Cytotoxicity of Boron-Doped Nanocrystalline Diamond Films Prepared by Microwave Plasma Chemical Vapor Deposition

Boron-doped nanocrystalline diamond（NCD） exhibits extraordinary mechanical properties and chemical stability,making it highly suitable for biomedical applications.For implant materials,the impact of boron-doped NCD films on the character of cell growth（i.e.,adhesion,proliferation） is very important.Boron-doped NCD films with resistivity of 10-2Ω·cm were grown on Si substrates by the microwave plasma chemical vapor deposition（MPCVD） process with H2 bubbled B2O3.The crystal structure,diamond character,surface morphology,and surface roughness of the boron-doped NCD films were analyzed using different characterization methods,such as X-ray diffraction（XRD）,Raman spectroscopy,scanning electron microscopy（SEM） and atomic force microscopy（AFM）.The contact potential difference and possible boron distribution within the film were studied with a scanning kelvin force microscope（SKFM）.The cytotoxicity of films was studied by in vitro tests,including fluorescence microscopy,SEM and MTT assay.Results indicated that the surface roughness value of NCD films was 56.6 nm and boron was probably accumulated at the boundaries between diamond agglomerates.MG-63 cells adhered well and exhibited a significant growth on the surface of films,suggesting that the boron-doped NCD films were non-toxic to cells.

Phenol degradation by anodic oxidation on boron-doped diamond electrode combining TiO_2 Photocatalysis

Boron-doped diamond （BDD） electrocatalysis is combined with photocatalysis using titanium dioxide （TiO2） as a catalyst to improve pollutant-oxidation efficiency. Phenol solution is chosen as model wastewater. Different methods involving BDD and/or TiO2 during the degradation processes are compared. Parameters such as the currency density and initial concentration are varied in order to determine their effects on the oxidation process. Moreover, the degradation kinetics of phenol is experimentally studied. The results reveal the superiority of series combination of BDD and TiO2, especially the treatment process of electrocatalysis and succedent photocatalysis, and the optimum working currency density for electrocatalysis is 25.48 mA/cm2. The removal rate decreases with the increase in the initial phenol concentration and the degradation reaction follows quasi-first-order kinetics equation.

EFFECT OF GRID BIAS ON DEPOSITION OF NANOCRYSTALLINE DIAMOND FILMS

A positive grid bias and a negative substrate bias voltages are applied to the self-made hot filament chemical vapor deposited （HFCVD） system. The high quality nanocrystalline diamond （NCD） film is successfully deposited by double bias voltage nucleation and grid bias voltage growth. The Micro-Raman XRD SEM and AFM are used to investigate the diamond grain size, microstructure, surface morphology, and nucleation density. Results show that the obtained NCD has grain size of about 20 nm. The effect of grid bias voltage on the nucleation and the diamond growth is studied. Experimental results and theoretical analysis show that the positive grid bias increases the plasma density near the hot filaments, enhances the diamond nucleation, keeps the nanometer size of the diamond grains, and improves the quality of diamond film.

Electrochemical incineration of dimethyl phthalate by anodic oxidation with boron-doped diamond electrode

The anodic oxidation of aqueous solutions containing dimethyl phthalate （DMP） up to 125 mg/L with sodium sulfate （Na2SO4） as supporting electrolyte within the pH range 2.0-10.0 was studied using a one-compartment batch reactor employing a boron-doped diamond （BDD） as anode. Electrolyses were carded out at constant current density （1.5-4.5 mA/cm^2）. Complete mineralization was always achieved owing to the great concentration of hydroxyl radical （-OH） generated at the BDD surface. The effects of pH, apparent current density and initial DMP concentration on the degradation rate of DMP, the specific charge required for its total mineralization and mineralization current efficiency were investigated systematically. The mineralization rate of DMP was found to be pH-independent and to increase with increasing applied current density. Results indicated that this electrochemical process was subjected, at least partially, to the mass transfer of organics onto the BDD surface. Kinetic analysis of the temporal change of DMP concentration during electrolysis determined by High Performance Liquid Chromatography （HPLC） revealed that DMP decay under all tested conditions followed a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids were identified by Gas Chromatography- Mass Spectrometry （GC-MS） and a general pathway for the electrochemical incineration of DMP on BDD was proposed.

Electrochemical oxidation of reactive brilliant orange X-GN dye on boron-doped diamond anode

In this study,the electrochemical oxidation of reactive brilliant orange X-GN dye with a boron-doped diamond(BDD)anode was investigated.The BDD electrodes were deposited on the niobium(Nb)substrates by the hot filament chemical vapor deposition method.The effects of processing parameters,such as film thickness,current density,supporting electrolyte concentration,initial solution pH,solution temperature,and initial dye concentration,were evaluated following the variation in the degradation efficiency.The microstructure and the electrochemical property of BDD were characterized by scanning electron microscopy,Raman spectroscopy,and electrochemical workstation;and the degradation of X-GN was estimated using UV-Vis spectrophotometry.Further,the results indicated that the film thickness of BDD had a significant impact on the electrolysis of X-GN.After 3 h of treatment,100%color and 63.2%total organic carbon removal was achieved under optimized experimental conditions:current density of 100 mA/cm2,supporting electrolyte concentration of 0.05 mol/L,initial solution pH 3.08,and solution temperature of 60°C.

Fabrication and characteristics of nitrogen-doped nanocrystalline diamond/p-type silicon heterojunction

Nitrogen-doped nanocrystalline diamond films(N-NDFs)have been deposited on p-type silicon(Si)by microwave plasma chemical vapor deposition.The reaction gases are methane,hydrogen,and nitrogen without the conventional argon(Ar).The N-NDFs were characterized by X-ray diffraction,Raman spectroscopy,and scanning electron microscopy.The grain sizes are of 8~10 nm in dimension.The N-NDF shows n-type behavior and the corresponding N-NDF/p-Si heterojunction diodes are realized with a high rectification ratio of 102 at^7.8 V,and the current density reaches to1.35 A/cm2 at forward voltage of 8.5 V.The findings suggest that fabricated by CH_4/H_2/N_2 without Ar,the N-NDFs and the related rectifying diodes are favorable for achieving high performance diamond-based optoelectronic devices.

Electrochemical treatment of wastewater containing chlorophenols using boron-doped diamond film electrodes

The electrochemical treatment of wastewater containing chlorophenols （2-monochlorophenol, 4-monochlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol） was carried out experimentally with synthetic boron-d0ped diamond （BDD） thin film electrodes. Current vs time curves under different cell voltages were measured. Removal rate of COD, instant current efficiency （ICE） and energy consumption were investigated under different current densities. The influence of supporting media is reported, which plays an important role in determining the global oxidation rate. The oxidative chloride is stronger than peroxodisulphate. The electrochemical characteristics of boron-doped diamond electrodes were investigated in comparison with active coating Ti substrate anode （ACT）. The experimental results show that BDD is markedly superior to ACT due to its different absorption properties.

Synthesis and characterization of p-type boron-doped IIb diamond large single crystals

High-quality p-type boron-doped IIb diamond large single crystals are successfully synthesized by the temperature gradient method in a china-type cubic anvil high-pressure apparatus at about 5.5 GPa and 1600 K. The morphologies and surface textures of the synthetic diamond crystals with different boron additive quantities are characterized by using an optical microscope and a scanning electron microscope respectively. The impurities of nitrogen and boron in diamonds are detected by micro Fourier transform infrared technique. The electrical properties including resistivities, Hall coefficients, Hall mobilities and carrier densities of the synthesized samples are measured by a four-point probe and the Hall effect method. The results show that large p-type boron-doped diamond single crystals with few nitrogen impurities have been synthesized. With the increase of quantity of additive boron, some high-index crystal faces such as {113} gradually disappear, and some stripes and triangle pits occur on the crystal surface. This work is helpful for the further research and application of boron-doped semiconductor diamond.

Effect of nitrogen on deposition and field emission properties of boron-doped micro-and nano-crystalline diamond films

In this paper,we report the effect of nitrogen on the deposition and properties of boron doped diamond films synthesized by hot filament chemical vapor deposition.The diamond films consisting of micro-grains(nano-grains) were realized with low(high) boron source flow rate during the growth processes.The transition of micro-grains to nano-grains is speculated to be strongly(weekly) related with the boron(nitrogen) flow rate.The grain size and Raman spectral feature vary insignificantly as a function of the nitrogen introduction at a certain boron flow rate.The variation of electron field emission characteristics dependent on nitrogen is different between microcrystalline and nanocrystalline boron doped diamond samples,which are related to the combined phase composition,boron doping level and texture structure.There is an optimum nitrogen proportion to improve the field emission properties of the boron-doped films.

Nanocrystalline Diamond Films Grown by Microwave Plasma Chemical Vapor Deposition and Its Biocompatible Property

Due to its unique properties such as high hardness, light transmittance, thermal conductance, chemical stability and corrosion resistance, diamond has drawn tremendous attention in last two decades. These specific properties made diamond film a promising material for cutting tools, microwave windows, heat sinks for electronic devices and diamond electrodes. However, the diamond film with grain sizes at microscale usually exhibits high surface roughness and hinders its applications in the microelectro mechanical system (MEMS) and biological field because it is difficult to be polished by mechanical and chemical methods. With the development of the chemical vapor deposition, the nanocrystalline diamond (NCD) film has been fabricated and found new applications. The grain size of NCD film is in the range of 10 to 100 nm, which inherits the properties of the diamond and possesses the unique properties of the nanoscale materials, and the morphology of the NCD film is granular or needle-like structure. The microwave plasma chemical vapor deposition (MPCVD) has been regarded as the most promising method to deposit NCD film at low temperature. Compared to the hot filament CVD, MPCVD can grow high quality NCD film avoiding of the contamination from the filament materials. The MPCVD technique has high plasma density to activate carbonaceous compound and grow NCD film in high growth rate and low substrate temperature. The unique properties of NCD film, such as the superior electrical, mechanical and biological properties facilitate their application in various fields. The biological application, especially as a biocompatible coating, mainly includes the joint replacement implants and protective coatings and the ophthalmological prosthesis.

Fabrication and application of nanocrystalline diamond films

Nanocrystalline diamond films were deposited on Co-cemented carbide substrates using acetone/ H2/Ar gas mixture by bias-enhanced hot filament chemical vapor deposition（HFCVD） technique.The evidence of nanocrystallinity,smoothness and purity was obtained by characterizing the sample with scanning electron microscopy（SEM）,X-ray diffraction（XRD）,Raman spectroscopy,atomic force microscopy （AFM ）,and field emission transmission electron microscopy（FE-TEM ）.The results show that nanocrystalline diamond films consists of nanocrystalline diamond grains with sizes range from 20 to 80 nm and contain a large amount of grain boundaries.The surface roughness of the films is measured as Ra【50nm.The Raman spectroscopy,XRD pattern,and FE-TEM image of the films indicate the presence of nanocrystalline diamond.A new process is used to deposit composite diamond coatings by a two-step chemical vapor deposition procedure,including first the deposition of the rough polycrystalline diamond and then the smooth fine-grained nanocrystalline diamond film.Such composite diamond coatings not only display good adhesion and wear resistant properties,but also have smooth surfaces that are liable to polishing.This coating technology can not only meet the requirement of the adhesion of diamond coatings,but also reduce surface roughness of diamond coatings effectively,thus remove the obstacles for the industrialization of CVD diamond coatings.The diamondcoated dies with these composite coatings show obvious effect in the practical application.

Effect of Argon Addition on Morphology and Structure of Diamond Films(from Microcrystalline to Nanocrystalline)

Micro-/nanocrystalline diamond films deposited in Ar/H2/CH4 microwave plasmas have been studied, with argon flow rates in the range of 70-100 sccm. The effects of argon addition on morphology, surface roughness, quality and structure were investigated by scanning electron microscopy, surface profiler, Raman spectrometer and X-ray diffraction （XRD）. It is demonstrated that when the argon flow rate is 70 sccm or 75 sccm, well-faceted polycrystalline diamond films can be grown at a low substrate temperature less than 610 ~C. With the increase in the argon flow rate, the smooth crystallographic planes disappear gradually. Instead, rough crystallographic planes made up of small aggregates begin to take shape, resulting from the increase in the secondary nucleation rate. Nanocrystalline diamond films were obtained at a flow rate of 100 sccm, and all of the prepared diamond films were smooth, with a surface roughness （Ra） less than 20 nm. Raman analyses reveal that the amount of amorphous carbon increases significantly with the increase in argon flow. The results of XRD show that crystalline size and preferential orientation of diamond films depend on the argon content in the plasmas.

Impact of nitrogen doping on growth and hydrogen impurity incorporation of thick nanocrystalline diamond films

A much larger amount of bonded hydrogen was found in thick nanocrystalline diamond （NCD） films produced by only adding 0.24% N2 into 4% CH4/H2 plasma, as compared to the high quality transparent microcrystalline diamond （MCD） films, grown using the same growth parameters except for nitrogen. These experimental results clearly evidence that defect formation and impurity incorporation （for example, N and H） impeding diamond grain growth is the main formation mechanism of NCD upon nitrogen doping and strongly support the model proposed in the literature that nitrogen competes with CHx （x = 1, 2, 3） growth species for adsorption sites.

Nanocrystalline Diamond Films Deposited by Electron Assisted Hot Filament Chemical Vapor Deposition

Nanocrystalline diamond films were deposited on polished Si wafer surface with electron assisted hot filament chemical vapor deposition at 1 kPa gas pressure, the deposited films were characterized and observed by Raman spectrum, X-ray diffraction, atomic force microscopy and semiconductor characterization system. The results show that when 8 A bias current is applied for 5 h, the surface roughness decreases to 28.5 nm. After 6 and 8 A bias current are applied for 1 h, and the nanocrystalline films deposition continue for 4 h with 0 A bias current at 1 kPa gas pressure. The nanocrystalline diamond films with 0.5×109 and 1×1010 Ω·cm resistivity respectively are obtained. It is demonstrated that electron bombardment plays an important role of nucleation to deposit diamond films with smooth surface and high resistivity.

Si/Nanocrystalline Diamond Film Heterojunction Diodes Preparation

With electron assisted hot filament chemical vapor deposition technology, nanocrystalline diamond films were deposited on polished n-(100)Si wafer surface. The deposited films were characterized and observed by Raman spectrum, X-ray diffraction, semiconductor characterization system and Hall effective measurement system. The results show that with EA-HFCVD, not only an undoped nanocrystalline diamond films with high-conductivity (p-type semiconducting) but also a p-n heterojunction diode between the nanocrystalline diamond films and n-Si substrate is fabricated successfully. The p-n heterojunction has smaller forward resistance and bigger positive resistance. The p-n junction effective is evident.

Ohmic and Schottky contacts of hydrogenated and oxygenated boron-doped single-crystal diamond with hill-like polycrystalline grains

Hill-like polycrystalline diamond grains(HPDGs)randomly emerged on a heavy boron-doped p+single-crystal diamond(SCD)film by prolonging the growth duration of the chemical vapor deposition process.The Raman spectral results confirm that a relatively higher boron concentration(~1.1×10^(21) cm^(-3))is detected on the HPDG with respect to the SCD region(~5.4×10^(20) cm^(-3)).It demonstrates that the Au/SCD interface can be modulated from ohmic to Schottky contact by varying the surface from hydrogen to oxygen termination.The current-voltage curve between two HPDGs is nearly linear with either oxygen or hydrogen termination,which means that the HPDGs provide a leakage path to form an ohmic contact.There are obvious rectification characteristics between oxygen-terminated HPDGs and SCD based on the difference in boron doping levels in those regions.The results reveal that the highly boron-doped HPDGs grown in SCD can be adopted as ohmic electrodes for Hall measurement and electronic devices.

Synthesis of Boron-doped Diamond/Porous Ti Composite Materials——Effect of Carbon Concentration

Highly boron-doped diamond films were deposited on porous titanium substrates by hot filament chemical vapor deposition technique. The morphology variation of highly boron-doped diamond films grown on porous titanium substrates was investigated, and the effects of carbon concentration on nucleation density and diamond growth were also studied. The continuous change of surface morphology and structure of diamond film were characterized by scanning electron microscopy. The structures of diamond film and interlayer were analyzed by X-ray diffraction. The quality of boron-doped diamond film was confirmed by visible Raman spectroscopy. The experimental results reveal that surface morphology and quality of boron-doped diamond films are various due to the change of carbon concentration. The thickness of intermediate layer decreases with the carbon concentration increasing.

Field emission from Si tips coated with nanocrystalline diamond films

The electron field emission from Si tips coated with nanocrystalline diamond films was investigated. The Si tips were formed by plasma etching, and nano-diamond films were deposited on the Si tips by hot filament chemical vapor deposition. The radius of curvature for the Si tips was averagely about 50 nm. The microstructure of the diamond films was examined by scanning electron microscopy and Raman spectroscopy. The field emission properties of the samples were measured in an ion-pumped vacuum chamber at a pressure of 106 Pa. The experimental results showed that the nanostructured films on Si tips exhibited a lower value of the turn-on electric field than those on flat Si substrates. It was found that the tip shape and non-diamond phase in the films had a significant effect on the field emission properties of the films.

Electrochemical Detection of Clenbuterol in Pig Liver at Pyrrole DNA Modified Boron-doped Diamond Electrode

The direct detection of clenbuterol（CL） in pig liver without any extraction separation at a pyrrole-DNA modified boron-doped diamond（BDD） electrode is reported. The pyrrole-DNA modified BDD electrode has a strong electrocatalytic effect on the redox reaction of CL. One oxidization and two reduction peaks of CL appear at 340. 2, 299. 8 and 166. 6 mV（ versus SCE）, respectively. The pyrrole polymer alone cannot electrocatalyze the above reaction at a BDD electrode ; the electrocatalytic effect of a BDD electrode modified with DNA membrane is unsufficient for the analytical detection of CL; the replacement of boron-doped diamond by glass carbon makes the electrocatalytic reaction impossible ; the redox process is pH dependent. The influences of various experimental parameters on the pyrrole-DNA modified BDD electrode were investigated. A sensitive cyclic vohammetric response for CL was obtained in a linear range from 3.4 × 10^-6 to 5 × 10^ -4 mol/L with a detection limit of 8.5 × 10^-7 mol/L. A mean recovery of 102. 7% of CL in the pig liver sample solution and a reproducibility of 3.2% were obtained.

Electroanalytical Investigation on Paracetamol on Boron-Doped Diamond Electrode by Voltammetry

An electroanalytical method was developed for the direct quantitative determination of paracetamol in tablets based on its oxidation behavior. The electrochemical oxidation and determination of paracetamol were easily carried out on born-doped diamond (BDD) electrode using two voltammetric techniques (CV and DPV). The electrochemical measurements performed by cyclic voltammetric (CV) and differential pulse voltammetry (DPV) techniques were carried out using a cathodically pretreated boron-doped diamond electrode in HClO4 and KClO4 electrolytes. HClO4 was then selected for analytical purposes and scan rate studies were also completed. The oxidation of the paracetamol is found to be irreversible and a diffusion-controlled nature of the paracetamol oxidation peak was established. A linear calibration curve for DPV analysis was constructed in the paracetamol concentration range from 0 μM to 13.87 μM, with 0.16 μM and 0.55 μM as the detection and quantification limit respectively.