Mechanical properties and platelet adhesion behavior of diamond-like carbon films synthesized by pulsed vacuum arc plasma deposition

Diamond-like carbon (DLC) is an attractive biomedical material due to its high inertness and excellent mechanical properties. In this study, DLC films were fabricated on Ti6Al4V and Si(1 0 0) substrates at room temperature by pulsed vacuum arc plasma deposition. By changing the argon flow from 0 to 13 sccm during deposition, the effects of argon flow on the characteristics of the DLC films were systematically examined to correlate to the blood compatibility. The microstructure and mechanical properties of the films were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) surface analysis, a nano-indenter and pin-on-disk tribometer. The blood compatibility of the films was evaluated using in vitro platelet adhesion investigation, and the quantity and morphology of the adherent platelets was investigated employing optical microscopy and scanning electron microscopy.The Raman spectroscopy results showed a decreasing sp³ fraction (an increasing trend in I_D/I_G ratio) with increasing argon flow from 0 to 13 sccm. The sp³:sp² ratio of the films was evaluated from the deconvoluted XPS spectra. We found that the sp³ fraction decreased as the argon flow was increased from 0 to 13 sccm, which is consistent with the results of the Raman spectra. The mechanical properties results confirmed the decreasing sp³ content with increasing argon flow. The Raman D-band to G-band intensity ratio increased and the platelet adhesion behavior became better with higher flow. This implies that the blood compatibility of the DLC films is influenced by the sp³:sp² ratio. DLC films deposited on titanium alloys have high wear resistance, low friction and good adhesion.     

Enhanced field emission characteristics of boron doped diamond films grown by microwave plasma assisted chemical vapor deposition

Boron doped diamond films were synthesized on silicon substrates by microwave plasma chemical vapor deposition (MPCVD) technique. The effect of B₂O₃ concentration varied from 1000 to 5000 ppm on the field emission characteristics was examined. The surface morphology and quality of films were characterized by scanning electron microscope (SEM) and Raman spectroscopy. The surface morphology obtained by SEM showed variation from facetted microcrystal covered with nanometric grains to cauliflower of nanocrystalline diamond (NCD) particles with increasing B₂O₃ concentration. The Raman spectra confirm the formation of NCD films. The field emission properties of NCD films were observed to improve upon increasing boron concentration. The values of the onset field and threshold field are observed to be as low as 0.36 and 0.08 V/μm, respectively. The field emission current stability investigated at the preset value of ∼1 μA is observed to be good, in each case. The enhanced field emission properties are attributed to the better electrical conductivity coupled with the nanometric features of the diamond films.     

纳米磷化镓粉体中混杂石墨和金刚石微晶的拉曼光谱分析

利用Raman光谱并结合能量色散X射线显微分析(EDX)和X射线衍射图谱(XRD)对混杂于纳米磷化镓粉体内的石墨和金刚石纳米微晶进行了分析。结果表明,在纳米GaP粉体Raman光谱中,位于1324 cm-1和1572 cm-1的两个宽强散射谱带分别归属于金刚石的F2g模和石墨的E2g模振动。EDX结果证实纳米GaP粉体材料中含有碳元素。XRD图谱中出现了石墨和金刚石的低晶面指数衍射峰。     

High-temperature oxidation behaviors of CVD diamond films

In this study, high-temperature oxidation of single-crystal diamond and diamond films prepared by hot filament chemical vapor deposition (HF-CVD), were characterized using thermal analysis and high-temperature in-situ Raman analysis. The measurements were performed in various temperatures up to 1300 °C in air and N₂ atmospheres. The results indicate that the initial oxidization temperature of diamond film deposited at 700 °C (D700 film) is ≈629 °C, lower than those of diamond film deposited at 900 °C (D900 film, ≈650 °C) and single-crystalline diamond (≈674 °C) in air. Oxidation rate of D700 film at high temperatures appeared to be the highest among the samples studied. A likely cause lies in the fact that, compared to their D900 sample, D700 diamond film contains a larger amount of non-diamond carbon and grain boundaries. However, D900 and D700 diamond films as well as single-crystalline diamond showed no detectable weight loss and oxidization when they were heated up to 1300 °C in N₂ atmosphere.     

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.     

Electrochemical properties of undoped CVD diamond films

The electrochemical properties of undoped diamond polycrystalline films grown on tungsten wire substrates using methanol as a precursor are described. The diamond film quality was changed by introducing sp²-bonded non-diamond carbon impurity through adjustment of the methanol-to-hydrogen (C/H) source gas ratio used for diamond growth.The electrodes were characterized by Raman spectroscopy, scanning electronic microscopy (SEM) and cyclic voltammetry (CV).Diamond coated tungsten wires were then used as a working electrode to ascertain their electrochemical behavior in electrolytic medium. Electrochemical windows of these films were found to be suitable in the potential range of [−2.5 V, +2.2 V] vs. Ag/AgCl in acid medium (0.1 M KCl).The electrochemical behavior was evaluated also using the Fe(CN)₆^3−/4−redox couple.The results demonstrate that the grain boundaries and sp²-hybridized carbon impurity can have a significant influence on electrochemical window of undoped diamond electrodes. It was observed that with increasing sp² carbon impurity concentration the electrochemical window decreases.     

Low energy repetitive miniature plasma focus device as high deposition rate facility for synthesis of DLC thin films

Diamond-like carbon (DLC) films were deposited on Si (1 0 0) substrate using a low energy (219 J) repetitive (1 Hz) miniature plasma focus device. DLC thin film samples were deposited using 10, 20, 50, 100 and 200 focus shots with hydrogen as filling gas at 0.25 mbar. The deposited samples were analyzed by XRD, Raman Spectroscopy, SEM and XPS. XRD results exhibited the diffraction peaks related to SiO₂, carbon and SiC. Raman studies verified the formation amorphous carbon with D and G peaks. Corresponding variation in the line width (FWHM) of the D and G positions along with change in intensity ratio (I_D/I_G) in DLC films was investigated as a function of number of deposition shots. XPS confirmed the formation sp² (graphite like) and sp³ (diamond like) carbon. The cross-sectional SEM images establish the 220 W repetitive miniature plasma focus device as the high deposition rate facility for DLC with average deposition rate of about 250 nm/min.     

Diamond deposition on siliconized stainless steel

Silicon diffusion layers in AISI 304 and AISI 316 type stainless steels were investigated as an alternative to surface barrier coatings for diamond film growth. Uniform 2 μm thick silicon rich interlayers were obtained by coating the surface of the steels with silicon and performing diffusion treatments at 800 °C. Adherent diamond films with low sp² carbon content were deposited on the diffused silicon layers by a modified hot filament assisted chemical vapor deposition (HFCVD) method. Characterization of as-siliconized layers and diamond coatings was performed by energy dispersive X-ray analysis, scanning electron microscopy, X-ray diffraction and Raman spectroscopy.     

An optical emission spectroscopy study of the plasma generated in the DC HF CVD nucleation of diamond

Optical emission spectroscopy (OES) was used to study the plasma generated by the activation of the gas phase CH₄ + H₂ both by hot filaments and by a plasma discharge (DC HF CVD) during the nucleation of CVD diamond. The effects of nucleation parameters, such as methane concentration and extraction potential, on the plasma chemistry near the surface were investigated. The density of the diamond nucleation and the quality of the diamond films were studied by scanning electron microscopy (SEM) and Raman scattering, respectively. The OES results showed that the methane concentration influenced strongly the intensity ratio of H_β-H_α implying an increase of electron mean energy, as well as CH, CH⁺, C₂. A correlation between the relative increase of CH⁺ and the diamond nucleation density was found, conversely the increase of C₂ contributed to the introduction of defects in the diamond nuclei.     

热丝CVD生长金刚石薄膜喇曼散射研究

本文报道热丝化学气相沉积法（ＨＦＣＶＤ）生长金钢石薄膜的喇曼散射结果。选取多种峰型，对金钢石薄膜喇曼谱（１１０－１８００ｃｍ－１）采用最小二乘法进行非线性拟合，得到最佳拟合模型，其计算得到的拟合曲线怀实验谱图符合得较好。该模型揭示，石墨Ｄ峰（１３５５ｃｍ－１）是金刚石薄膜喇曼谱中不可缺少的一个组份，并且结合石墨Ｄ峰和金刚石喇曼的空间相关线型，可以解释金刚石喇曼区特殊峰形的物理机制，拟合参量的进一步     

Modified π-states in ion-irradiated carbon

CVD polycrystalline diamond film, pulse laser-deposited (PLD) carbon film and highly oriented pirolitical graphite (HOPG) as reference, were modified by means of Ar⁺ ion bombardment and characterized by means of Raman scattering, transmission electron microscopy, electron-diffraction (TEM), reflected electron energy loss specroscopy (REELS) and X-ray photoelectron spectroscopy (XPS) techniques. It was found that the diamond was transferred to a carbon with halo-like morphology and disordered stack of graphene segments. Instead of the well-known electron energy loss peak of graphite at 6.5 eV, a new REELS peak appeared at 4-5 eV energies. The observed effect was explained by the modification of π-system in carbon films as a consequence of the formation of non-planar, nanometer-sized graphitic planes.     

Effect of titanium powder assisted surface pretreatment process on the nucleation enhancement and surface roughness of ultrananocrystalline diamond thin films

A superior, easy and single-step titanium (Ti) powder assisted surface pretreatment process is demonstrated to enhance the diamond nucleation density of ultrananocrystalline diamond (UNCD) films. It is suggested that the Ti fragments attach to silicon (Si) surface form bond with carbon at a faster rate and therefore facilitates the diamond nucleation. The formation of smaller diamond clusters with higher nucleation density on Ti mixed nanodiamond powder pretreated Si substrate is found to be the main reason for smooth UNCD film surface in comparison to the conventional surface pretreatment by only nanodiamond powder ultrasonic process. The X-ray photoelectron spectroscopic study ascertains the absence of SiC on the Si surface, which suggests that the pits, defects and Ti fragments on the Si surface are the nucleation centers to diamond crystal formation. The glancing-incidence X-ray diffraction measurements from 100 nm thick UNCD films evidently show reflections from diamond crystal planes, suggesting it to be an alternative powerful technique to identify diamond phase of UNCD thin films in the absence of ultra-violet Raman spectroscopy, near-edge X-ray absorption fine structure and transmission electron microscopy techniques.     

金刚石膜微结构的慢正电子束测量研究

用慢正电子束辅助以拉曼光谱方法对一批较高质量的PECVD金刚石膜的微结构进行测量研究．拉曼光谱实验结果显示,这批金刚石膜中金刚石相含量比较高,正电子湮没实验进一步从微观结构上指出各个金刚石膜之间存在很大差异,并且从缺陷角度发现各样品中缺陷尺寸和缺陷浓度不一样,造成膜质量不同．S-E曲线变化趋势反映出各样品金刚石晶体结构存在明显不同．这表明正电子湮没技术是测量金刚石膜微结构的有力手段．     

沉积时间对球状微米金刚石聚晶结构的生长及其场发射特性影响

利用微波等离子体化学气相沉积法,在覆盖金属钛层的陶瓷衬底上,通过改变沉积时间制备出不同结构的类球状微米金刚石聚晶碳膜.通过扫描电子显微镜、喇曼光谱、X射线衍射谱对碳膜进行了分析测试,并研究了不同沉积时间下沉积的类球状微米金刚石聚晶薄膜的场致电子发射特性,结果显示:不同的沉积时间所制备的碳膜形貌有很大变化,场致电子发射的...     

CVD金刚石膜中1145cm~(-1)拉曼峰的研究

用拉曼光谱手段对CVD方法生长的金刚石膜,特别是其中最有争议的1145cm-1附近的拉曼峰进行了研究。用不同波长激光激发得到此峰的拉曼谱与量子尺寸选择效应所预期规律的相反,反驳了将1145cm-1附近的拉曼峰指认为纳米晶金刚石本征峰的说法。而通过对不同样品的比较,从侧面支持了将它归结为杂质,即反式聚乙炔的指认。更进一步通过分析不同尺寸的样品中杂质峰的相对强度,提出了这个峰的强度或许可以作为金刚石晶粒尺寸判据的建议。     

MPCVD金刚石的Raman光谱分析

用微波等离子体化学气相淀积法（MPCVD）在Si基片上生长了金刚石薄膜，通过对其进行Raman光谱分析，一次表征了金刚石的结构，纯度及应力状况等材料性能，同时并研究了生长过程中微波功率与金刚石性质的关系。研究表明，微波等离子体化学气相溶积法生长的金刚石薄膜，除了金刚石成分的生长外，还会有部分非金刚石成分的生长，金刚石的纯度与微波功率的关系不明显，另外此种方法生长的金刚石薄膜主要表现为张应力。     

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.     

Effects of N2 addition on nanocrystalline diamond films by HFCVD in Ar/CH4 gas mixture

Nanocrystalline diamond (NCD) films were grown on silicon substrates by hot filament chemical vapor deposition in Ar/N₂/CH₄ gas mixtures. The effects of seeding process prior to deposition, the total gas pressure, and concentration of nitrogen on the grain size, morphology and bonding nature in HFCVD technique were investigated. The results indicated that a low total gas pressure is favorable for nanosized diamond crystallites. Films micrograph obtained from scanning electron microscopy showed diamond nanograins elongated with the addition of nitrogen in the plasma. Crystal structure investigations were carried out by X-ray diffraction measurements for deposited films. An increase in the size of crystallite is also observed from XRD measurements in NCD film when nitrogen was added in plasma. From Raman spectra, it was observed that the relative intensity of G peak increases indicating more graphite content after nitrogen added in the plasma. The effects of the nitrogen incorporation in nanocrystalline films in HFCVD are discussed.     

The effect of boron ion implantation and annealing on the microstructure and electrical characteristics of the diamond films

Diamond films were doped by boron ion-implantation with the energy of 120 keV. The implantation dose ranged from 10¹⁴ to 10¹⁷ cm⁻². After the implantation, the diamond films were annealed at different temperatures (600–750°C) for different times (2–15 min). Scanning Electronic Microscope, Raman and Secondary Ion Mass-spectrum were used to investigate the effect of boron ion implantation and annealing on the microstructure of the diamond films. The electrical resistivities of the diamond films were also measured. It was found that the best dose of boron ion-implantation into the diamond film was around 10¹⁶ cm⁻². The appropriate annealing temperature and time was 700°C and 2–5 min, respectively. After implantation, the resistivities were reduced to 0.1 Ω cm (almost nine orders lower than the unimplanted diamond films). These results show that boron ion implantation can be an effective way to fabricate P-type diamond films.