用于高频声表面波器件的CVD金刚石衬底的研究

使用纳米金刚石粉研磨工艺预处理硅片衬底抛光面,在低气压成核的条件下,以丙酮和氢气为反应物,采用传统的热丝辅助化学气相沉积法,制备了自支撑金刚石膜;通过射频磁控溅射法沉积氧化锌薄膜在自支撑金刚石膜的成核面,形成氧化锌/自支撑金刚石膜结构.通过光学显微镜、扫描电镜及原子力显微镜测试自支撑金刚石膜成核面的表面形貌.研究结果表明:成核期的低气压有助于提高成核密度,成核面表面粗糙度约为1.5 nm;拉曼光谱显示1334 cm-1附近尖锐的散射峰与金刚石SP3键相对应,成核面含有少量的石墨相,且受到压应力的作用;ZnO/自支撑金刚石膜结构的XRD谱显示,氧化锌薄膜有尖锐的(002)面衍射峰,是c轴择优取向生长的.     

High velocity SAW using aluminum nitride film on unpolished nucleation side of free-standing CVD diamond

High performances surface acoustic wave (SAW) filters based on aluminium nitride (AlN)/diamond layered structure have been fabricated. The C-axis oriented aluminum nitride films with various thicknesses were sputtered on unpolished nucleation side of free-standing polycrystalline chemical vapor deposition (CVD) diamond obtained by silicon substrate etching. Experimental results show that high order modes as well as Rayleigh waves are excited. Experimental results are in good agreement with the theoretical dispersion curves determined by software simulation with Green's function formalism. We demonstrate that high phase velocity first mode wave (so-called Sezawa wave) with high electromechanical coupling coefficient are obtained on AlN/diamond structure. This structure also has a low temperature coefficient of frequency (TCF), and preliminary results suggest that a zero TCF could be expected.     

Study of the moderate-temperature growth process of optical quality synthetic diamond films on quartz substrates

Growth of undoped and boron-doped diamond films on quartz substrates at moderate temperature of 500 °C by microwave plasma chemical vapor deposition method was studied in terms of growth rate, surface roughness and optical transmittance. Similar density of diamond seed particles on quartz surfaces seeded mechanically before the deposition process and diamond grains within diamond films grown on those substrates is observed. The growth rate is found similar to that reported for diamond deposited on silicon substrates in the same plasma deposition system, although with substantially higher activation energy. Furthermore, increased level of dopant concentration in the gas mixture resulted in a decrease of the growth rate, while a gradual reduction of the surface roughness occurred at high dopant levels. Overall, the highest measured regular optical transmittance of the undoped diamond film on quartz was 45% at 1100 nm (including quartz absorption), whereas that of boron-doped diamond peaked 5% at 700 nm (tail absorption of boron centers).     

微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石

研究了衬底温度、核化密度、衬底表而预处理等工艺参数对微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石的影响.采用扫描电镜、X-射线衍射、喇曼光谱和红外光谱对样品进行了表征.结果表明:从高核化密度生长的金刚石膜中探测不到碳化硅;不论对硅衬底进行抛光预处理还是未抛光预处理,从低核化密度牛长的金刚石厚膜中总能探测到碳化硅.碳化硅生长在硅衬底上未被金刚石覆盖的地方,或者是在金刚石晶核之间的空洞处.碳化硅形成和金刚石生长是同时发生的两个竞争过程.此研究结果为制备金刚石和碳化砟复合材料提供了一种新的方法.     

Nanocrystalline diamond growth on different substrates

Nanocomposite films consisting of diamond nanoparticles of 3-5 nm diameter embedded in an amorphous carbon matrix have been deposited by means of microwave plasma chemical vapour deposition (MWCVD) from CH₄/N₂ gas mixtures. Si wafers, Si coated with TiN, polycrystalline diamond (PCD) and cubic boron nitride films, and Ti-6Al-4V alloy have been used as substrates. Some of the substrates have been pretreated ultrasonically with diamond powder in order to enhance the nucleation density n_nuc. It turned out that n_nuc depends critically on the chemical nature of the substrate, its smoothness and the pretreatment applied. No differences to the nucleation behaviour of CVD PCD films were observed. On the other hand, the growth process seems to be not affected by the substrate material. The crystallinity (studied by X-ray diffraction) and the bonding environment (investigated by Raman spectroscopy) show no significant differences for the various substrates. The mechanical and tribological properties, finally, reflect again the influence of the substrate material: on TiN, a lower hardness was measured as compared to Si, PCD and c-BN, whereas the adhesion of c-BN/nanocrystalline diamond (NCD) system was determined by that of the c-BN film on the underlying Si substrate.     

Surface acoustic wave properties of freestanding diamond films

"Ideal" diamond has the highest acoustic velocity of any material known, and is of great interest as a substrate material for high frequency surface acoustic wave (SAW) device structures. However, little is known of the acoustic wave propagation properties of polycrystalline diamond grown by chemical vapour deposition (CVD) techniques, the commercially accessible form of this material. We report on propagation of laser-generated SAW on three forms of freestanding CVD diamond samples, "white" polycrystalline, "black" polycrystalline, and "highly oriented" diamond. Despite differing sample nature, SAW waves propagating along the smooth (nucleation) side of the diamond showed similar velocities in the range 10600-11900 ms(-1). These results are discussed in terms of the potential of each form of CVD diamond for SAW device fabrication.     

Freestanding ultrananocrystalline diamond films with homojunction insulating layer on conducting layer and their high electron field emission properties

Freestanding ultrananocrystalline diamond (UNCD) films with homojunction insulating layer in situ grown on a conducting layer showed superior electron field emission (EFE) properties. The insulating layer of the films contains large dendrite type grains (400-600 nm in size), whereas the conducting layer contains nanosize equi-axed grains (5-20 nm in size) separated by grain boundaries of about 0.5-1 nm in width. The conducting layer possesses n-type (or semimetallic) conductivity of about 5.6 × 10(-3) (Ω cm)(-1), with sheet carrier concentration of about 1.4 × 10(12) cm(-2), which is ascribed to in situ doping of Li-species from LiNbO(3) substrates during growth of the films. The conducting layer intimately contacts the bottom electrodes (Cu-foil) by without forming the Schottky barrier, form homojunction with the insulating layer that facilitates injection of electrons into conduction band of diamond, and readily field emitted at low applied field. The EFE of freestanding UNCD films could be turned on at a low field of E(0) = 10.0 V/μm, attaining EFE current density of 0.2 mA/cm(2) at an applied field of 18.0 V/μm, which is superior to the EFE properties of UNCD films grown on Si substrates with the same chemical vapor deposition (CVD) process. Such an observation reveals the importance in the formation of homojunction on enhancing the EFE properties of materials. The large grain granular structure of the freestanding UNCD films is more robust against harsh environment and shows high potential toward diamond based electronic applications.     

Bias enhanced nucleation of diamond thin films in a modified HFCVD reactor

In this study we investigated the nucleation of synthetic diamond thin films on Si substrates by double bias enhanced Hot Filament Chemical Vapour Deposition (HFCVD) method. First, we investigated the influence of the bias voltage and secondly the influence of the nucleation time under different bias voltages. The bias voltage was varied from −120 V up to −220 V as well as the nucleation time was changed from 30 up to 120 min in order to obtain the optimized nucleation conditions for following growth of continuous diamond layer. Samples were analyzed by Scanning Electron Microscopy (SEM) and Raman Spectroscopy. SEM was used for determination of cluster sizes and their distribution on the Si surface, while Raman Spectroscopy for determination and analysis of carbon phases.     

Study of carbide-forming element interlayers for diamond nucleation and growth on silicon and WC-Co substrates

Diamond nucleation and growth on several typical carbide-forming elements (CFE) (Ti, Cr and W) coated Si and WC-Co substrates were studied. The ion beam sputtered CFE interlayers show an amorphous/nanocrystalline microstructure. The diamond formed on the CFE coated substrates shows higher nucleation density and rate and finer grain structure than on uncoated substrates. Consequently, nanocrystalline diamond thin films can be formed on the CFE coated substrates under conventional microcrystalline diamond growth conditions. Among the three tested CFE interlayers, diamond has the highest nucleation density and rate on W layer and the lowest on Ti layer. The diamond nucleation density and rate on CFE coated WC-Co are much higher than those on widely used metal nitride coated WC-Co.     

Chemical vapour deposition of oriented diamond nanocrystallites by a bias-enhanced nucleation method

A microwave plasma chemical vapour deposition (MPCVD) system has been used to deposit nanometre-sized single-crystalline diamonds on 1 × 1?cm(2) Si(100) substrates. The distribution of deposited diamonds has good uniformity over the whole Si substrate surface by using a dome-shaped Mo anode which allows the application of bias-enhanced nucleation. The morphology and crystallinity of the deposits on Si were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) with electron diffraction and lattice images. SEM and TEM observations show that oriented diamond nuclei as single crystals with facets can form on self-formed Si cones through epitaxial SiC within a short bias period. After a longer bias time, it has been observed that polycrystalline diamonds formed as a result of secondary nucleation.     

MPCVD法在氧化铝陶瓷上的金刚石膜沉积及其成核分析

用微波等离子体化学气相沉积（ＭＰＣＶＤ）法在氧化铝陶瓷基片上沉积了金刚石薄膜。实验表明，对基片进行适当的预处理，包括用金刚石研磨膏仔细研磨和沉积前原位沉积一层无定形碳层，可显著提高成核密度；对硅衬底和氧化铝基片上金刚石膜的成核过程进行了对比分析，并提出了提高氧化铝基片上沉积金刚石的成核的措施。     

Characteristics of a well-adherent nanocrystalline diamond thin film grown on titanium in Ar/CH4 microwave CVD plasma

The fabrication of a well-adherent diamond film on titanium and its alloys is always problematical due to the different thermal expansion coefficients of the two materials, the complex nature of the interlayer formed during diamond deposition, and the difficulty in achieving very high nucleation density. In this work, well-adherent and smooth nanocrystalline diamond (NCD) thin film is successfully deposited on pure titanium substrate by microwave plasma-assisted chemical vapor deposition (MWPCVD) method in Ar/CH₄ environment. It is found that the average grain size is less than 20 nm with a surface roughness value as low as 12 nm. Morphology, surface roughness, diamond crystal orientation and quality are obtained by characterizing the sample with field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy, respectively. Detailed experimental results and mechanisms for NCD film deposition are discussed.     

Investigation of the nucleation mechanism in bias-enhanced diamond deposition on silicon and molybdenum

Polycrystalline diamond films were deposited on Si and Mo substrates in a microwave plasma-enhanced chemical vapour deposition reactor employing bias-enhanced nucleation. The deposition process was subdivided into two consecutive steps: the pretreatment (bias-enhanced nucleation) and the diamond growth step. To investigate the nucleation process we kept the deposition parameters during the diamond growth step constant and only changed the parameters during the pretreatment. The methods employed to analyze the deposited films after the pretreatment step were electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy.

The nucleation density (N_D) on Si following the complete deposition cycle (pretreatment and diamond growth step) increases considerably from 5 × 10⁸ cm⁻² to 5 × 10¹⁰ cm⁻² with an increase in the substrate temperature during the pretreatment (T_p) in the temperature range from 680 to 750 °C. For T_p ≥ 770 °C continuous films are formed. The structure of the pretreatment deposit undergoes likewise considerable changes: if T_p exceeds 770 °C the appearance of an intense diamond plasmon at 34 eV is observed, indicative of an increase in the concentration of diamond crystallites embedded in an otherwise amorphous carbon matrix. Our experiments suggest that diamond crystallites formed during the pretreatment serve as nucleation centres for the subsequent diamond growth.

The same deposition parameters which result in the formation of a continuous diamond film on Si, yield only low nucleation densities on Mo. An increase in N_D from 6 × 10⁶ cm⁻² to 2 × 10⁸ cm⁻² can be achieved by raising the methane concentration [CH₄] in the gas phase during the pretreatment from 5 to 50% (T_p = 820 °C). The carbon concentration at the surface for the pretreatment deposit, determined by XPS analysis, increases likewise with [CH₄]. According to the EELS analysis the structure of the pretreatment deposit is comparable with disordered graphite or a-C and no diamond plasmon is observed. The high [CH₄] is required to form the Mo-carbide interface and balance the diffusion of carbon into the metal before the a-C layer can be formed.

The formation of nucleation centres during the bias-enhanced nucleation seems under these deposition conditions to proceed via different pathways on Si and Mo. While the nucleation on Si appears to be linked to the formation of diamond nanocrystals during the pretreatment, this is not the case for Mo.     

CVD diamond films with hydrophilic micro-patterns for self-organisation of human osteoblasts

Nanocrystalline diamond (NCD) films were prepared by microwave plasma-enhanced chemical vapour deposition (CVD) on Si substrates of different roughness (1 and 500 nm). Diamond nano-crystals are up to 50 nm in size and RMS surface roughness is less than 20 nm. The NCD films were cleaned chemically and terminated by hydrogen using plasma treatment (800 °C, 10 min) to generate a hydrophobic surface. Photolithography mask and oxygen plasma (300 W r.f. power, 3 min) were used to generate O-terminated (hydrophilic) patterns (30-200 μm wide) separated by a H-terminated (hydrophobic) surface. Osteoblast-like human cells were seeded on the patterned flat and rough NCD films in McCoy's 5A medium supplemented with 15% fetal bovine serum (FBS). After two days incubation the cells preferentially adhered on the O-terminated stripes. This phenomenon is not suppressed by the surface roughness and is general for other cell types (fibroblast and cervical carcinoma cells), too. The data are discussed with view to further application of NCD thin films in biotechnology and bio-electronics applications.     

Growth of nanocrystalline diamond films in CCl4/H2 ambient

We investigated the growth characteristics of the nanocrystalline diamond films using CCl₄/H₂ as gas sources in a hot-filament chemical vapor deposition (CVD) reactor. Successful growth of nanocrystalline diamond at typical growth condition of 1.5-2.5% CCl₄ and 550-730 °C substrate temperature has been demonstrated. Glancing angle X-ray diffraction (XRD) clearly indicated the formation of diamond in the films. Typical root-mean-square surface roughness of 10-15 nm and an optimal root-mean-square surface roughness of 6 nm have been achieved. Transmission electron microscopy (TEM) analyses indicated that nanocrystalline diamond film with an average grain size in the range of 10-20 nm was deposited from 2.5% CCl₄/H₂ at 610 °C. Effects of different source gas composition and substrate temperature on the grain nucleation and grain growth processes, whereby the grain size of the nanocrystalline film could be controlled, were discussed.     

Synthesis of ultrasmooth nanostructured diamond films by microwave plasma chemical vapor deposition using a He/H(2)/CH(4)/N(2) gas mixture

Ultrasmooth nanostructured diamond (USND) films were synthesized on Ti-6Al-4V medical grade substrates by adding helium in H(2)/CH(4)/N(2) plasma and changing the N(2)/CH(4) gas flow from 0 to 0.6. We were able to deposit diamond films as smooth as 6 nm (root-mean-square), as measured by an atomic force microscopy (AFM) scan area of 2 μm(2). Grain size was 4-5 nm at 71% He in (H(2) + He) and N(2)/CH(4) gas flow ratio of 0.4 without deteriorating the hardness (~50-60 GPa). The characterization of the films was performed with AFM, scanning electron microscopy, x-ray diffraction (XRD), Raman spectroscopy, and nanoindentation techniques. XRD and Raman results showed the nanocrystalline nature of the diamond films. The plasma species during deposition were monitored by optical emission spectroscopy. With increasing N(2)/CH(4) feedgas ratio (CH(4) was fixed) in He/H(2)/CH(4)/N(2) plasma, a substantial increase of CN radical (normalized by Balmer H(α) line) was observed along with a drop in surface roughness up to a critical N(2)/CH(4) ratio of 0.4. The CN radical concentration in the plasma was thus correlated to the formation of ultrasmooth nanostructured diamond films.     

Effects of enhanced nucleation on the growth and thermal performance of diamond films deposited on BeO by hot filament CVD technique

A method of controlling the feeding concentration of methane was applied in a hot-filament chemical vapor deposition (HFCVD) in order to improve the nucleation of diamond on the beryllium oxide substrates. The nucleation density and the morphologies of diamond were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM) while the thermal conductivities of substrates and the composites were detected by laser-diathermometer. The results show that the diamond thin film is in larger grain size with lower roughness when CH₄ and H₂ enter the chamber, respectively, rather than as a mixture, and the composites’ conductivity soared by 21%–31% compared with BeO substrates. At the conditions of separated gas entry, several projects with changes of the CH₄ flux during depositing were designed to discuss the influence of CH₄ concentration on diamond nucleation. The uniform and compact diamond thin films were acquired when the ratio of CH₄:H₂ at nucleation stage was in the range of 4%–8%.     

Superfinishing polish of diamond substrates for epitaxial technology

The regimes of superfinishing vibropolish of single-crystal synthetic diamond substrates have been optimized. It has been established that after polishing for 100 h the surface roughness was 0.43 nm. A method for controlling the structural perfection of the near-surface layers of diamond substrates upon their grinding and polishing has been proposed and substantiated. X-ray diffraction studies point to the possibility of using the given method in selecting suitable substrates for the technology of growing diamond films in micro- and nanoelectronics.     

采用MPCVD法在硅衬底上选择性生长金刚石膜

采用微波等离子体化学气相沉积（MPCVD）法在附有SiO2掩摸的硅衬底上选择性沉积出了金刚石膜。采用扫描电子显微镜（SEM）和Raman光谱仪对金刚石膜的表面形貌和结构进行了表征。并讨论了衬底温度对金刚石薄膜选择性沉积的影响。得出了较佳的沉积条件。     

SAW COM-parameter extraction in AlN/diamond layered structures

Highly c-axis oriented aluminum nitride (AlN) thin piezoelectric films have been grown on polycrystalline diamond substrates by pulsed direct current (DC) magnetron reactive sputter-deposition. The films were deposited at a substrate temperature below 50/spl deg/C (room temperature) and had a typical full width half maximum (FWHM) value of the rocking curve of the AlN-002-peak of 2.1 degrees. A variety of one-port surface acoustic wave (SAW) resonators have been designed and fabricated on top of the AlN films. The measurements indicate that various SAW modes are excited. The SAW phase velocities of up to 11.800 m/s have been measured. These results are in agreement with calculated dispersion curves of the AlN/diamond structure. Finally, the coupling of modes parameters have been extracted from S/sub 11/ measurements using curve fitting for the first SAW mode, which indicate an effective coupling K/sup 2/ of 0.91% and a Q factor of about 600 at a frequency of 1050 MHz.