NEXAFS characterization of nanocrystalline diamond thin films synthesized with high methane concentrations

Diamond thin films were deposited on silicon in gas mixtures of methane and hydrogen with different methane concentrations ranging from 1% to 100% using microwave plasma assisted chemical vapor deposition. Both Raman spectroscopy and synchrotron near edge extended X-ray absorption fine structure spectroscopy (NEXAFS) were used to characterize the electronic structure and chemical bonding of the synthesized films. The NEXAFS spectra of the nanocrystalline diamond (NCD) films exhibit clear spectral characteristics of diamond. Close observation reveals that the films (10% CH₄ or above) exhibit a slightly broadened exciton transition with a 0.25 eV blue shift. With the increase in methane concentration, the growth rate, the surface smoothness, and the sp² carbon concentration of the films increase while the grain size decreases. Well-faceted microcrystalline diamond films were synthesized with a methane concentration of 5% or lower, while NCD films were formed with a methane concentration of 10% or higher. Diamond thin films with low surface roughness and fine nanocrystalline structure have been synthesized with high methane concentrations (50% or above). It has been observed that the diamond growth rate increases with methane concentration. The growth rate at 100% methane concentration is approximately 10 times higher than at 1%.     

Fluorinated a-C:H films investigated by thermal-induced gas effusion

Using thermal-induced gas effusion the decomposition of plasma deposited fluorinated a-C:H films has been investigated. The main contributions to the effusion spectra were found to come from hydrogen, hydrocarbons, CF₄ and HF. It is observed that hydrogen-related effusion is progressively substituted by the effusion of CF₄-related species as the fluorine content is increased, confirming that fluorine atoms substitute hydrogen in the amorphous network. At low fluorine contents (<10 at.%) the material is relatively compact and the effusion of hydrogen-related species (hydrogen molecules and hydrocarbons) dominate. For high enough fluorine concentrations a strong change in the effusion characteristics indicates that an interconnected network of voids is present. Strong effusion of CF₄-related species is found to be consistent with a surface desorption process and can be observed when CF_n bonds are present in the film microstructure and the void network dimensions are large enough, i.e. for films with the highest fluorine contents (∼20 at.%). The effusion results can be correlated to a structural transition from diamond-like to polymer-like film.     

Effects of Hydrogen-Dilution on Opto-Structural Properties of Hot-wire CVD Grown a-Si:H/nc-Si:H Multilayer for Photovoltaics

The multilayered thin film structure of amorphous silicon (a-Si:H) and nanocrystalline silicon (nc-Si:H) provides the possibility of bandgap tuning for fabrication of multijunction solar cells. This paper communicates a detailed analysis of optical and structural properties of a-Si:H/nc-Si:H multilayer thin films by hot-wire chemical vapor deposition at low hydrogen (H₂) and silane (SiH₄) flow rates. A set of multilayer films with 25 bilayers of a-Si:H/nc-Si:H are prepared using different hydrogen-dilution of SiH₄ in the alternating nc-Si:H layers. The first and the second order Raman scattering studies reveal the presence of mixed phases of silicon in the nc-Si:H layers. Raman and XRD investigation of the films confirm the presence of different sizes of the silicon nanocrystals. The optical spectroscopic analysis instead of FTIR analysis of multilayer films is utilized uniquely to determine the hydrogen content in the a-Si:H/nc-Si:H multilayers and is related to the amorphous phase of the films. No significant change in hydrogen content is observed and the amorphous phase is found to decrease with increase in hydrogen dilution. Further, no quantum size effect (QSE) was observed due to the large growth time of nc-Si:H layers. Thus the experimental result shows that the bandgap of multilayer films decreases due to reduction in amorphous silicon phase, ineffective QSE and relative loss of hydrogen content.

     

Low-temperature synthesis of graphene on Cu using plasma-assisted thermal chemical vapor deposition

Plasma-assisted thermal chemical vapor deposition (CVD) was carried out to synthesize high-quality graphene film at a low temperature of 600°C. Monolayer graphene films were thus synthesized on Cu foil using various ratios of hydrogen and methane in a gaseous mixture. The in situ plasma emission spectrum was measured to elucidate the mechanism of graphene growth in a plasma-assisted thermal CVD system. According to this process, a distance must be maintained between the plasma initial stage and the deposition stage to allow the plasma to diffuse to the substrate. Raman spectra revealed that a higher hydrogen concentration promoted the synthesis of a high-quality graphene film. The results demonstrate that plasma-assisted thermal CVD is a low-cost and effective way to synthesis high-quality graphene films at low temperature for graphene-based applications.     

Growth of microcrystalline and nanocrystalline diamond films by microwave plasmas in a gas mixture of 1% methane/5% hydrogen/94% argon

Well-faceted microcrystalline diamond (MCD) films were deposited along with nanocrystalline diamond (NCD) films on the same substrate by a microwave plasma in the gas mixture of 1% CH₄+5% H₂+94% Ar. This was achieved by forcing a microwave plasma ball generated at 170 torr gas pressure to touch a silicon substrate that was pre-seeded by nanocrystalline diamond powder resulting in a high concentration of atomic hydrogen on the surface of growing diamond. Previously reported compositional mapping of the argon–methane–hydrogen system for MCD and NCD growth was not valid in this process parameter space. The non-uniform concentrations of atomic hydrogen and carbon containing radicals such as C₂ as well as varied local substrate temperature resulted in the simultaneous deposition of well-faceted MCD films in some areas with nanograined NCD films in others. Dilution of methane/hydrogen microwave plasmas by as much as 94% of argon alone could not suppress the growth of MCD.     

Electrochemical behavior of the Ti–6Al–4V alloy coated with a-C:H films

In this work diamond-like carbon films were deposited on the Ti–6Al–4V alloy, which has been used in aeronautics and biomedical fields, by electrical discharges using a magnetron cathode and a 99.999% graphite target in two different atmospheres, the first one constituted by argon and hydrogen and the second one by argon and methane. Films deposited using the argon/hydrogen mixture were called a-C:H, while films deposited using the argon/methane mixture were called DLC. Raman spectroscopy was used to study the structure of the films. The Raman spectra profile of the a-C:H films is quite different from that of the DLC films. The disorder degree of the graphite crystalline phase in a-C:H films is higher than in DLC films (a-C:H films present small values for the the I_D/I_G ratio). Potentiodynamic corrosion tests in 0.5 mol l⁻¹ NaCl aqueous solution, pH 5.8, at room temperature (≈25 °C) were carried out as for the a-C:H as for the DLC coated surfaces. Comparison between the corrosion parameters of a-C:H and DLC coated surfaces under similar deposition time, showed that DLC coated surfaces present bigger corrosion potential (E_corr) and polarization resistance than those coated with a-C:H films. Electrochemical impedance spectroscopy (EIS) was also used to study the electrochemical behavior of a-C:H and DLC coated surfaces exposed to 0.5 mol l⁻¹ aqueous solution. The EIS results were simulated with equivalent electrical circuit models for porous films. The results of these simulations showed similar tendency to the one observed in the potentiodynamic corrosion tests. The DLC film resistance and the charge transfer resistance (R_ct) for the DLC coated surface/electrolyte interface were bigger than the ones determined for the a-C:H coated surfaces.     

Spectroscopic characterization of thin SiC films

The electrical, structural and optical properties of thin SiC films were investigated. A new approach based on high temperature annealing of layered carbon–silicon structures was used for the formation of the films. The SiC films were prepared by deposition of 30 nm thick carbon films on crystalline silicon (c-Si) and on porous silicon layers grown on c-Si. The layers were annealed to temperatures between 800 and 1400°C for different annealing times ranging between 15 and 180 s. The structure of the resulting SiC films was analyzed by Raman spectroscopy. The Raman spectra of as-deposited films consist of two broad bands at 1350 and 1580 cm⁻¹ characteristic of the presence of amorphous carbon. These bands were shifted to lower frequencies in the spectra of annealed layers and were assigned to the hexagonal and cubic SiC phases. The photoluminescence spectra of the studied layers show a broad band at 550 nm. The most intense photoluminescence was observed from non-annealed porous silicon layers covered with thin carbon films. A degradation of the luminescence and a simultaneous increase of the conductivity of the layers with increasing annealing temperature and/or duration of annealing was observed. This behavior strongly suggests the creation of defect states which determine the conductivity of the layers and at the same time act as non-radiative centers. The increase of defect states was explained as originating from the dehydrogenation of the silicon carbide layers by annealing.     

Ordered mesoporous carbide derived carbons for high pressure gas storage

The design of advanced porous materials is crucial for the development of new energy storage systems for mobile applications. In the following a new class of highly porous carbon structures is applied in gas storage. Ordered mesoporous carbide derived carbons (OM-CDC) were synthesized by chlorination of mesostructured silicon carbide ceramics (OM-SiC). Resulting OM-CDC structures were characterized by nitrogen physisorption methods and small angle X-ray scattering demonstrating high specific surface areas and bimodal pore size distributions by varying the synthesis and chlorination conditions. The adsorption properties could be further enhanced by reductive hydrogen treatment. Storage capacities for mobile applications dependant on the synthesis conditions were investigated in high pressure hydrogen and methane adsorption with extraordinary high uptakes compared to micro- and mesoporous reference materials. In addition, the adsorption kinetics are studied in dynamic n-butane adsorption.     

Comparative study of diamond films grown on silicon substrate using microwave plasma chemical vapor deposition and hot-filament chemical vapor deposition technique

Diamond films on the p-type Si(111) and p-type(100) substrates were prepared by microwave plasma chemical vapor deposition (MWCVD) and hot-filament chemical vapor deposition (HFCVD) by using a mixture of methane CH₄ and hydrogen H₂ as gas feed. The structure and composition of the films have been investigated by X-ray Diffraction, Raman Spectroscopy and Scanning Electron Microscopy methods. A high quality diamond crystalline structure of the obtained films by using HFCVD method was confirmed by clear XRD-pattern. SEM images show that the prepared films are poly crystalline diamond films consisting of diamond single crystallites (111)-orientation perpendicular to the substrate. Diamond films grown on silicon substrates by using HFCVD show good quality diamond and fewer non-diamond components.     

Friction force microscopy study of diamond films modified by a glow discharge treatment

A glow discharge treatment technique has been developed which enables control of the surface roughness and morphology of diamond films for applications in optical and electrical components. A conventional hot filament chemical vapour deposition (CVD) system was used to deposit the diamond films onto silicon substrates via a three-step sequential process: (i) deposition under normal conditions; (ii) exposure to either a pure hydrogen plasma or 3% methane in an excess of hydrogen using DC-bias; and (iii) diamond deposition for a further 2 h under standard conditions. The frictional characteristics and roughness of the film surfaces were investigated by atomic force microscopy (AFM) and the morphology and the growth rates determined from scanning electron microscope images. Lateral force microscopy (LFM) has revealed significant differences in frictional behaviour between the high quality diamond films and those modified by a glow discharge treatment. Friction forces on the diamond films were very low, with coefficients ∼0.01 against silicon nitride probe tips in air. However, friction forces and coefficients were significantly greater on the DC-biased films indicating the presence of a mechanically weaker material such as an amorphous carbon layer. A combination of growth rate and frictional data indicated that the exposure to the H₂ plasma etched the diamond surface whereas exposure to CH₄/H₂ plasma resulted in film growth. Re-Nucleation of diamond was possible (stage iii) after exposure to either plasma treatment. The resultant friction forces on these films were as low as on the standard diamond film.     

Growth of nanocrystalline diamond films by biased enhanced microwave plasma chemical vapor deposition

Nanocrystalline diamond (NCD) films were grown using biased enhanced growth (BEG) in microwave plasma chemical vapor deposition on mirror polished silicon substrates at temperatures in the range from 400 to 700°C. The films were characterized by Raman spectroscopy, X-ray diffraction (XRD), Auger electron spectroscopy and atomic force microscopy (AFM). Hardness of the films was measured by nano-indentor. Apart from graphitic D and G bands in the films, the Raman spectra exhibit NCD features near 1140 cm⁻¹. The relative intensity of the NCD to graphitic G band in the Raman spectra of the films is negligible in the films grown at 400°C. It increases with temperature and attains a maximum at 600°C following a sharp decrease in the films grown at higher temperatures. XRD results also indicate a maximum concentration of NCD in the film grown at 600°C. Average hardness of the films increases with temperature from ∼5 GPa to ∼40 GPa up to 600°C followed by a decrease (∼24 GPa) in the film grown at 700°C. Substrate temperature seems to play a crucial role in the growth of NCD in BEG processes. An increase in growth temperature may be responsible for evolving bonded hydrogen and increasing mobility of carbon atoms. Both factors help in developing NCD in the films grown at 500 and 600°C with a combination of subplantation mechanism, due to biasing, and a high concentration of H atoms in the gas-phase, typical of CVD diamond process. At 700°C the implanted carbon atoms may be migrating back to the surface resulting in domination of surface processes in the growth, which in turn should result in increase in graphitic content of the films at such a high methane concentration and continuous biasing used in the present study.     

Sensitivity of Porous Silicon Photoluminescence to Low Concentrations of CH4 and CO

In this paper we report the sensitivity of porous silicon photoluminescence (PL) to diluted mixtures of methane and carbon monoxide in synthetic air. We also investigate the separate effect of synthetic air, purified nitrogen and relative humidity on both photoluminescence and conductance (G). Porous silicon samples have been prepared from n-type silicon substrates. We find that PL intensity and G decrease in synthetic air with respect to their values in N₂. Presence of carbon monoxide reduces the PL intensity while methane provokes the opposite behaviour. The dependence of the PL spectra on methane and carbon monoxide concentrations has been investigated. The observed effects can be related to gas induced modifications in porous surface and suggest that porous silicon can be employed in gas sensor technology.     

Metal-organic framework carbide enhances interspecies electron transfer to produce methane

To solve the problem that the hydrogen partial pressure in the anaerobic fermentation system limits the hydrogen diffusion rate among species, porous metal materials derived from the metal-organic framework ZIF-8 are used to promote the anaerobic fermentation of ethanol to produce methane, and the mechanism for enhancing the electron transfer between microorganism species is explored. Scanning electron microscopy (SEM) shows that ZIF-8 derived porous carbon plays immobilized role of microbial communities and promotes nanowires generation. The results show that the methane yield and the maximum methane production rate increase with an increase of ZIF-8 derived porous carbon addition. When 200 mg/L ZIF-8 derived porous carbon is added, the system conductivity increases by 3.58-fold. Moreover, three-dimensional fluorescence spectroscopy analysis (3D-EEM) showed that ZIF-8 derived porous carbon promotes the relative content of fulvic acid in extracellular polymeric substance (EPS) from 18.0% to 23.6%, corresponding to methane yield and maximum methane production rate increasing by 18.81% and 19.04% respectively.     

碳化金属-有机骨架强化种间电子传递产甲烷

为了解决厌氧发酵系统中氢分压限制种间氢扩散速率问题,利用金属-有机骨架ZIF-8衍生多孔碳材料促进乙醇厌氧发酵生产甲烷,探究其对微生物种间电子传递的增强机理。扫描电镜SEM表明ZIF-8衍生多孔碳起到菌群固定化作用,并且能促进纳米导线产生。实验结果表明,随着ZIF-8衍生多孔碳添加量的增加,甲烷产量和最大产甲烷速率逐渐提高。添加200 mg/L ZIF-8衍生多孔碳时,系统导电性提高了3.58倍,三维荧光光谱分析表明ZIF-8衍生多孔碳能够促进微生物胞外聚合物（EPS）中类富里酸的相对含量由18.0%提高到23.6%,对应的甲烷产量和最大产甲烷速率分别增加了18.81%和19.04%。     

Boron doped diamond deposited by microwave plasma-assisted CVD at low and high pressures

Boron doped diamond is deposited over a range of pressures and chemistries including pressures from 35–120 Torr and gas chemistries including hydrogen–methane–diborane and argon–methane–hydrogen–diborane mixtures. The diamond deposition system is a 2.45 GHz microwave resonant cavity system. Diborane (B₂H₆) gas chemistry has been utilized with flow rates of 2.5–100 ppm. At low pressures of 35 Torr polycrystalline films are deposited using a feed gas mixture of hydrogen and 0.5% methane. At moderate pressures of 95 Torr, diamond films are grown using 60% Ar, 39% H₂ and 1% CH₄. For the high pressure experiments of 120 Torr, polycrystalline films are deposited using 98% H₂ and 2% CH₄. The deposition rate ranges from 0.3 to 1.6 μm/h. This investigation describes the relationship of the diborane flow rate and pressure versus the resulting film morphology, electrical properties, and morphology of the deposited films. The deposition of boron-doped polycrystalline diamond is done on 5 cm diameter silicon and silicon dioxide coated substrates. The resistivity spatial variation across the wafer was ± 5% indicating a good uniformity.     

Diamond nucleation and growth under very low-pressure conditions

The synthesis of thin diamond films using various chemical vapor deposition methods has received significant attention in recent years due to the unique characteristic of diamond, which make it an attractive candidate for a wide range of applications. In order to grow diamond epitaxially, the proper control of diamond nucleation on mirror-polished Si is essential. Adding the negative bias voltage to the substrate is the most popular method. This paper has proposed a new method to greatly enhance the nuclear density. Under very low pressure (1 torr), the high-density nucleation of diamond is achieved on mirror-polished silicon in a hot-filament chemical vapor deposition (HFCVD). Scanning electron microscopy has demonstrated that the nuclear density can be as high as 10¹⁰–10¹¹ cm⁻². Raman spectra of the sample have shown a dominant diamond characteristic peak at 1332 cm⁻¹. The pressure effect has been discussed in detail and it has been shown that the very low pressure is a very effective means to nucleate and grow diamond films on mirror-polished silicon. Extraordinary pure hydrogen (purity=99.9999%) was used as the source. Compared with the highly pure hydrogen (purity=99.99%), we found that the density of nucleation was greatly increased. The residual oxygen in the hydrogen displayed a very obvious negative effect on the nucleation of diamond, although it can accelerate the growth of diamond. Based on these results, it was suggested that the enhanced nucleation at very low pressure should be attributed to an increased mean free path, which induced a high density of atomic hydrogen and hydrocarbon radicals near the silicon surface. Atomic hydrogen can effectively etch the oxide layer on the surface of silicon and so greatly enhance the nucleation density.     

Vibrational Spectra of Vitreous B2O3.xH2O

The infrared absorption spectra of boron oxide glasses of low and high water content have been obtained in the 400- to 4000-cm.⁻¹ region using thin films or fine powders dispersed in a liquid. A structural interpretation of the glass spectra has been made with the aid of the spectra of the closely related materials boric acid, orthorhombic metaboric acid, and partly deuterated boron oxide glass of high water content. It has been shown that the glass spectra are consistent with a random-network structure in which each boron is triangularly coordinated by three oxygens and that the presence of water leads to weak hydrogen bonding between oxygen atoms. No evidence for a substantial amount of tetrahedral coordination of boron by oxygen has been found in glasses of either low or high water content.     

Tuning oxygen impurities and microstructure of nanocrystalline silicon photovoltaic materials through hydrogen dilution

As a great promising material for third-generation thin-film photovoltaic cells, hydrogenated nanocrystalline silicon (nc-Si:H) thin films have a complex mixed-phase structure, which determines its defectful nature and easy residing of oxygen impurities. We have performed a detailed investigation on the microstructure properties and oxygen impurities in the nc-Si:H thin films prepared under different hydrogen dilution ratio treatment by the plasma-enhanced chemical vapor deposition (PECVD) process. X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and optical transmission spectroscopy have been utilized to fully characterize the microstructure properties of the nc-Si:H films. The oxygen and hydrogen contents have been obtained from infrared absorption spectroscopy. And the configuration state of oxygen impurities on the surface of the films has been confirmed by X-ray photoelectron spectroscopy, indicating that the films were well oxidized in the form of SiO₂. The correlation between the hydrogen content and the volume fraction of grain boundaries derived from the Raman measurements shows that the majority of the incorporated hydrogen is localized inside the grain boundaries. Furthermore, with the detailed information on the bonding configurations acquired from the infrared absorption spectroscopy, a full explanation has been provided for the mechanism of the varying microstructure evolution and oxygen impurities based on the two models of ion bombardment effect and hydrogen-induced annealing effect.     

High resolution TEM and triple-axis XRD investigation into porous silicon formed on highly conducting substrates

The microstructure of thin porous silicon films (∼1 μm) formed potentiostatically on p⁺-type silicon in dilute HF solutions is investigated via high resolution TEM and triple-axis XRD. Average pore diameters were found to increase with increasing etching potential, changing from a mixture of micro- and mesopores to predominately square macropores once oxide growth commences. It is postulated that these square pores result from crystallographic etching. High resolution TEM images revealed that stresses within porous silicon are sufficient to cause lattice distortions of the order of a few percent and that once oxide formation occurs areal defects are generated. Although the high resolution TEM analysis suggests that the lattices of the majority of the nanocrystals are compressed relative to bulk silicon and explanations for this are proposed, the combination of the porous silicon film's high porosity and thinness meant that this could not be confirmed by the more reliable triple-axis XRD measurements. Conversely, the triple-axis XRD revealed that thicker films grown under the same conditions had expanded lattices. The results also highlight the drawbacks of relying solely on high resolution TEM or double-axis XRD data when investigating the nature of lattice distortions.     

Poly(ethyl glycol) assisting water sorption enhancement of poly(ε‐caprolactone) blend for drug delivery

Poly(ε‐caprolactone) (PCL) has been thermally synthesized, and then fractionated to blend with poly(ethyl glycol) (PEG). Blend films of PCL and PEG have been prepared by solution casting. Fourier transform infrared spectrum and differential scanning calorimetry of the films have been carried out, and the results indicate some hydrogen bonding interaction between the two components, which is resulted from the carbonyl groups of PCL and the hydroxyl end‐groups of the low‐molecular‐weight PEG. Scanning electron microscope images of the blend films reveal porous network structures for their surfaces and for their inner parts and the porous structure becomes more pronounced with the increase of PEG in the blend film. Ibuprofen (IBU) was used as the model drug to test the drug release behavior for the PCL/PEG blend matrices. The results show that IBU could be released from the blend tablets rapidly, and the release rate increases with PEG content. Analysis of the release profiles indicates PCL erosion control release mechanism of pure PCL tablet, but drug diffusion control of the blend tablet, because PEG can absorb water to allow water feasible to diffuse into drug core and dissolve drug. Therefore, the interconnected channels in the blend matrices and the hydrophilic nature of PEG contribute to the improvement of the IBU release rate. The research indicates that drug release rate from PCL based material could be efficiently improved by addition of small amount of hydrophilic low‐molecular‐weight PEG. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011