栅极偏压对纳米金刚石薄膜沉积过程的影响

在HFCVD系统中施加栅极偏压和衬底偏压,采用双偏压成核和栅极偏压生长的方法成功制备了高质量的纳米金刚石薄膜.采用显微Raman高分辨率SEM和AFM等现代理化分析手段分析纳米金刚石膜的微结构,结果表明双偏压显著促进了金刚石的成核密度,平均晶粒尺寸在20 nm以内.试验观察和理论分析表明栅极偏压促进了热丝附近的等离子体浓度,提高了衬底附近的碳氢基团和氢原子浓度,提高了金刚石的成核密度、在保持晶粒的纳米尺寸的同时保持了较高的成膜质量和较低的生长缺陷.     

Current issues and problems in the chemical vapor deposition of diamond

Current issues and problems in the chemical vapor deposition (CVD) of diamond are those which relate to its characterization, its nucleation on foreign surfaces, the question of its formation in preference to the other phases of solid carbon (for example, graphite, chaoite, or lonsdaleite), why different morphologies and crystallographic orientations (textures) are seen in different experiments or with different parameters in the same experiment, and finally whether well-crystallized metastable phases can be obtained by CVD in other material systems or are only a peculiarity of carbon chemistry. Whether a given carbon coating is justly described as diamond has been such an issue, and coatings should clearly show evidence for diamond by x-ray diffraction and Raman spectroscopy before the claim of diamond is made. Experimental results have not been consistent in many cases, and much work remains to be done before an accurate assessment can be made of the technological impact of the development.     

The mechanism of diamond nucleation from energetic species

A model for diamond nucleation by energetic species (for example, bias-enhanced nucleation) is proposed. It involves spontaneous bulk nucleation of a diamond embryo cluster in a dense, amorphous carbon hydrogenated matrix; stabilization of the cluster by favorable boundary conditions of nucleation sites and hydrogen termination; and ion bombardment-induced growth through a preferential displacement mechanism. The model is substantiated by density functional tight-binding molecular dynamics simulations and an experimental study of the structure of bias-enhanced and ion beam-nucleated films. The model is also applicable to the nucleation of other materials by energetic species, such as cubic boron nitride.     

Block copolymer self-assembly-directed single-crystal homo- and heteroepitaxial nanostructures

Epitaxy is a widely used method to grow high-quality crystals. One of the key challenges in the field of inorganic solids is the development of epitaxial single-crystal nanostructures. We describe their formation from block copolymer self-assembly-directed nanoporous templates on single-crystal Si backfilled with Si or NiSi through a laser-induced transient melt process. Depending on thickness, template removal leaves either an array of nanopillars or porous nanostructures behind. For stoichiometric NiSi deposition, the template pores provide confinement, enabling heteroepitaxial growth. Irradiation through a mask provides access to hierarchically structured materials. These results on etchable and non-etchable materials suggest a general strategy for growing epitaxial single-crystal nanostructured thin films for fundamental studies and a wide variety of applications, including energy conversion and storage.     

Van der Waals Epitaxial Growth of agr-Alumina Nanocrystals on Mica

Lattice mismatch stresses, which severely restrict heteroepitaxial growth, are greatly minimized when thin alumina films are grown by means of van der Waals forces on inert mica substrates. A 10-nanometer-thick epitaxial film exhibits crystallographic sixfold symmetry, a lattice constant close to that of the basal plane [0001] of alpha-alumina (sapphire), and an aluminum: oxygen atomic ratio of 1:1.51 +/- 0.02 (measured by x-ray photoelectron spectroscopy), again the same as for bulk sapphire. The film is free of steps and grain boundaries over large areas and appears to be an ideal model system for studying adhesion, tribology, and other surface phenomena at atomic scales.     

Electrochemical defect-mediated thin-film growth

An electrodeposition technique is described that produces atomically flat epitaxial metal overlayers of quality similar to that obtained by ultrahigh vacuum techniques at elevated temperature. In this approach, a metal of interest such as silver is co-deposited with a reversibly deposited mediator metal. The mediator is periodically deposited and stripped from the surface, and this serves to significantly increase the density of two-dimensional islands of silver atoms, promoting a layer-by-layer thin-film growth mode. In situ scanning tunneling microscopy was used to demonstrate the growth process for the heteroepitaxial system silver/gold (111) with either lead or copper as the mediator.     

Polycrystalline CVD Diamond Films with High Electrical Mobility

Advances in the deposition process have led to dramatic improvements in the electronic properties of polycrystalline diamond films produced by chemical vapor deposition (CVD). It is now possible to produce CVD diamond with properties approaching those of IIa natural diamonds. The combined electron-hole mobility, as measured by transient photoconductivity at low carrier density, is 4000 square centimeters per volt per second at an electric field of 200 volts per centimeter and is comparable to that of the best single-crystal IIa natural diamonds. Carrier lifetimes measured under the same conditions are 150 picoseconds for the CVD diamond and 300 picoseconds for single-crystal diamond. The collection distance at a field of 10 kilovolts per centimeter is 15 micrometers for the CVD diamond as compared to 30 micrometers for natural diamonds. The electrical qualities appear to correlate with the width of the diamond Raman peak. Also, although the collection distance at the highest fields in the films nearly equals the average grain size, there is no evidence of deleterious grain boundary effects.     

Heterogeneous and epitaxial nucleation of protein crystals on mineral surfaces

Fifty different mineral samples were tested as potential heterogeneous or epitaxial nucleants for four commonly crystallized proteins. It was found, by conventional protein crystallization techniques, that for each protein there was a set of mineral substrates that promoted nucleation of crystals at lower critical levels of supersaturation than required for spontaneous growth. Numerous examples, involving all four proteins, were observed of modification of crystal habit and, in some cases, unit cell properties promoted by the presence of the mineral nucleants. In at least one case, the growth of lysozyme on the mineral apophyllite, it was shown by lattice analysis and x-ray diffraction that the nucleation and growth of the protein crystal on the mineral was likely to involve a direct lattice match.     

Low-pressure, metastable growth of diamond and "diamondlike" phases

Diamond may be grown at low pressures where it is the metastable form of carbon. Recent advances in a wide variety of plasma and electrical discharge methods have led to dramatic increases in growth rates. All of these methods have certain aspects in common, namely, the presence of atomic hydrogen and the production of energetic carbon-containing fragments under conditions that support high mobilities on the diamond surface. Some understanding of the processes taking place during nucleation and growth of diamond has been achieved, but detailed molecular mechanisms are not yet known. Related research has led to the discovery of a new class of materials, the "diamondlike" phases. Vapor-grown diamond and diamondlike materials may have eventual applications in abrasives, tool coatings, bearing surfaces, electronics, optics, tribological surfaces, and corrosion protection.     

Adatom pairing structures for Ge on si(100): the initial stage of island formation

With the use of scanning tunneling microscopy, it is shown that germanium atoms adsorbed on the (100) surface of silicon near room temperature form chainlike structures that are tilted from the substrate dimer bond direction and that consist of two-atom units arranged in adjoining substrate troughs. These units are distinctly different from surface dimers. They may provide the link missing in our understanding of the elementary processes in epitaxial film growth: the step between monomer adsorption and the initial formation of two-dimensional growth islands.     

Electronic confinement and coherence in patterned epitaxial graphene

Ultrathin epitaxial graphite was grown on single-crystal silicon carbide by vacuum graphitization. The material can be patterned using standard nanolithography methods. The transport properties, which are closely related to those of carbon nanotubes, are dominated by the single epitaxial graphene layer at the silicon carbide interface and reveal the Dirac nature of the charge carriers. Patterned structures show quantum confinement of electrons and phase coherence lengths beyond 1 micrometer at 4 kelvin, with mobilities exceeding 2.5 square meters per volt-second. All-graphene electronically coherent devices and device architectures are envisaged.     

Crack-like sources of dislocation nucleation and multiplication in thin films

With the combination of the height sensitivity of atomic force microscopy and the strain sensitivity of transmission electron microscopy, it is shown that near singular stress concentrations can develop naturally in strained epitaxial films. These crack-like instabilities are identified as the sources of dislocation nucleation and multiplication in films of high misfit. This link between morphological instability and dislocation nucleation provides a method for studying the basic micromechanisms that determine the strength and mechanical properties of materials.     

A hexagonal (wurtzite) form of silicon

The existence of a hexagonal (wurtzite) form of silicon, similar to that form of diamond (carbon) observed in meteorites and in the laboratory, has been identified by x-ray diffraction in reaction-bonded silicon nitride containing unreacted silicon. The presence of this phase is due to stresses created in the silicon by the nitridation reaction.     

汽相生长金刚石微粒及金刚石薄膜分析

用化学汽相沉积法已长出金刚石微粒及金刚石薄膜,并对它进行了扫描电镜观查,X-射线衍射分析,喇曼光谱分析,硬度测试,证明它确是金刚石并具有金刚石的性能.     

Melting of diamond at high pressure

Melting of diamond at high pressure and the properties of liquid carbon at pressures greater than 1 megabar were investigated with a first-principles molecular dynamics technique. The results indicate an increase of the diamond melting temperature with pressure, which is opposite to the behavior of silicon and germanium. This is contrary to long-held assumptions, but agrees with recent experiments, and has important implications for geology and astrophysics. As is the case for the solid phase of carbon at low temperature, which changes greatly with pressure from graphite to diamond, the structural and bonding properties of liquid carbon vary strongly with pressure.     

Epitaxial growth of diamond films on si(111) at room temperature by mass-selected low-energy c+ beams

Diamond films ( approximately 0.7 micrometer thick) have been epitaxially grown on Si(111) substrates at room temperature with mass-selected 120-electronvolt C(+) ions. The diamond reflections observed in x-ray diffraction are well localized at their predicted positions, indicating that (i) the diamond(111) and (220) planes are parallel to the Si(111) and (220), respectively; (ii) the diamond rotational spread around its (111) normal is approximately 1.7 degrees ; and (iii) the mosaic block size is approximately 150 A. The film growth is discussed in terms of subplantation-a shallow subsurface implantation model. This discovery is an important step toward diamond semiconductor devices.     

Growth of diamond from atomic hydrogen and a supersonic free jet of methyl radicals

The growth of small ( approximately 10-micrometer) diamond particles (on 0.1-or 0.25-micrometer seed crystals) using an effusive glow discharge nozzle for H.and a separate supersonic pyrolysis jet for .CH(3) is reported. Laser micro-Raman, scanning electron microscopy, and x-ray photoelectron spectroscopy data are presented as evidence that well-crystallized diamond is indeed formed. Resonant multiphoton ionization spectroscopy is used as a diagnostic for the gas-phase chemistry indicating that the radical sources are clean and quantitative and that there is no detectable interconversion of .CH(3) to C(2)H(2) under the conditions of the experiment. Diamond growth is found at substrate temperatures greater than or equal to 650 degrees C with no marked increase in the rate of growth up to 850 degrees C. Acetylene does not give good quality diamond under similar conditions.     

Nanometer-size alpha-PbO(2)-type TiO(2) in garnet: A thermobarometer for ultrahigh-pressure metamorphism

A high-pressure phase of titanium dioxide (TiO(2)) with an alpha-PbO(2)-type structure has been identified in garnet of diamondiferous quartzofeldspathic rocks from the Saxonian Erzgebirge, Germany. Analytical electron microscopy indicates that this alpha-PbO(2)-type TiO(2) occurred as an epitaxial nanometer-thick slab between twinned rutile bicrystals. Given a V-shaped curve for the equilibrium phase boundary of alpha-PbO(2)-type TiO(2) to rutile, the stabilization pressure of alpha-PbO(2)-type TiO(2) should be 4 to 5 gigapascals at 900 degrees to 1000 degrees C. This suggests a burial of continental crustal rocks to depths of at least 130 kilometers. The alpha-PbO(2)-type TiO(2) may be a useful pressure and temperature indicator in the diamond stability field.     

"Molecule corrals" for studies of monolayer organic films

Scanning tunneling microscopy (STM) studies have demonstrated that monolayer-deep, flat-bottomed, circular etch pits can be grown on highly ordered pyrolytic graphite by high-temperature etching in the presence of oxygen. In this work, these graphite etch pits are used as "molecule corrals" to isolate ensembles of molecules for study by STM. The nucleation of self-assembled molecular films in the corrals took place by nucleation events separate from those leading to self-assembly on the surrounding terrace and allowed the measurement of the nucleation rate constant in the corrals. The dependence of the nucleation rate for self-assembly on pit size shows that nucleation occurs at open terrace sites and that step edges (that is, the corral's perimeter) and confinement inhibit film growth.     

Particle nucleation in the tropical boundary layer and its coupling to marine sulfur sources

New particle formation in a tropical marine boundary layer setting was characterized during NASA's Pacific Exploratory Mission-Tropics A program. It represents the clearest demonstration to date of aerosol nucleation and growth being linked to the natural marine sulfur cycle. This conclusion was based on real-time observations of dimethylsulfide, sulfur dioxide, sulfuric acid (gas), hydroxide, ozone, temperature, relative humidity, aerosol size and number distribution, and total aerosol surface area. Classic binary nucleation theory predicts no nucleation under the observed marine boundary layer conditions.