氢终止金刚石表面的形成机理

为考察金刚石形成氢终止表面的反应机制,采用微波氢等离子体处理以及电阻丝氢气气氛加热处理进行对比研究.利用光发射谱(OES)和漫反射傅里叶变换红外光谱(DRIFTS)分别表征了微波氢等离子体中的活性基团和金刚石表面氢终止浓度.结果表明,微波氢等离子体环境下,随着衬底温度、等离子体密度和能量的增加,温度至700 ℃ (800 W/3 kPa)时,等离子体中出现了明显的CH基团;相应地,金刚石表面氢终止浓度随温度、等离子体密度和能量的增加而增加.采用氢气气氛下电阻丝加热的方法同样形成了氢终止金刚石表面,表明微波等离子体处理金刚石表面形成氢终止主要源于由温度控制的表面化学反应,而非等离子体的物理刻蚀作用.氧终止金刚石表面形成氢终止的机制是表面C=O键在高于500 ℃时分解为CO,相应的悬挂键由氢原子或氢分子占据.     

Cell adhesion properties on photochemically functionalized diamond

The biocompatibility of diamond was investigated with a view toward correlating surface chemistry and topography with cellular adhesion and growth. The adhesion properties of normal human dermal fibroblast (NHDF) cells on microcrystalline and ultrananocrystalline diamond (UNCD) surfaces were measured using atomic force microscopy. Cell adhesion forces increased by several times on the hydrogenated diamond surfaces after UV irradiation of the surfaces in air or after functionalization with undecylenic acid. A direct correlation between initial cell adhesion forces and the subsequent cell growth was observed. Cell adhesion forces were observed to be strongest on UV-treated UNCD, and cell growth experiments showed that UNCD was intrinsically more biocompatible than microcrystalline diamond surfaces. The surface carboxylic acid groups on the functionalized diamond surface provide tethering sites for laminin to support the growth of neuron cells. Finally, using capillary injection, a surface gradient of polyethylene glycol could be assembled on top of the diamond surface for the construction of a cell gradient.     

金刚石附氢(100)面脱氢势垒的量子化学研究

采用MNDO（UHF）方法计算了金刚石（100）－（1×1）：2H双氢化表面和（100）－（2×1）：H单氢化表面的脱氢势垒，论证了决定金刚石附氢表面脱氢势垒大小的主要因素是气相－表面吸附氢原子间的相互排斥大小，得出（100）面两种表面结构脱氢势垒的理论预言值分别为71和59kJ·mol-1，均大于（111）面脱氢势垒的理论预言值42kJ·mol-1．揭示了在同等生长条件下金刚石（111）面可供成核和生长的反应基多于（100）面，与实验上得到的同等生长条件下（111）面的相对生长率大于（100）面的结论是一致的。     

The Chemistry of C?H Bond Activation on Diamond

The surface of hydrogen‐terminated diamond resembles a solid hydrocarbon substrate. Interestingly, the C? H bonds on the diamond surface are not as unreactive as that of saturated hydrocarbon molecules owing to its unique surface electronic properties. The invention of C? H bond activation and C? C coupling reactions on the diamond surface allows chemists to develop powerful chemical transistors, biosensors, and photovoltaic cells on the diamond platform.     

Optimizing biosensing properties on undecylenic Acid-functionalized diamond

The optimization of biosensing efficiency on a diamond platform depends on the successful coupling of biomolecules on the surface, and also on effective signal transduction in the biorecognition events. In terms of biofunctionalization of diamond surfaces, surface electrochemical studies of diamond modified with undecylenic acid (UA), with and without headgroup protection, were performed. The direct photochemical coupling method employing UA was found to impart a higher density of carboxylic acid groups on the diamond surface compared to that using trifluoroethyl undecenoate (TFEU) as the protecting group during the coupling process. Non-faradic impedimetric DNA sensing revealed that lightly doped diamond gives better signal transduction sensitivity compared to highly doped diamond.     

Imaging SIMS for the investigation of substrate surfaces for CVD diamond deposition

The influence of substrate surface preparation on diamond nucleation is a major topic in the investigation of CVD-diamond deposition. The substrate, polishing material, its grain size, and the resulting surface roughness all influence diamond nucleation. Diamond can nucleate at scratches or residues of the polishing process which are providing nucleation sites. In this paper the surface of molybdenum and substrates polished with SiC and diamond powder was studied by imaging (2- and 3-dimensional) secondary ion mass spectrometry. The distribution and grain size of polishing residues (SiC, diamond) were determined and the reaction of diamond with the substrate during heating to deposition temperature was investigated. In this case a laterally inhomogeneous system of carbon containing species had to be characterized. Therefore compound-specific secondary ion mass spectrometry had to be performed. The results suggested that diamond residues on molybdenum substrates are partly dissolved during the heat treatment. The measurements indicate that a fraction of the diamond residues is still present after heat treatment and can provide nucleation sites for diamond deposition.     

金刚石（111）清洁／附氢表面与甲基的相互作用

利用Ａｍｌ分子轨道法计算了金刚石（１１１）清洁／附氢表面与甲基相互作用的特殊势能曲线，深入研究了清洁、附氢表面与甲基相互作用下基底弛豫重建、四甲基构型及成键能的差别，进而得到附氢表面较清洁表面更适合于甲基吸附，是更好的金刚石薄膜生长址的结论。在距基底表面０．５ｎｍ内，甲基与清洁、附氢表面皆有强烈的相互作用。     

Whole cell environmental biosensor on diamond

A whole-cell environmental biosensor was fabricated on a diamond electrode. Unicellular microalgae Chlorella vulgaris was entrapped in the bovine serum albumin (BSA) membrane and immobilized directly onto the surface of a diamond electrode for heavy metal detection. We found that the unique surface properties of diamond reduce the electrode fouling problem commonly encountered with metal electrodes. The cell-based diamond biosensor can attain a detection limit of 0.1 ppb for Zn(2+) and Cd(2+), and exhibits higher detection sensitivity and stability compared to platinum electrodes.     

Cycloadditions on diamond (100) 2 x 1: observation of lowered electron affinity due to hydrocarbon adsorption

The adsorption of allyl alcohol, acrylic acid, and allyl chloride, as well as unsaturated organic molecules such as acetylene and 1,3 butadiene, on reconstructed diamond (100) 2 x 1 have been investigated using high-resolution electron energy loss (HREELS) spectroscopy and synchrotron radiation spectroscopy. The cycloadditions of these organic molecules produce chemically adsorbed adlayers with varying degree of coverages on the clean diamond. The organic adsorbed surface has a lowered electron affinity and shows a secondary electron yield that varies between 12 and 40% of the yield obtained from a fully hydrogenated diamond surface. The diamond surface can be functionalized with hydroxyl, carboxylic, and chlorine functionalities by the adsorption of these allyl organics. The [2 + 2] adduct of acetylene on the diamond (100) 2 x 1 surface can be observed. 1,3-butadiene attains a higher coverage as well as forms a thermally more stable adlayer on the diamond surface compared to the other organic molecules, due to its ability to undergo [4 + 2] cycloaddition.     

Interaction of Chlorine with Hydrogenated Diamond Surface

The interaction of chlorine with the hydrogenated diamond surface has been investigated by diffuse reflectance Fourier-transform Infrared (FTIR) spectroscopy, temperature-programmed desorption (TPD) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The hydrogenated diamond surface is chlorinated by thermal reaction in chlorine. Hydrogen chemisorbed on the diamond surface is abstracted by chlorine and the chemisorption of chlorine is yielded. Hydroxyl groups are produced by treatment of the chlorinated diamond with water vapor at room temperature. Amino groups are produced by treatment of the chlorinated diamond with ammonia at 425 °C.     

Predicting facile epoxidation of the diamond (100) surface by dioxiranes and subsequent ring-opening reactions with nucleophiles

By means of density functional theory coupled with effective cluster models, we have theoretically predicted the viability of epoxidation of the diamond (100) surface by organic dioxiranes. In addition, subsequent ring-opening reactions of the as-formed epoxide surface species with some nucleophiles, including water, ammonia, and alcohol, have also been explored. The facile epoxidation of diamond (100) by dioxiranes presents a new alternative for oxidation of the diamond (100) surface. More importantly, the as-formed epoxide-like surface species would be a useful springboard for further functionalizations of the diamond surface given the well-known abundant chemistry of organic epoxides. Therefore, this approach provides another new route to chemical functionalization of the diamond surface, which is potentially useful for leading to the improvement of diamond behavior and constructing new hybrid diamond-based materials for wide potential applications in many fields. In perspective, implications for other theoretical work are also discussed.     

Scanning Probe Microscopy and Spectroscopy of CVD Diamond Films

 The surface morphology and electronic properties of as-deposited CVD diamond films and the diamond films which have been subjected to boron ion implantation or hydrogen plasma etching have been systematically studied by high resolution scanning probe microscopy and spectroscopy techniques. AFM and STM image observations have shown that (a) both the as-deposited CVD diamond films and the boron ion implanted films exhibit similar hillock morphologies on (100) crystal faces and these surface features are formed during the deposition process; (b) boron ion implantation does not cause a discernible increase in surface roughness; (c) atomic flatness can be achieved on crystal faces by hydrogen plasma etching of the film surface. Scanning tunnelling spectroscopy analysis has indicated that (a) the as-deposited diamond films and the hydrogen plasma etched diamond films possess typical p-type semiconductor surface electronic properties; (b) the as-deposited diamond films subjected to boron implantation exhibit surface electronic properties which change from p-type semiconducting behaviour to metallic behaviour; (c) the damage in the boron implanted diamond films is restricted to the surface layers since the electronic properties revert to p-type on depth profiling.     

Study of the Interface Microstructures of CVD Diamond Films by TEM

 The characteristics of the interface microstructures between a CVD diamond film and the silicon substrate have been studied by transmission electron microscopy and electron energy loss spectroscopy. The investigations are performed on plan-view TEM specimens which were intentionally thinned only from the film surface side allowing the overall microstructural features of the interface to be studied. A prominent interfacial layer with amorphous-like features has been directly observed for CVD diamond films that shows a highly twinned defective diamond surface morphology. Similar interfacial layers have also been observed on films with a <100> growth texture but having the {100} crystal faces randomly oriented on the silicon substrate. These interfacial layers have been unambiguously identified as diamond phase carbon by both electron diffraction and electron energy loss spectroscopy. For the CVD diamond films that exhibit heteroepitaxial growth features, with the {100} crystal faces aligned crystallographically on the silicon substrate, such an interfacial layer was not observed. This is consistent with the expectation that the epitaxial growth of CVD diamond films requires diamond crystals to directly nucleate and grow on the substrate surface or on an epitaxial interface layer that has a small lattice misfit to both the substrate and the thin film material.     

Covalent adlayer growth on a diamond thin film surface

The surface of boron-doped diamond thin films can be modified by exposure to a strong oxidizing agent, resulting in the formation of -OH and =O terminated diamond. The -OH groups are reacted with an acid chloride to produce a covalently bound, modified diamond thin film surface. The demonstration of these reactions allows for the facile modification of diamond surfaces using techniques well established for oxide surfaces. Characterization of the covalently bound species shows submonolayer coverage, and time-resolved fluorescence measurements are reflective of the highly featured nature of the diamond film.     

Organic functionalization of diamond (100) by addition reactions of carbene, silylene, and germylene: a theoretical prediction

We present a theoretical prediction of the facile cycloadditions of carbene, silylene, and germylene onto the diamond (100) surface, a new type of surface reaction that can be employed to functionalize diamond surface at low temperature. This finding renders the plausibility that the diamond surface can be chemically modified by the well-known carbene addition chemistry, which might introduce new functionalities to the diamond surface for novel applications in a diversity of fields.     

High sensitivity of diamond resonant microcantilevers for direct detection in liquids as probed by molecular electrostatic surface interactions

Resonant microcantilevers have demonstrated that they can play an important role in the detection of chemical and biological agents. Molecular interactions with target species on the mechanical microtransducers surface generally induce a change of the beam's bending stiffness, resulting in a shift of the resonance frequency. In most biochemical sensor applications, cantilevers must operate in liquid, even though damping deteriorates the vibrational performances of the transducers. Here we focus on diamond-based microcantilevers since their transducing properties surpass those of other materials. In fact, among a wide range of remarkable features, diamond possesses exceptional mechanical properties enabling the fabrication of cantilever beams with higher resonant frequencies and Q-factors than when made from other conventional materials. Therefore, they appear as one of the top-ranked materials for designing cantilevers operating in liquid media. In this study, we evaluate the resonator sensitivity performances of our diamond microcantilevers using grafted carboxylated alkyl chains as a tool to investigate the subtle changes of surface stiffness as induced by electrostatic interactions. Here, caproic acid was immobilized on the hydrogen-terminated surface of resonant polycrystalline diamond cantilevers using a novel one-step grafting technique that could be also adapted to several other functionalizations. By varying the pH of the solution one could tune the -COO(-)/-COOH ratio of carboxylic acid moieties immobilized on the surface, thus enabling fine variations of the surface stress. We were able to probe the cantilevers resonance frequency evolution and correlate it with the ratio of -COO(-)/-COOH terminations on the functionalized diamond surface and consequently the evolution of the electrostatic potential over the cantilever surface. The approach successfully enabled one to probe variations in cantilevers bending stiffness from several tens to hundreds of millinewtons/meter, thus opening the way for diamond microcantilevers to direct sensing applications in liquids. The evolution of the diamond surface chemistry was also investigated using X-ray photoelectron spectroscopy.     

Functionalization of diamond (100) by organic cycloaddition reactions of nitrenes: a theoretical prediction

[structure: see text] We predict the viability of organic cycloadditions of nitrenes onto the diamond (100) surface. This new type of surface reaction can be employed to functionalize diamond surface at low temperature, which might introduce new functionalities to the diamond surface for novel applications in a diversity of fields.     

Characterization of diamond surface terminations using electrochemical grafting with diazonium salts

A new characterization technique to identify qualitatively diamond surface terminations and to measure quantitatively the density of hydrogen atoms bonded to the diamond surface is introduced using electrochemical grafting of diamond with diazonium salts. The cathodic peak potentials for the grafting of nitrophenyl layers reveal qualitative information about surface terminations ranging from –H, to –OH to –O–. The charges consumed during the conversion of nitro- to aminophenyl are used to calculate quantitatively the density of hydrogen atoms bonded to the diamond surface. As hydrogen is generally very difficult to detect by other methods like X-ray Photon Spectroscopy, this new method will add significantly to the understanding of surface related properties of transducers.     

Nanomolar hydrogen peroxide detection using horseradish peroxidase covalently linked to undoped nanocrystalline diamond surfaces

In this article, we report on the low-level detection of hydrogen peroxide, a key player in the redox signaling pathway and a toxic product in the cellular system, using a colorimetric solution assay. Amine-terminated undoped nanocrystalline diamond thin films were grown on glass using a linear-antenna microwave plasma CVD process. The diamond surface consists mainly of -NH(2) termination. The aminated diamond surface was decorated with horseradish peroxidase (HRP) enzyme using carbodiimide coupling chemistry. The success of the HRP immobilization was confirmed by X-ray photoelectron spectroscopy (XPS). The enzymatic activity of immobilized HRP was determined with a colorimetric test based on the HRP-catalyzed oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sufonic acid (ABTS) in the presence of hydrogen peroxide. The surface coverage of active HRP was estimated to be Γ = 7.3 × 10(13) molecules cm(-2). The use of the functionalized diamond surface as an optical sensor for the detection of hydrogen peroxide with a detection limit of 35 nM was demonstrated.     

The Influence of Doping Levels and Surface Termination on the Electrochemistry of Polycrystalline Diamond

The influence of surface chemistry and boron doping density on the redox chemistry of Fe(CN) at CVD polycrystalline diamond electrodes is considered. It is demonstrated that for this couple both the doping density and the surface chemistry are important in determining the rate of charge transfer at the electrode/electrolyte interface. For hydrogen terminated CVD diamond metallic electrochemical behavior is always observed, even at boron doping densities as low as 7×10¹⁸ cm^?3. In contrast, the electrochemical behavior of oxygen terminated CVD diamond varies with doping density, a metallic response being observed at high doping density and semiconductor behavior at low doping density. It is shown that the results attained may be explained by a surface state mediated charge transfer mechanism, thus demonstrating the importance of controlling surface chemistry in electroanalytical applications of diamond.