrostatic self-assembly method with nanodiamond particles

Micron-sized and precise patterns of nanocrystalline CVD diamond were fabricated successfully on substrates using dispersed nanodiamond particles, charge connection by electrostatic self-assembly, and photolithography processes. Nanodiamond particles which had been dispersed using an attritional milling system were attached electrostatically on substrates as nuclei for diamond growth. In this milling process, poly sodium 4-styrene sulfonate (PSS) was added as an anionic dispersion agent to produce the PSS/nanodiamond conjugates. Ultra dispersed nanodiamond particles with a ζ-potential and average particle size of - 60.5 mV and ～ 15 nm, respectively, were obtained after this milling process. These PSS/nanodiamond conjugates were attached electrostatically to a cationic polyethyleneimine (PEI) coated surface on to which a photoresist had been patterned in an aqueous solution of the PSS/nanodiamond conjugated suspension. A selectively seeded area was formed successfully using the above process. A hot filament chemical vapor deposition system was used to synthesize the nanocrystalline CVD diamond on the seeded area. Micron-sized, thin and precise nanocrystalline CVD diamond patterns with a high nucleation density (3.8 ± 0.4 × 10(11) cm(-2)) and smooth surface were consequently fabricated.     

Protein-modified nanocrystalline diamond thin films for biosensor applications

Diamond exhibits several special properties, for example good biocompatibility and a large electrochemical potential window, that make it particularly suitable for biofunctionalization and biosensing. Here we show that proteins can be attached covalently to nanocrystalline diamond thin films. Moreover, we show that, although the biomolecules are immobilized at the surface, they are still fully functional and active. Hydrogen-terminated nanocrystalline diamond films were modified by using a photochemical process to generate a surface layer of amino groups, to which proteins were covalently attached. We used green fluorescent protein to reveal the successful coupling directly. After functionalization of nanocrystalline diamond electrodes with the enzyme catalase, a direct electron transfer between the enzyme's redox centre and the diamond electrode was detected. Moreover, the modified electrode was found to be sensitive to hydrogen peroxide. Because of its dual role as a substrate for biofunctionalization and as an electrode, nanocrystalline diamond is a very promising candidate for future biosensor applications.     

Thermal stability of nanocrystalline diamond films grown by biased enhanced microwave plasma chemical vapor deposition

The thermal stability of nanocrystalline diamond (NCD) films grown on mirror-polished silicon substrates by biased enhanced microwave plasma chemical vapor deposition was investigated. Different pieces of a NCD sample were annealed for 1 h in an ambient argon atmosphere at 200, 400, 600, and 800 degrees C. The structural and mechanical properties of as-grown and annealed samples were assessed. The surface roughness and high hardness of the samples remained fairly constant with annealing temperature.     

Simplified procedure for patterned growth of nanocrystalline diamond micro-structures

Two technological strategies to generate patterned diamond growth have been tested. The diamond micro-structures (i.e. linear stripes and 5 µm narrow channels) were grown in the thickness of 450 nm on Si/SiO₂ substrates by a microwave plasma chemical vapor deposition process. Strategy 1, employing a metal mask, resulted in unsatisfying patterned diamond growth due to instability of metal mask. Strategy 2 was based on a direct lithographic patterning of the seeding layer and resulted in a strongly selective, homogenous, and compact growth of diamond on the polymer-coated seeding patterns. This is assigned to the high seeding yield. The diamond micro-structures formed in this way exhibit surface conductivity of 10^− 7 (Ω/□)^− 1 as assessed by I–V characteristics. The observed results appear promising for the development of directly grown diamond-based transistors.     

Simulation and bonding of dopants in nanocrystalline diamond

The doping of the wide-band gap semiconductor diamond has led to the invention of many electronic and optoelectronic devices. Impurities can be introduced into diamond during chemical vapor deposition or high pressure-high temperature growth, resulting in materials with unusual physical and chemical properties. For electronic applications one of the main objectives in the doping of diamond is the production of p-type and n-type semiconductors materials; however, the study of dopants in diamond nanoparticles is considered important for use in nanodevices, or as qubits for quantum computing. Such devices require that bonding of dopants in nanodiamond must be positioned substitutionally at a lattice site, and must exhibit minimal or no possibility of diffusion to the nanocrystallite surface. In light of these requirements, a number of computational studies have been undertaken to examine the stability of various dopants in various forms of nanocrystalline diamond. Presented here is a review of some such studies, undertaken using quantum mechanical based simulation methods, to provide an overview of the crystal stability of doped nanodiamond for use in diamondoid nanodevices.     

Biological evaluation of ultrananocrystalline and nanocrystalline diamond coatings

Nanostructured biomaterials have been investigated for achieving desirable tissue-material interactions in medical implants. Ultrananocrystalline diamond (UNCD) and nanocrystalline diamond (NCD) coatings are the two most studied classes of synthetic diamond coatings; these materials are grown using chemical vapor deposition and are classified based on their nanostructure, grain size, and sp³ content. UNCD and NCD are mechanically robust, chemically inert, biocompatible, and wear resistant, making them ideal implant coatings. UNCD and NCD have been recently investigated for ophthalmic, cardiovascular, dental, and orthopaedic device applications. The aim of this study was (a) to evaluate the in vitro biocompatibility of UNCD and NCD coatings and (b) to determine if variations in surface topography and sp³ content affect cellular response. Diamond coatings with various nanoscale topographies (grain sizes 5–400?nm) were deposited on silicon substrates using microwave plasma chemical vapor deposition. Scanning electron microscopy and atomic force microscopy revealed uniform coatings with different scales of surface topography; Raman spectroscopy confirmed the presence of carbon bonding typical of diamond coatings. Cell viability, proliferation, and morphology responses of human bone marrow-derived mesenchymal stem cells (hBMSCs) to UNCD and NCD surfaces were evaluated. The hBMSCs on UNCD and NCD coatings exhibited similar cell viability, proliferation, and morphology as those on the control material, tissue culture polystyrene. No significant differences in cellular response were observed on UNCD and NCD coatings with different nanoscale topographies. Our data shows that both UNCD and NCD coatings demonstrate in vitro biocompatibility irrespective of surface topography.     

Correlation between diamond grain size and hydrogen incorporation in nanocrystalline diamond thin films

Hydrogen-incorporated nanocrystalline diamond thin films have been deposited in microwave plasma enhanced chemical vapour deposition (CVD) system with various hydrogen concentrations in the Ar/CH₄ gas mixture. The bonding environment of carbon atoms was detected by Raman spectroscopy and the hydrogen concentration was determined by elastic recoil detection analysis. Incorporation of H₂ species into Ar-rich plasma was observed to markedly alter the microstructure of diamond films. Raman spectroscopy results showed that part of the hydrogen is bonded to carbon atoms. Raman spectra also indicated the increase of non-diamond phase with the decrease in crystallite size. The study addresses the effects of hydrogen trapping in the samples when hydrogen concentration in the plasma increased during diamond growth and its relation with defective grain boundary region.     

Development of nanocrystalline diamond windows for application in synchrotron beamlines

A multistep growth and masking method allowed developing windows with controlled geometry inside a silicon frame. In this paper, we present a new method to produce nanocrystalline diamond windows with thickness of about 200 nm to 40 μm, with different areas and shapes (circular, rectangular and rounded rectangle). The nanocrystalline diamond (NCD) films deposited on a silicon substrate (100) p-type, had a nucleation density of about 10¹¹ part/cm². Electrostatic self-assembly of nanodiamond seeds (4 nm powder) improved nucleation. Silicon anisotropic etching reveals the window geometry. The high nucleation density enabled smooth surfaces on both sides without the need for polishing the window. Pressure tests were performed in windows of varying thickness. The windows with thickness larger than 10 μm supported a pressure gradient of 1 atm.     

A study of polyaniline deposited nanocrystalline diamond films for glucose detection

Nitrogen-doped nanocrystalline diamond (NCD) films have been deposited on Si substrates in CH4/Ar/N2 gas mixtures by the microwave plasma enhanced chemical vapor deposition (MPECVD) technique. Such films contain very small diamond grains (10 to 30 nm) with high electrical conductivity (126 ohms(-1) cm(-1)) compared to un-doped ones. The films were characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Near edge X-ray fine structure studies showed that the nitrogen-doped NCD had slightly higher sp2/sp3 bonding ratio compared to the un-doped sample. A nitrogen-doped NCD electrode was functionalized by conducting polymer films (polyaniline) to work as an interface for biomedical applications. Glucose sensing has been demonstrated based on this functionalized electrode. Linear response of the sensor has been observed for glucose concentration up to 9 mM.     

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.     

Effect of carbon concentration on the optical properties of nanocrystalline diamond films deposited by hot-filament chemical vapor deposition method

With reducing diamond grain size to nano-grade, the increase of grain boundaries and non-diamond phase will result in the change of the optical properties of chemical vapor deposition (CVD) diamond films. In this paper, the structure, morphology and optical properties of nanocrystalline diamond (NCD) films, deposited by hot-filament chemical vapor deposition (HFCVD) method under different carbon concentration, are investigated by SEM, Raman scattering spectroscopy, as well as optical transmission spectra and spectroscopic ellipsometry. With increasing the carbon concentration during the film deposition, the diamond grain size is reduced and thus a smooth diamond film can be obtained. According to the data on the absorption coefficient in the wavelength range from 200 to 1100 nm, the optical gap of the NCD films decreases from 4.3 eV to 3.2 eV with increasing the carbon concentration from 2.0% to 3.0%. From the fitting results on the spectroscopic ellipsometric data with a four-layer model in the photon energy range of 0.75-1.5 eV, we can find the diamond film has a lower refractive index (n) and a higher extinction coefficient (k) when the carbon concentration increases.     

掺氮N型纳米金刚石薄膜的电化学表面氢化及表征

针对掺氮N型纳米金刚石薄膜独特的结构特征,采用温和的电化学阴极表面极化处理成功实现了掺氮N型纳米金刚石薄膜的表面氢化。通过X射线光电子能谱(XPS)、表面接触角、电化学电容-电压分析、Raman光谱、扫描电子显微镜(SEM)表征,详细分析了阴极极化处理前后掺氮N型纳米金刚石薄膜的表面结构以及微观结构。结果表明,该阴极极化处理工艺不仅能够成功获得表面氢终止状态,而且对薄膜的微观结构尤其是晶界处sp2杂化态碳相无明显影响,说明该工艺是一种高效无损的掺氮N型纳米金刚石薄膜表面氢化工艺。