TEM and HREM of diamond crystals grown on Si tips: structure and results of ion-beam-treatment

Diamond single crystals were grown on the silicon whiskers by a hot filament chemical vapor deposition technique at the filament temperature about 2100 degrees C and the temperature of support 800 degrees C. Specimens were examined by SEM, TEM, HRTEM and SAED. When the filament temperature was about 1900 degrees C globular polycrystalline diamond particles were grown. At a support temperature more then 800 degrees C SiC nanoparticles were formed. To investigate the ion etching process of the silicon tip/diamond system, tips were treated with an Ar(+) beam with energy up to 30 kV. The results depend on fluence: at 4 x 10(18)ion/cm(2) diamonds and partially Si tips were destroyed, amorphous layer was formed (sometimes with nanometric size fragments of diamond); at 1 x 10(18)ion/cm(2) sharpened diamonds (radius of curvature about 20 nm) covered with amorphous layer (radius about 80 nm) probably with nanoclusters of diamond were observed; at 4.4 x 10(17) ion/cm(2) there was no visible tip sharpening but formation of amorphous thick layer occurred. The emission characteristics of Si tips covered with diamond were improved due to ion treatment. Since such tips in our case were covered with amorphous layer containing nanometric size fragments of diamond, we suppose this layer is responsible for electron emission improvement.     

等离子体诱导碳纳米管到纳米金刚石的相变

采用氢等离子体，实现了碳纳米管向金刚石的结构相变，并实现了金刚石的高密度成核，有效成核密度可达10\+\{11\}／cm\+2以上，处于目前金刚石成核密度的最高行列，为制备优质的金刚石薄膜提供了保证.高分辨透射电镜、x射线衍射和拉曼光谱都证实了金刚石的形成.同时，对纳米金刚石晶粒的生成机理进行了初步探讨. 关键词： 等离子体 碳纳米管 纳米金刚石 结构相变     

Hydrogen incorporation in ultrananocrystalline diamond/amorphous carbon films

The incorporation of hydrogen within ultrananocrystalline diamond/amorphous carbon composite films has been investigated by nuclear reaction analysis (NRA) and Fourier transform infrared spectroscopy (FTIR). The film bulk contains ca. 7.5–8% H (for a deposition temperature of 600 °C), while the H concentration in the surface region is considerably higher. FTIR measurements show that the hydrogen‐rich surface is formed right at the beginning of the deposition process and grows outward as the film thickness increases. It can thus be concluded that surface hydrogen species play an active role in the formation of ultrananocrystalline diamond/amorphous carbon films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Analysis of polished polycrystalline diamond using dual beam focused ion beam microscopy

This paper presents a study on polycrystalline diamond (PCD) polished by dynamic friction polishing (DFP) with the aid of advanced dual beam FIB (focused ion beam) microscopy. After disclosing a variety of wear tracks by DFP using electron imaging in combination with the ion channelling effect, a dual beam FIB was successfully employed at wear track sites to specifically create both the large cross-sectional specimen for microanalysis and thin foil for nanoanalysis. The study concluded that the polished PCD subsurface was free from microscale cracking. However, the attached debris layer on the top surface contained metal oxides and non-diamond carbon phase with inhomogeneous distributions of C, Fe, Cr, Ni, Si and O across the layer. An attached layer directly above a diamond grain was composed of essentially amorphous carbon, suggesting that a direct phase transformation from diamond crystalline to amorphous occurred during DFP.     

Electrical and mechanical properties of C70 fullerene and graphite under high pressures studied using designer diamond anvils

We compare electrical and mechanical properties of C70 fullerene with high purity graphite to 48 GPa at room temperature using designer diamond anvils with embedded electrical microprobes. The electrical resistance of C70 shows a minimum at 20 GPa with transformation to an amorphous insulating phase complete above 35 GPa, while graphite remains conducting. Nanoindentation shows hardness values 220 times larger for the pressure quenched amorphous phase than for similarly treated graphite. Our studies establish that the amorphous carbon phase produced from C70 has unique properties not attainable from graphite.     

Combustion synthesis of high-quality diamond film suitable for application in electronic devices

The purpose of this research is to elucidate the electrical characteristics of a diamond film synthesized by combustion flame and synthesize a diamond film suitable for application in electronic devices. When the film contains amorphous carbon, the dielectric loss increases, i.e., the electrical characteristics of the diamond film are degraded. We employed three methods to decrease the amorphous carbon in the diamond film—the detection of the optimal equivalence ratio, addition of hydrogen into synthesizing gas, and heat treatment (annealing) of the diamond film. All these methods can decrease the amount of amorphous carbon effectively, thus systematically changing the factors influencing the optimal synthesis for improving the electric characteristics of the film. We have successfully developed a method for preparing a high-quality diamond film with excellent electrical characteristics that has no dielectric loss in the wide frequency range (10²–10⁸ Hz).     

Semiconductor diamond heater in the Kawai multianvil apparatus: an innovation to generate the lower mantle geotherm

Semiconductor diamond is considered the best heater material to generate ultra-high temperatures in a Kawai cell. In two pioneering studies, a mixture of graphite and amorphous boron (or boron carbide, B₄C) was converted to semiconductor diamond in the diamond stability field and was confirmed to generate 2000°C and 3500°C, respectively. Following these works, we synthesized a homemade boron-doped graphite block with fine machinability. With this technical breakthrough, we developed a semiconductor diamond heater in a smaller Kawai-type cell assembly. Here, we report the procedure for making machinable boron-doped graphite, and the performance of the material as a heater in a Kawai cell at 15?GPa using tungsten carbide anvils and at ～50?GPa using sintered diamond anvils. Furthermore, we present a finite element simulation of the temperature distribution generated by a semiconductor diamond heater, which is much more homogeneous than that generated by a metal heater.     

Anomalous two-phonon absorption in diamond nanocrystals embedded in amorphous carbon

Observation of anomalously strong IR absorption are reported in the region of two-phonon diamond frequencies in amorphous hydrogenated carbon films grown by cosputtering graphite and copper in a plasma. Up to five structural elements of bands having frequencies close to or coinciding with the figures quoted in the literature for two-phonon absorption bands in bulk diamond were observed. This suggests the presence of diamond nanocrystals in the grown layers. Observation of two-phonon absorption in thin films is in itself remarkable because of the smallness of its coefficient in bulk diamond. An estimate of the absorption coefficient in the dominant band at 2140 cm^?1 yields about 200 cm^?1, which exceeds by more than an order of magnitude that for bulk diamond. This can be assigned to an anomalous enhancement of the two-phonon absorption coefficient due to phonon confinement in the small diamond particles nucleated in the amorphous carbon matrix. An estimate of these inclusions from the band width yields about 20 Å. The reasons for the catalytic activity of copper in diamond nucleation are analyzed.     

Visualization of diamond nucleation and growth from energetic species

The mystery of diamond nucleation by energetic species is resolved via a special deposition scheme. The evolution of the precursor material for diamond nucleation and the development of the nanodiamond crystallites are visualized by high resolution electron microscopy and other spectroscopies. The diamond precipitation and growth are explained in terms of our recently proposed mechanism [Science 297, 1531 (2002)]]: (i) precipitation of sp(3) clusters a small fraction of which are perfect diamond; (ii) growth of diamond crystallites by preferential displacement of amorphous carbon atoms leaving diamond atoms intact. This general scheme is applicable to other materials such as cubic boron nitride.     

Mechanism of the formation of a diamond nanocomposite during transformations of C60 fullerite at high pressure

The results of an investigation of the transformation of C₆₀ fullerite to diamond under pressure through intermediate three-dimensionally polymerized and amorphous phases are reported. It is found that treatment of fullerite C₆₀ at pressures 12–14 GPa and temperatures ∼1400°C produces a nanocrystalline graphite-diamond composite with a concentration of the diamond component exceeding 50%. At lower temperatures (700–1200°C) nanocomposites consisting of diamondlike (sp ³) and graphitic (sp ²) amorphous phases are formed. The nanocomposites obtained have extremely high mechanical characteristics: hardness comparable to that of best diamond single crystals and fracture resistance two times greater than that of diamond. Mechanisms leading to the transformation of C₆₀ fullerite into diamond-based nanocomposites and the reasons for the high mechanical characteristics of these nanocomposites are discussed. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 11, 822–827 (10 June 1999)     

磷离子注入纳米金刚石薄膜的n型导电性能与微结构研究

系统研究了磷离子注入并在不同温度退火后的纳米金刚石薄膜的微结构和电学性能.研究表明,当退火温度达到800 ℃以上时,薄膜呈良好的n型电导.Raman光谱和电子顺磁共振谱的结果表明,薄膜中金刚石相含量越高和完整性越好,薄膜电阻率越低. 这说明纳米金刚石晶粒为薄膜提供了电导.1000 ℃退火后,薄膜晶界中的非晶石墨相有序度提高,碳悬键数量降低,薄膜电阻率升高.薄膜导电机理为磷离子注入的纳米金刚石晶粒提供了n型电导,非晶碳晶界为其电导提供了传输路径. 关键词： 纳米金刚石薄膜 n型 磷离子注入     

Luminescence excitation and its relation to the structures of natural crystalline diamond and diamond-like films

The luminescence excitation spectra (LES) of natural crystalline diamond and amorphous diamond-like films are measured at energies from 4 to 20 eV at the LOCUS station for luminescence and optical studies of the Kurchatov Institute synchrotron radiation source. Two sharp peaks at 5.5 and 10.5 eV are observed in the LES of diamond, while the LES of the film demonstrate only one peak at 10.5 eV. For crystalline diamond, the peaks can be explained within the framework of the diamond band structure and the processes of inelastic scattering of photoexcited holes. Dark-field electron microscope images of the diamond-like film show that, in spite of its amorphous structure, this film contains regions of coherent electron scattering whose dimensions are on the order of 2–5 nm, which is sufficient to describe the film LES using a model for crystalline diamond. The absence of the first peak in the film LES is related to the fact that the absorption coefficient of diamond is very small at 5.5 eV and radiation is only slightly absorbed by the thin film.     

Picosecond-laser-induced structural modifications in the bulk of single-crystal diamond

Arrays of through laser-graphitized microstructures have been fabricated in type IIa single-crystal 1.2-mm-thick diamond plates by multipulse laser irradiation with 10-ps pulses at λ=532 nm wavelength. Raman and photoluminescence (PL) spectroscopy studies of the bulk microstructures have evidenced the diamond transformation to amorphous carbon and graphitic phases and the formation of radiation defects pronounced in the PL spectra as the self-interstitial related center, the 3H center, at 504 nm. It is found that the ultrafast-laser-induced structural modifications in the bulk of single-crystal diamond plates occur along {111} planes, known as the planes of the lowest cleavage energy and strength in diamond.     

Demonstration of diamond field effect transistors by AlN/diamond heterostructure

This is the first report on an AlN/diamond heterojunction field effect transistor (HFET). The AlN epilayer is grown on oxygen‐terminated (111) diamond substrates using metalorganic vapor phase epitaxy at a temperature as high as 1240 °C. The transistor and gate capacitance–voltage characteristics indicate that the HFET behaves as a p‐channel FET with a normally‐on depletion mode. The HFET channel is located at the AlN/diamond interface, and holes are accumulated in diamond close to the interface. The development of the AlN/diamond HFET creates a new possibility for diamond‐based power electronics. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Amorphization of diamond by low temperature133Xe ion implantation

The structure of the amorphous layer in¹³³Xe implanted diamond is investigated by Mössbauer spectroscopy. Very different Debye Waller factors are measured after room temperature and liquid nitrogen temperature implantation.     

Microstructure and tribological performance of self-lubricating diamond/tetrahedral amorphous carbon composite film

In order to smooth the rough surface and further improve the wear-resistance of coarse chemical vapor deposition diamond films, diamond/tetrahedral amorphous carbon composite films were synthesized by a two-step preparation technique including hot-filament chemical vapor deposition for polycrystalline diamond (PCD) and subsequent filtered cathodic vacuum arc growth for tetrahedral amorphous carbon (ta-C). The microstructure and tribological performance of the composite films were investigated by means of various characterization techniques. The results indicated that the composite films consisted of a thick well-grained diamond base layer with a thickness up to 150 μm and a thin covering ta-C layer with a thickness of about 0.3 μm, and sp³-C fraction up to 73.93%. Deposition of a smooth ta-C film on coarse polycrystalline diamond films was proved to be an effective tool to lower the surface roughness of the polycrystalline diamond film. The wear-resistance of the diamond film was also enhanced by the self-lubricating effect of the covering ta-C film due to graphitic phase transformation. Under dry pin-on-disk wear test against Si₃N₄ ball, the friction coefficients of the composite films were much lower than that of the single PCD film. An extremely low friction coefficient (∼0.05) was achieved for the PCD/ta-C composite film. Moreover, the addition of Ti interlayer between the ta-C and the PCD layers can further reduce the surface roughness of the composite film. The main wear mechanism of the composite films was abrasive wear.     

Luminescence induced in diamond by He+ ion implantation into SiC/C composites with an inverse opal structure

The photoluminescence induced in diamond by helium ion implantation into SiC/C nanocomposite samples and their structure revealed by high-resolution transmission electron microscopy have been investigated. It has been found that, apart from crystallites of silicon carbide, graphite, and amorphous carbon, in the structure of the composites there are spherical carbon particles containing concentric graphite-like shells (onion-like particles). It has been established that onion-like particles are formed during high-temperature treatment of SiC/C nanocomposites in the course of their preparation. It has been shown that, after the implantation with the subsequent thermal treatment, nanocomposite samples exhibit a luminescence characteristic of N-V centers in diamonds. The assumption has been made that the diamond crystallites are formed at the center of onion-like particles during high-temperature treatment of the composite.     

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.     

Diamond-like amorphous carbon and nanocrystalline diamond obtained by detonation method

Abstract

The diamond-like amorphous carbon phase was obtained by means of detonation compression of mixtures of an explosive with soot or graphite. The pycnometric density of powders after compression and treatment in boiling acids achieved 3.42 g/cm³. The X-ray and TEM study showed that fine-grained crystalline and nanocrystalline diamond was also present in the samples in addition to the diamond-like amorphous phase.     

Disorder and optical gaps in strained dense amorphous carbon and diamond nanocomposites

We employ empirical tight-binding simulations on strained tetrahedral amorphous carbon and diamond nanocomposite networks. For each applied strain, the optoelectronic properties are monitored through the absorption coefficient and the dielectric function. These lead to the optical gaps and are able to quantify the amount of disorder in the structures. We compare our results to those of unstrained nanostructured diamond and amorphous carbon (a-C) phases and link the degree of disorder in these materials to their structural details as a function of the external load. The atomic rearrangements and distortions imposed by the external strain in these structures are directly observable in their optoelectronic properties. We thoroughly discuss the interplay between increased external strain, structural and topological disorder, atomic rearrangements and their effect on the calculated optoelectronic properties.