Nucleation and growth mechanism of diamond during hot-filament chemical vapour deposition

High-resolution transmission electron microscopy (HRTEM) was employed to study the nucleation and subsequent growth mechanism of crystalline diamond grown on copper TEM grids by the hot-filament chemical vapour deposition process. The HRTEM revealed direct evidence for the formation of a diamond-like amorphous carbon layer 8–14 nm thick, in which small diamond microcrystallites about 2–5 nm across were embedded. These diamond microcrystallites were formed as a result of direct transformation of the diamond-like carbon into diamond. Large diamond crystallites were observed to grow from these microcrystallites. The diamond surface was found to be non-uniform. It is envisaged that the diamond microcrystallites present in the amorphous, diamond-like carbon layer provide nucleation sites on which the large diamond crystallites grew. A mechanism of diamond growth has been proposed, based on the experimental findings, and is consistent with available theoretical models and numerous experimental observations reported in the literature.     

Growth of diamond thin films by chemical vapour deposition

Deposition of diamond thin films on non-diamond substrates at low pressures (<760 torr) and low temperatures (<2000°C) by chemical vapour deposition (CVD) has been the subject of intense research in the last few years. The structural and the electrical properties of CVD diamond films grown on p-type 〈111〉 and high-resistivity (>100 kΩ-cm) 〈100〉 oriented silicon substrates by hot filament chemical vapour deposition technique are described in this review paper.     

Tuning the conditions for the deposition of nanocrystalline diamond by hot filament chemical vapour deposition

Although large focus has been placed into the deposition of nanocrystalline and ultra-nanocrystalline diamond films, most of this research uses microwave plasma assisted CVD systems. However, the growth conditions used in microwave systems cannot be directly used in hot-filament CVD systems. This paper, aims to enlarge the knowledge of the diamond film depositing process. H2/CH4/Ar gas mixtures have been used to deposit micro, nano and ultra-nanocrystalline diamond films by hot-filament CVD systems. Additionally, the distance between the filaments array and the substrate was varied, in order to observe its effect and consequently the effect of a lower substrate temperature in the nucleation density and deposition. All the samples were characterized for microstructure and quality, using scanning electron microscopy and Raman spectroscopy.     

The effective chemical vapour deposition rate of diamond

The effective chemical vapour deposition (CVD) rate of diamond, defined as the total thickness of diamond or as the mass of diamond deposited per unit time, may be increased by orders of magnitude by increasing the substrate area per unit volume. To obtain these high deposition rates, novel substrate designs are proposed that exploit three-dimensional arrays of small diameter wires or fibres. The analysis suggests that the increased diamond output should be achieved with no increase in the net gas flow or power consumption, which could lead to the more economic production of solid diamond shapes and of composites containing continuous or short diamond fibres, or particulate diamond. Estimates for the cost of CVD diamond made by the fibre array technique are compared with reported current and predicted costs for CVD diamond and estimates for the cost of CVD SiC.     

Rheotaxial diamond growth by chemical vapor deposition

This paper is to report a novel method to synthesize diamond crystal by using a well developed chemical vapor deposition process, but on a liquid substrate, while substrates of prevailing practice are solid. The substrate materials are metals which become liquid at diamond deposition temperature, such as elements Sn and Ga, and eutectic alloys of Cu-Ge, Sn-Ge. One result is that, while reported diamond crystal size was about 10 to 40 micrometers on the solid substrate, on the liquid substrate, the crystal size has reached so far about 300 micrometers. Received: 17 May 2000 / Reviewed and accepted: 8 June 2000     

The morphology and growth mechanism of TiC whisker prepared by chemical vapour deposition

TiC whiskers with good quality and high yield are prepared by a modified chemical vapour deposition (CVD). The whisker morphology and factors affecting its formation have been investigated. Various whisker morphologies such as Wool-, Hassock-, Cluster-, bar-, Hedgehog-, and bamboo-like, are observed under different conditions. The morphologies of TiC whiskers are markedly affected by the gas flow rate and the C/Ti ratio, which is supposed to be related to concentration variation and the formation of Ni-Ti eutectic liquid phase. The growth characteristics of TiC whiskers are also affected by the stability of deposition parameters. It is found that in the course of whisker growth on nickel substrate, the well known VLS mechanism is not necessarily dominant. It is effective in the initial stage, but then might change to the VS mechanism with the dissipation of liquid droplets at the whisker tips. The deposition temperature plays an important role in changing from the VLS to the VS mechanism.     

化学气相沉积法制备定向碳纳米管及其生长机理的研究

以环己烷为碳源,二茂铁作催化剂,采用浮动催化化学气相沉积法制备了定向碳纳米管,并用SEM、TEM及Raman光谱对样品进行了鉴定和表征.并从不同的角度,提出了定向碳纳米管遵循底部生长的机理.     

High thermal conductivity diamond coated graphite by microwave plasma chemical vapour deposition

Diamond film was grown on high thermal conductivity graphite substrate using microwave plasma chemical vapour deposition method. Nanodiamond particles were uniformly seeded on the substrate to generate high nucleation density by a spray gun. The continuous and high purity diamond film was obtained, and growth rate was up to 2.7 μm h^??1. The thickness, surface morphology, quality and composite phase of the film were analysed by SEM, Raman and X-ray diffraction. It was shown that graphite coated with diamond presented a higher thermal conductivity (520?W?m^??1 k^??1) than copper. Furthermore, this coated material with high thermal conductivity, good strength and non-conductive surface will make it possible to be widely used in thermal management field.     

Formation of large diamond crystals in oxyacetylene flame chemical vapour deposition

Diamond coatings were deposited on diamond-polished molybdenum substrates from a premixed oxyacetylene flame for a long time (up to 4 h) at substrate temperatures between 700 and 950°C, acetylene-to-oxygen ratios 1.02–1.07 and total flow rates between 230 and 310 standard Lh^–1. The coatings contain, in addition to the densely populated octahedral crystals making a continuous layer of determined thickness, a number of individual large cuboctahedral crystals sticking out far above the layer. A large cuboctahedral crystal is formed from an octahedral one when the latter reaches a certain height at which its temperature becomes sufficiently high for the octahedron-to-cuboctahedron conversion to take place. This conversion was found to occur by a flattening of the octahedron pyramid tip whereby a {100} face perpendicular to the growth direction is formed. Both the height of the crystal and size of the {100} face increase upon further deposition, reaching up to 230 m above the octahedral crystals layer and up to about 200 m, respectively. The large crystals have smooth {100} faces, but otherwise often have an irregular shape which may be due to a high temperature favouring deposition of non-diamond carbon.     

Structure of diamond and diamond like carbon thin films grown by hot-filament chemical vapour deposition technique

Micro-crystalline diamond (MCD) and diamond like carbon (DLC) thin films were deposited on silicon (100) substrates by hot-filament CVD process using a mixture of CH₄ and H₂ gases at substrate temperature between 400–800°C. The microstructure of the films were studied by X-ray diffraction and scanning electron microscopy. The low temperature deposited films were found to have a mixture of amorphous and crystalline phases. At high temperatures (> 750°C) only crystalline diamond phase was obtained. Scanning electron micrographs showed faceted microcrystals of sizes up to 2μm with fairly uniform size distribution. The structure of DLC films was studied by spectroscopic ellipsometry technique. An estimate of the amount of carbon bonds existing insp ² andsp ³ form was obtained by a specially developed modelling technique. The typical values ofsp ³/sp ² ratio in our films are between 1·88–8·02. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995     

Ion irradiation-induced modifications of diamond nanorods synthesised by microwave plasma chemical vapour deposition

Diamond nanorods (DNRs) synthesised by the high methane content in argon rich microwave plasma chemical vapour deposition (MPCVD) have been implanted with nitrogen ions. The nanorods were characterised by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The DNRs consist of single-crystalline diamond cores of 3–5?nm in diameter and several tens of nanometres in length. For purification from non-diamond contents, hydrogen plasma etching of DNRs was performed. Structural modifications of etched DNRs were studied after irradiating with 50?keV nitrogen ions under the fluence of 5?×?10¹⁴, 1?×?10¹⁵, 5?×?10¹⁵ and 1?×?10¹⁶?ions?cm^?2. Nitrogen-ion implantation changes the carbon–carbon bonding and structural state of the nanocrystalline diamond (NCD). Raman spectroscopy was used to study the structure before and after ion irradiation, indicating the coexistence of diamond and graphite in the samples. The results indicated the increase in graphitic and sp²-related content, at the expense of decrease in diamond crystallinity, for ion implantation dose of 5?×?10^15?cm^?2 and higher. The method proves valuable for the formation of hybrid nanostructures with controlled fractions of sp³–sp² bonding.     

Grain growth of copper films prepared by chemical vapour deposition

Copper films having thickness 600 nm were prepared on TiN using chemical vapour deposition (CVD). The deposited films were annealed at various temperatures (350–550°C) in Ar and H₂(10%)-Ar ambients. The changes in the grain size of the films upon annealing were investigated. Annealing in an H₂(10%)-Ar ambient produced normal grain growth; annealing in an Ar ambient caused grain growth to stop at 550°C. The grain size followed a monomodal distribution and the mean size increased in proportion to the square root of the annealing time, indicating the curvature of the grain is the main driving force for grain growth. Upon annealing at 450°C for 30 min in an H₂(10%)-Ar ambient, the average grain size of the film increased from 122 nm to 219 nm, and the resistivity decreased from 2.35 μΩ cm to 2.12 μΩ cm at a film thickness of 600 nm. This revised version was published online in July 2006 with corrections to the Cover Date.