Cathodic and anodic pre-treated boron doped diamond with different sp content: Morphological,structural, and impedance spectroscopy characterizations

In this work, the influence of cathodic (Red) and anodic (Ox) pre-treatment on boron doped diamond (BDD) films grown with different sp²/sp³ ratios was systematically studied. The sp²/sp³ ratios were controlled by the addition of CH₄ of 1,3,5 and 7 sccm in the gas inlet during the growth process. The electrodes were treated in 0.5 mol L⁻¹ H₂SO₄ at −3 and 3 V vs Ag/AgCl, respectively, for 30 min. The electrochemical response of BDD films was investigated using electrochemical impedance spectroscopy (EIS) and Mott–Schottky Plot (MSP) measurements. Four film sample sets were produced in a hot filament chemical vapor deposition reactor. During the growth process, an additional H₂ line passing through a bubbler containing the B₂O₃ dissolved in methanol was used to carry the boron. The scanning electron microscopy morphology showed well faced films with a small decrease in their grain size as the CH₄ concentration increased. The Raman spectra depicted a pronounced sp² band, mainly for films with 5 and 7 sccm of CH₄. MSP showed a decrease in the acceptor concentration as the CH₄ increased indicating the CH₄ influence on the doping process for Red–BDD and Ox–BDD samples. Nonetheless, an apparent increase in the acceptor concentrations for both Ox–BDD samples was observed compared to that for Red–BDD samples, mainly attributed to the surface conductive layer (SCL) formation after this strong oxidation process. The EIS Nyquist plots for Red–BDD showed a capacitance increase for the films with higher sp² content (5 and 7 sccm). On the other hand, the Nyquist plots for Ox–BDD can be described as semicircles near the origin, at high frequencies, where their charge transfer resistance strongly varied with the sp² increase in such films.     

Carbon nano dots scale by focused ion beam system for MIS diode nano devices

Metal-insulator-semiconductor (MIS) structures with a nanocrystal carbon (nc-C) embedded in SiO₂ thin films were fabricated using a focused ion beam (FIB) system with a precursor of low-energy Ga⁺ ion and carbon source. The crystallinity of nc-C was investigated by Raman spectroscopy and atomic force microscopy (AFM). Raman spectra indicate the evidence of crystallization of nc-C after annealed at 600 °C by the sharp peak at 1565 cm⁻¹ in graphite (sp²), while no peak of diamond (sp³) could be seen at 1333 cm⁻¹. The AFM images showed the nc-C dots controlled with diameter of 100 nm, 200 nm and 300 nm, respectively. The above results revealed that the nc-C dots had sufficiently stuck onto SiO₂ films. The hysterisis loop in the capacitance-voltage characteristics appeared in the MIS device with SiO₂/nc-C/SiO₂ structure in which voltage shift is 0.32 V for radical oxidation and 0.14 V for dry oxidation, respectively.     

X-ray photoelectron spectroscopic study of nitrogen incorporated amorphous carbon films embedded with nanoparticles

The effect of substrate bias on X-ray photoelectron spectroscopy (XPS) study of nitrogen incorporated amorphous carbon (a-C:N) films embedded with nanoparticles deposited by filtered cathodic jet carbon arc technique is discussed. High resolution transmission electron microscope exhibited initially the amorphous structure but on closer examination the film was constituted of amorphous phase with the nanoparticle embedded in the amorphous matrix. X-ray diffraction study reveals dominantly an amorphous nature of the film. A straight forward method of deconvolution of XPS spectra has been used to evaluate the sp³ and sp² contents present in these a-C:N films. The carbon (C 1s) peaks have been deconvoluted into four different peaks and nitrogen (N 1s) peaks have been deconvoluted into three different peaks which attribute to different bonding state between C, N and O. The full width at half maxima (FWHM) of C 1s peak, sp³ content and sp³/sp² ratio of a-C:N films increase up to −150 V substrate bias and beyond −150 V substrate bias these parameters are found to decrease. Thus, the parameters evaluated are found to be dependent on the substrate bias which peaks at −150 V substrate bias.     

Low voltage electrodeposition of diamond like carbon (DLC)

Attempt has been made to deposit diamond like carbon (DLC) films from ethanol through electrodeposition at low voltages (80-300 V) at 1 mm interelectrode separation. The films were characterized by atomic force microscopy (AFM), Scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and Auger electron Spectroscopy (AES). AFM investigations revealed the grain sizes are of tens of nanometers. The films were found to be continuous, smooth and close packed. Presence of peaks at 2958, 2929 and 2869 cm⁻¹ in FTIR spectrum indicates the bonding states to be of predominantly sp³ type (C-H). Raman spectroscopy analysis revealed two broad bands at ∼1350 and ∼1570 cm⁻¹. The downshift of the G-band of graphite is indicative of presence of DLC. Analysis of the Raman spectra for the samples revealed an improvement in the film quality with increase in the voltage. Micro Raman investigations indicate the formation of diamond phase at the deposition potential of 80 V. The sp² contents the films calculated from Auger electron spectra were calculated and were found to be 31, 19 and 7.8% for the samples prepared at 80, 150 and 300 V, respectively. A tentative mechanism for the formation of DLC has been proposed. These results indicate the possibility of deposition of DLC at low voltage.     

Effect of nickel on the structure and bond type in amorphous diamond-like carbon films

Experimental data are presented from studies of the structure and bond type of carbon atoms in amorphous carbon-nickel films deposited from pulsed vacuum-arc discharge plasma sources. X-ray photoelectron spectroscopy was used. The characteristics of the plasmon loss spectra depend significantly on the deposition parameters. Carbon exists in a mixed sp²+sp³ hybridized state in the carbon–nickel films. The ratio of sp³/sp² carbon bonds increases when the nickel content is reduced (from 5.5 to 1.0 atomic %) and the deposition angle is increased. The structure closest to that of diamond was with a substrate bias voltage of –80 to –100 V and a deposition angle of 90°.     

Electrochemical, morphological and microstructural characterization of carbon film resistor electrodes for application in electrochemical sensors

The electrochemical and microstructural properties of carbon film electrodes made from carbon film electrical resistors of 1.5, 15, 140 Ω and 2.0 kΩ nominal resistance have been investigated before and after electrochemical pre-treatment at +0.9 V vs SCE, in order to assess the potential use of these carbon film electrodes as electrochemical sensors and as substrates for sensors and biosensors. The results obtained are compared with those at electrodes made from previously investigated 2 Ω carbon film resistors. Cyclic voltammetry was performed in acetate buffer and phosphate buffer saline electrolytes and the kinetic parameters of the model redox system Fe(CN)₆^3−/4− obtained. The 1.5 Ω resistor electrodes show the best properties for sensor development with wide potential windows, similar electrochemical behaviour to those of 2 Ω and close-to-reversible kinetic parameters after electrochemical pre-treatment. The 15 and 140 Ω resistor electrodes show wide potential windows although with slower kinetics, whereas the 2.0 kΩ resistor electrodes show poor cyclic voltammetric profiles even after pre-treatment. Electrochemical impedance spectroscopy related these findings to the interfacial properties of the electrodes. Microstructural and morphological studies were carried out using contact mode Atomic Force Microscopy (AFM), Confocal Raman spectroscopy and X-ray diffraction. AFM showed more homogeneity of the films with lower nominal resistances, related to better electrochemical characteristics. X-ray diffraction and Confocal Raman spectroscopy indicate the existence of a graphitic structure in the carbon films.     

Electrochemical and surface characterisation of carbon-film-coated piezoelectric quartz crystals

The electrochemical properties of carbon films, of thickness between 200 and 500 nm, sputter-coated on gold- and platinum-coated 6 MHz piezoelectric quartz crystal oscillators, as new electrode materials have been investigated. Comparative studies under the same experimental conditions were performed on bulk electrodes. Cyclic voltammetry was carried out in 0.1 M KCl electrolyte solution, and kinetic parameters of the model redox systems Fe(CN)₆^3−/4− and [Ru(NH₃)₆]^3+/2+ as well as the electroactive area of the electrodes were obtained. Atomic force microscopy was used in order to examine the surface morphology of the films, and the properties of the carbon films and the electrode-solution interface were studied by electrochemical impedance spectroscopy. The results obtained demonstrate the feasibility of the preparation and development of nanometer thick carbon film modified quartz crystals. Such modified crystals should open up new opportunities for the investigation of electrode processes at carbon electrodes and for the application of electrochemical sensing associated with the EQCM.     

Effects of hydrogen and oxygen on the electrochemical corrosion and wear-corrosion behavior of diamond films deposited by hot filament chemical vapor deposition

A diamond film was deposited on silicon substrate using hot filament chemical vapor deposition (HFCVD), and H₂ and O₂ gases were added to the deposition process for comparison. This work evaluates how adding H₂ and O₂ affects the corrosion and wear-corrosion resistance characteristics of diamond films deposited on silicon substrate. The type of atomic bonding, structure, and surface morphologies of various diamond films were analyzed by Raman spectrometry, X-ray diffraction (XRD) and atomic force microscopy (AFM). Additionally, the mechanical characteristics of diamond films were studied using a precision nano-indentation test instrument. The corrosion and wear-corrosion resistance of diamond films were studied in 1 M H₂SO₄ + 1 M NaCl solution by electrochemical polarization. The experimental results show that the diamond film with added H₂ had a denser surface and a more obvious diamond phase with sp³ bonding than the as-deposited HFCVD diamond film, effectively increasing the hardness, improving the surface structure and thereby improving corrosion and wear-corrosion resistance properties. However, the diamond film with added O₂ had more sp² and fewer sp³ bonds than the as-deposited HFCVD diamond film, corresponding to reduced corrosion and wear-corrosion resistance.     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

Diamond-like phase formation in an amorphous carbon films prepared by periodic pulsed laser deposition and laser irradiation method

Diamond-like carbon (DLC) films were fabricated by pulsed laser ablation of a liquid target. During deposition process the growing films were exited by a laser beam irradiation. The films were deposited onto the fused silica using 248 nm KrF eximer laser at room temperature and 10⁻³ mbar pressure. Film irradiation was carried out by the same KrF laser operating periodically between the deposition and excitation regimes. Deposited DLC films were characterized by Raman scattering spectroscopy. The results obtained suggested that laser irradiation intensity has noticeable influence on the structure and hybridization of carbon atoms deposited. For materials deposited at moderate irradiation intensities a very high and sharp peak appeared at 1332 cm⁻¹, characteristic of diamond crystals. At higher irradiation intensities the graphitization of the amorphous films was observed. Thus, at optimal energy density the individual sp³-hybridized carbon phase was deposited inside the amorphous carbon structure. Surface morphology for DLC has been analyzed using atomic force microscopy (AFM) indicating that more regular diamond cluster formation at optimal additional laser illumination conditions (∼20 mJ per impulse) is possible.     

Field emission from nitrogen-implanted CVD diamond film grown on silicon wafer

Nitrogen was implanted into chemical vapor deposition (CVD) diamond films and the electron field emission properties of the nitrogenated diamond films were investigated. Nitrogen implantation was carried out using 10 keV in the dose range from 1×10¹⁶ to 5×10¹⁷ cm^-2 at room temperature. Raman and X-ray photoelectron spectroscopy measurements revealed that nitrogen implantation damaged the structure of the diamond film and promoted the formation of sp² C–C and sp² C–N bondings. Increasing the implantation dose could lower the threshold field of the emission of the diamond film from 18 V/m to 4 V/m. The effective work function of the nitrogen-implanted CVD diamond films was estimated to be in the range of 0.01–0.1 eV. The enhancement of field emission for nitrogen-implanted CVD diamond films was attributed to the increase of the sp² C bonds fraction and the formation of defect bands within the bulk diamond band gap induced by nitrogen implantation, which could alter the work function and elevate the Fermi level. Consequently, the energy barrier for electron tunneling was reduced.     

Effect of ECR-assisted microwave plasma nitriding treatment on the microstructure characteristics of FCVA deposited ultra-thin ta-C films for high-density magnetic storage applications

There are higher technical requirements for protecting layer of magnetic heads and disks used in future high-density storage fields. In this paper, ultra-thin (2 nm thickness) tetrahedral amorphous carbon (ta-C) films were firstly prepared by filtered cathodic vacuum arc (FCVA) method, then a series of nitriding treatments were performed with nitrogen plasma generated using electron cyclotron resonance (ECR) microwave source. Here it highlighted the influence of nitrogen flow and applied substrate bias voltage on the structural characteristics of ta-C films during the plasma nitriding process. The chemical compositions, element depth distribution profiles, physical structures and bonding configurations of plasma-nitrided ta-C films were investigated by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and UV-vis Raman spectroscopy. The experimental results show that the carbon nitride compounds (CN_x) are formed in nitrogenated ta-C films in which the N content and its depth distribution depends on bias voltage to large extent rather than N₂ flow. The N content of nitrogenated ta-C films can reach 16 at.% for a substrate bias of −300 V and a N₂ flow of 90 sccm. With increasing nitrogen content, there is less G peak dispersion and more ordering of structure. Furthermore, appropriate nitriding treatment (substrate bias: −100 V, N₂ flow: 150 sccm) can greatly increase the fraction of sp³ and sp³C-N bonds, but the values begin to fall when the N content is above 9.8 at.%. All these indicate that suitable ECR-assisted microwave plasma nitriding is a potential modification method to obtain ultra-thin ta-C films with higher sp³ and sp³C-N fractions for high-density magnetic storage applications.     

Field emission properties of polymer-converted carbon films by heat treatment

Carbon films were prepared on single crystal silicon substrates by heat-treatment of a polymer-poly(phenylcarbyne) at 800 °C in Ar atmosphere. The heat-treatment caused the change of the polymer into carbon film, which exhibited good field emission properties. Low turn-on emission field of 4.3 V/μm (at 0.1 μA/cm²) and high emission current density of 250 μA/cm² (at 10 V/μm) were observed for the polymer-converted carbon films. This behavior was demonstrated to be mainly related to the microstructure of the carbon films, which consisted of fine carbon nanoparticles with high sp² bonding. The carbon films, which can be deposited simply with large areas, are promising for practical applications in field emission display.     

不同能级加速过滤电弧沉积四面体非晶碳膜的结构和性能

采用过滤阴极真空电弧技术，通过施加0—2000 V衬底负偏压使沉积离子获得不同能级的入射能量，在单晶硅上制备了四面体非晶碳薄膜.拉曼光谱分析表明，薄膜的结构为非晶sp³骨架中镶嵌着平面关联长度小于1 nm的sp²团簇.原子力显微镜研究表明：在低能级、富sp³能量窗口和次高能级，薄膜中sp³的含量越多，其表面就越光滑，应用sp³浅注入生长机制能够圆满地解释薄膜表面形态与离子入射能量之间的关系；但在高 关键词： 四面体非晶碳 过滤阴极真空电弧 能级     

退火对B掺杂纳米金刚石薄膜微结构和电化学性能的影响

采用热丝化学气相沉积法制备B掺杂纳米金刚石薄膜,并对薄膜进行真空退火处理,系统研究了不同退火温度对B掺杂纳米金刚石薄膜的微结构和电化学性能的影响.结果表明,当退火温度升高到800 ℃后,薄膜的Raman谱图中由未退火时在1157,1346,1470,1555 cm^-1处的4个峰转变为只有D峰和G峰,说明晶界上的氢大量解吸附量减少,并且D峰和G峰的积分强度比I_D/I_G值变为最小,即sp²相团簇     

Laser fluence dependence of the elastic properties of diamond-like carbon films prepared by pulsed-laser deposition

We studied the temperature dependence of internal friction of variety of amorphous diamond-like carbon films prepared by pulsed-laser deposition. Like the most of amorphous solids, the internal friction below 10 K exhibits a temperature independent plateau, which is caused by the atomic tunnelling states—a measure of structure disorder. In this work, we have varied the concentration of sp³ versus sp² carbon atoms by increasing laser fluence from 1.5 to 30 J/cm². Our results show that the internal friction has a nonmonotonic dependence on sp³/sp² ratio with the values of the internal friction plateaus varying between 6×10⁻⁵ and 1.1×10⁻⁴. We explain our findings as a result of a possible competition between the increase of atomic bonding and the increase of internal strain in the films, both of which are important in determining the tunneling states in amorphous solids. The importance of the internal strain in diamond-like carbon films is consistent with our previous study on laser fluence, doping, and annealing, which we will review as well. In contrast, no significant dependence of laser fluence is found in shear moduli of the films, which vary between 220 and 250 GPa.     

Electrochemical corrosion behaviors of a-C:H and a-C:NX:H films

The a-C:H and a-C:N_X:H films were deposited onto silicon wafers using radio frequency (rf) plasma enhanced chemical vapor deposition (PECVD) and pulsed-dc glow discharge plasma CVD, respectively. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize chemical nature and bond types of the films. The results demonstrated that the a-C:H film prepared by rf-CVD (rf C:H) has lower I_D/I_G ratio, indicating smaller sp² cluster size in an amorphous carbon matrix. The nitrogen concentrations of 2.9 at.% and 7.9 at.% correspond to carbon nitride films prepared with rf and pulse power, respectively.Electrochemical corrosion performances of the carbon films were investigated by potentiodynamic polarization test. The electrolyte used in this work was a 0.89% NaCl solution. The corrosion test showed that the rf C:H film exhibited excellent anti-corrosion performance with a corrosion rate of 2 nA cm⁻², while the carbon nitride films prepared by rf technique and pulse technique showed a corrosion rate of 6 nA cm⁻² and 235 nA cm⁻², respectively. It is reasonable to conclude that the smaller sp² cluster size of rf C:H film restrained the electron transfer velocity and then avoids detriment from the exchange of electrons.     

Investigation of properties of Cu containing DLC films produced by PECVD process

Copper containing diamond like carbon (Cu-DLC) thin films were deposited on various substrates at a base pressure of 1×10^?3 Torr using a hybrid system involving DC-sputtering and radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD) techniques. The compressive residual stresses of these films were found to be considerably lower, varying between 0.7 and 0.94 GPa and Cu incorporation in these films improve their conductivity significantly. Their structural properties were studied by Raman spectroscopy, atomic force microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction techniques that clearly revealed the presence of Cu in the DLC structure. Raman analysis yields that Cu incorporation in DLC enhances the graphite-like sp² bonding. However, the sp² bonding was found to continuously reduce with the increasing C₂H₂ gas pressure, this may be due to reduction of Cu nanocrystal at the higher pressure. FTIR results inferred various bonding states of carbon with carbon, hydrogen and oxygen. In addition, hydrogen content and sp³ and sp² fractions in different Cu-DLC films were also estimated by FTIR spectra and were correlated with stress, electrical, optical and nano-mechanical properties of Cu-DLC films. The effect of indentation load (4–10 mN) on nano-mechanical properties of these films was also explored.     

Bias voltage effect on the structure and property of chromium copper-diamond-like carbon multilayer films fabricated by cathodic arc plasma

Chromium copper-diamond-like carbon (Cr:Cu)-DLC films were deposited onto silicon and by cathodic arc evaporation process using chromium (Cr) and copper (Cu) target arc sources to provide Cr and Cu in the Me-DLC. Acetylene reactive gases were the carbon source and activated at 180 °C at 13 mTorr, and a substrate bias voltage was varied from −50 V to −200 V to provide the (Cr:Cu)-DLC structure. The structure, interface, and chemical bonding state of the produced film were analyzed by transmission electron microscope (TEM), IR Fourier transform (FTIR) spectra, and X-ray photoelectron spectroscopy (XPS). The results showed that the Cr-containing a-C:H/Cu coatings exhibited an amorphous layer of DLC:Cr layer and a crystalline layer of Cu multilayer structure. The profiles of sp³/sp² (XPS) ratios corresponded to the change of microhardness profile by varying the pressure of the negative DC bias voltage. These (Cr:Cu)-DLC coatings are promising materials for soft substrate protective coatings.     

Ultraviolet Raman analysis of the formation of diamond from C60

The ultraviolet (257 nm) Raman spectrum of C₆₀ compressed to 30 GPa in a Mao–Bell diamond anvil cell with no pressure transmitting medium at ambient temperature indicates the formation of diamond after release of pressure. Previously, more extreme non-hydrostatic compression was reported to be required to form diamond from C₆₀. These results provide confirmation of the transformation of C₆₀ to diamond upon non-hydrostatic compression at room temperature and illustrate the utility of UV Raman spectroscopy for the analysis of carbon phases containing both sp² and sp³ bonding.