自支撑硼掺杂金刚石膜残余应力和微观应力的XRD分析

利用XRD(包括sin2ψ法)研究了电子辅助热灯丝化学气相沉积法(EA-HFCVD)生长的自支撑硼掺杂多晶金刚石薄膜的残余应力和微观应力.结果表明,薄膜的残余应力为压应力,随着薄膜制备过程中硼流量的增加,应力值有减小的趋势.薄膜的微观应力随着硼流量的增加,由拉应力转变为压应力然后又转变为拉应力.残余应力和微观应力的变化归因于一定量的硼掺杂导致的多晶膜中晶粒尺寸、晶面取向及孪晶变化的共同作用.     

A comparative study of p-type diamond films using Raman and transport measurements

The influence of deposition temperature in the properties of synthetic diamond films grown by two different chemical vapor deposition (CVD) techniques, hot-filament- and microwave-plasma-assisted, was investigated. These samples were obtained using the optimal growth conditions previously achieved in this work. Raman spectroscopy was employed in order to investigate the diamond film quality as a function of the deposition temperature. It was found that the nondiamond carbon bands decrease as the deposition temperature increases for both the deposition methods, leading to higher-quality diamond films. The micro- and macro-Raman spectra showed that the nondiamond band is already present in a single diamond grain. Both techniques provided well homogeneous diamond films and with equivalently good quality. Boron-doped diamond films with different carrier concentration levels were also studied. In order to get details about the electrical properties of the films, resistivity as a function of the boron concentration—in association with Raman spectra—and temperature-dependent transport measurements were employed. The results showed that the boron doping is the main responsible for the conductivity and that the variable range hopping (VRH) mechanism dominates the transport in these doped diamond films.     

Residual stress, Young''s modulus and fracture stress of hot flame deposited diamond

Chemical vapour deposition (CVD) diamond coatings deposited on various substrates usually contain residual stresses. Since the residual stress affects the adhesion of the coating to the substrate, as well as the performance of the coating/substrate composite in many technical applications it is of importance to study the magnitude of these stresses.

In the present study the hot flame method was used to deposit diamond coatings on cemented carbide inserts by scanning the surface with a nine flame nozzle. By varying the oxygen to acetylene flow ratio and the deposition time coatings of different qualities and thicknesses were obtained. The residual strain/stress of the coatings was measured by three different methods: X-ray diffraction using the sin² (Ψ) method, Raman spectroscopy and disc deflection measurements. To extract the residual stress from the strain data the Young's modulus was obtained from bending tests of diamond cantilever beams manufactured from free standing diamond films. The latter technique was also used to determine the fracture stress of the diamond films.

All deposited coatings displayed a residual compressive strain/stress state. The residual strain in the diamond coatings did not vary with coating thickness (1.5 μm to 20 μm) but was found to increase from −1.8 × 10⁻³ to −2.2 × 10⁻³ with decreasing diamond quality. The compressive residual stress was found to decrease from −2 GPa to −1.3 GPa with decreasing diamond quality. This is mainly due to a decrease in Young's modulus (from 1.1 TPa to 0.6 TPa) with decreasing diamond quality. Also the fracture stress was found to decrease (from 1.8 GPa to 0.8 GPa) with decreasing diamond quality. The three methods used for measuring the stress state in the coatings, X-ray diffraction, Raman spectroscopy and deflection measurement, all give the same result. The deflection technique has the advantage that no information about the elastic properties of the coating is needed, whereas Raman spectroscopy has the best lateral resolution (≈5 μm) and is the fastest method (≈5 min).     

Variation of residual stress in cubic boron nitride film caused by hydrogen addition during unbalanced magnetron sputtering

The effect of hydrogen on compressive residual stress of cubic boron nitride (cBN) was investigated. The deposition was performed by unbalanced magnetron sputtering of a hexagonal boron nitride (hBN) target connected to radio-frequency electric power of 400 W. Up to 2 sccm of hydrogen was added to a gas mixture of argon and nitrogen flowing at 9 and 1 sccm, respectively. The compressive stress rapidly decreased from 10.5 GPa to 3 GPa, with increasing hydrogen flow up to 1.0 sccm. The cBN fraction in these films, however, remained over 60%, with only a trivial decrease with increasing hydrogen. This reduction was discussed in terms of the relation between the penetration probabilities of hydrogen and argon ions into the film, which was main origin of compressive residual stress of the hBN layer.     

Crystalline quality and phase purity of CVD diamond films studied by Raman spectroscopy

Two series of diamond films grown—at different temperatures—by two chemical vapor deposition (CVD) methods, i.e., hot filament (HFCVD) and microwave-plasma (MPCVD), were investigated. Raman spectroscopy and scanning electron microscopy were employed to perform a study of both crystalline quality and phase purity of the films grown by the two techniques. It was found that high phase purity can be attained by both methods. However, at high temperatures, the MPCVD technique produced films with higher crystalline quality as compared to those grown by HFCVD. Finally, in order to shed some light into the mechanisms responsible for the lower crystalline quality observed in the HFCVD films, a study based in the phonon confinement model and stress was accomplished.     

Influence of WC-Co substrate pretreatment on diamond film deposition by laser-assisted combustion synthesis

The quality of diamond films deposited on cemented tungsten carbide substrates (WC-Co) is limited by the presence of the cobalt binder. The cobalt in the WC-Co substrates enhances the formation of nondiamond carbon on the substrate surface, resulting in a poor film adhesion and a low diamond quality. In this study, we investigated pretreatments of WC-Co substrates in three different approaches, namely, chemical etching, laser etching, and laser etching followed by acid treatment. The laser produces a periodic surface pattern, thus increasing the roughness and releasing the stress at the interfaces between the substrate and the grown diamond film. Effects of these pretreatments have been analyzed in terms of microstructure and cobalt content. Raman spectroscopy was conducted to characterize both the diamond quality and compressive residual stress in the films.     

硼磷共掺杂n型金刚石薄膜的Hall效应、红外光谱和EPR研究

用离子注入方法,在CVD金刚石薄膜中共注入硼离子和磷离子,得到了电阻率较低的n型金刚石薄膜。Hall效应测试表明,800℃退火后,在注入的磷离子剂量相同的情况下,共注入硼的金刚石薄膜的载流子浓度与单一掺磷的相近,但Hall迁移率高,电阻率低。FTIR结果表明B-H结的形成钝化了硼的受主特性,使磷的施主特性没有被补偿,共掺杂薄膜中载流子浓度没有大幅度减少。EPR和Raman测试结果证实了较高温度退火后的共掺杂薄膜的晶格结构比单掺杂薄膜的更完整,从而有利于提高载流子迁移率,降低电阻率。     

Raman spectroscopy characterization of diamond films on steel substrates with titanium carbide arc-plated interlayer

Diamond chemical vapour deposition (CVD) on steel represents a difficult task. The major problem is represented by large diffusion of carbon into steel at CVD temperatures. This leads to very low diamond nucleation and degradation of steel microstructure and properties. Recent work [R. Polini, F. Pighetti Mantini, M. Braic, M. Amar, W. Ahmed, H. Taylor, Thin Solid Films 494 (2006) 116] demonstrated that well-adherent diamond films can be grown on high-speed steels by using a TiC interlayer deposited by the PVD-arc technique. The resulting multilayer (TiC/diamond) coating had a rough surface morphology due to the presence of droplets formed at the substrate surface during the reactive evaporation of TiC. In this work, we first present an extensive Raman investigation of 2 μm, 4 μm and 6 μm thick diamond films deposited by hot filament CVD on TiC interlayers obtained by the PVD-arc technique. The stress state of the diamond was dependent on both the films thickness and the spatial position of the coating on the substrate. In fact, on the top of TiC droplets, the stress state of the diamond was much lower than that of diamond in flatter substrate areas. These results showed that diamond films deposited on rough TiC interlayers exhibited a wide distribution of stress values and that very large compressive stress exists in the diamond film grown on flat regions of steel substrates with a TiC interlayer. Diamond films could accommodate stresses as large as 10 GPa without delamination.     

Growth and characterization of diamond films deposited at high-pressure using a low-power microwave plasma reactor

Diamond films were deposited on molybdenum substrates from mixtures of methane diluted in hydrogen using a high-pressure microwave plasma reactor. In this reactor, a compressed waveguide structure was used to increase the electric field strength, and accordingly the reactor was able to operate stably with low gas flow rate and microwave power. The films deposited on 12 mm diameter substrates were characterized by film morphology, Raman spectra, growth rate and crystalline quality. The morphology of diamond films deposited in this reactor depends mainly on the substrate temperature. When the deposition pressure was 48 kPa and microwave power was only 800 W, high quality diamond films could be uniformly deposited with a growth rate around 20 μm/h.     

Structural evolution of boron nitride films grown on diamond buffer-layers

Boron nitride films on diamond buffer layers of varying grain size, surface roughness and crystallinity are deposited by the reaction of B₂H₆ and NH₃ in a mixture of H₂ and Ar via microwave plasma-assisted chemical vapor deposition. Various forms of boron nitride, including amorphous α-BN, hexagonal h-BN, turbostratic t-BN, rhombohedral r-BN, explosion E-BN, wurzitic w-BN and cubic c-BN, are detected in the BN films grown on different diamond buffer layers at varying distances from the interface of diamond and BN layers. The c-BN content in the BN films is inversely proportional to the surface roughness of the diamond buffer layers. Cubic boron nitride can directly grow on smooth nanocrystalline diamond films, while precursor layers consisting of various sp²-bonded BN phases are formed prior to the growth of c-BN film on rough microcrystalline diamond films.     

掺硼浓度对金刚石薄膜二次电子发射特性的影响

掺硼金刚石薄膜具有负电子亲和势和良好的电子运输性能且容易制备,作为冷阴极材料在图像显示技术和真空技术等领域都存在巨大的应用价值,引起人们的广泛关注。采用MPCVD法利用氢气、甲烷和硼烷的混合气体,制备出不同浓度的掺硼金刚石薄膜。结果表明,掺硼浓度影响金刚石薄膜的物相结构、组织形貌,进而影响其二次电子发射性能,当硼烷的流量为4mL/min时,制备的金刚石薄膜质量最好,二次电子发射系数约为90。     

硼掺杂对金刚石薄膜生长特性的影响

采用HFCVD方法制备了掺硼金刚石薄膜,通过扫描电子显微镜和X射线衍射光谱对样品的表面形貌及结构进行了分析.结果表明,随着硼含量的增加,薄膜中晶粒的取向由(100)变为(111),然后趋向于无序化.硼的掺入同样影响到孪晶晶粒的形态及生长因子α,使得α变小.通过对样品的Raman光谱分析,得出在适当的硼掺杂浓度下,孪晶的出现使金刚石薄膜中的应力得到松弛,从而中心声子线Raman位移红移较小.     

New approach in depositing thick, layered cubic boron nitride coatings by oxygen addition—structural and compositional analysis

Cubic boron nitride (c-BN) can be produced by PVD and PA-CVD techniques by intensive ion bombardment leading to highly stressed films limiting its use in industrial applications. Various attempts have been undertaken to reduce the compressive stress of c-BN thin films. A significant reduction in compressive stress and a substantially improved adhesion was achieved by a new coating concept consisting of a two-step adhesion-promoting base layer, a compositional-graded nucleation layer obtained by a stepwise decrease of the oxygen content in the Ar/N₂/O₂ atmosphere and a low-stressed c-BN:O top layer with controlled oxygen addition. The four-layer c-BN:O film with a thickness of 3 μm was deposited by unbalanced radio frequency magnetron sputtering of a hot-pressed hexagonal boron nitride target on silicon substrates. The adhesion layer was deposited in a mixed Ar/O₂ atmosphere of 0.26 Pa with a stepwise increased nitrogen gas flow and a subsequent increase of the ion energy by increasing the substrate bias from 0 to − 250 V. The c-BN nucleation was gradually initiated by decreasing the O₂ gas flow. The present study was focused on the investigation of the morphology, the microstructure on the nanoscale, and the bonding structure using scanning electron microscopy (SEM), Fourier-Transmission infra-red spectroscopy (FTIR), high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) employing analytical scanning transmission electron microscopy (ASTEM). The HRTEM images revealed a four-layer coating consisting of a gradual nucleation of t-BN, on which a gradual nucleation of c-BN was achieved by decreasing the oxygen gas flow.     

激光拉曼光谱在CVD金刚石薄膜质量表征中的应用

激光拉曼光谱是一种优异的，灵敏的，应用广泛的无损表征技术，对于评估碳物质质量及其键合状态，也是有效的手段。     

高结晶度氮化硼纳米片的制备及其与聚乙烯醇复合薄膜的性能

以具有特殊花瓣状形貌的硼酸镁纳米片为模板、前驱体和硼源, 以氨气为氮源合成了氮化硼纳米片(BNNSs), 通过 SEM、TEM、XRD、Raman和FT-IR等对其形貌和结构等进行了分析。结果表明: 合成的BNNSs为厚度仅约5 nm、横向尺寸150~300 nm、结晶度极高的单晶片层状h-BN, 多个BNNSs聚集形成了形貌与硼酸镁纳米片类似的形状。以所合成的BNNSs为填料, 制备了不同BNNSs添加量的BNNSs/聚乙烯醇(PVA)复合材料薄膜, 结果表明添加30% BNNSs的复合薄膜的弹性模量较纯PVA薄膜提高了约39.8%, 面内热扩散系数和热导率则分别最大提高了约7和8倍, 说明以此BNNSs做为填料能明显改善BNNSs/PVA复合薄膜的热学性能。     

Selective Oxidation of Graphite on Diamond Films Induced by UV Exposure

A selective oxidation technique for diamond films based on the extended exposure to UV light in air at room temperature was developed and studied by Raman Spectroscopy and Scanning Electron Microscopy. The diamond films were synthesized by the combustion flame technique in open atmosphere by using an oxy-acetylene gas mixture as the carbon source. A 125 W UV lamp was used to irradiate the films in the wavelength range of 180–250 nm, from 2 to 10 days. The Raman spectrum from the as-deposited diamond films shows the typical band at 1333 cm^–1, characteristic of the sp ³diamond structure, with a certain nondiamond or graphite content. After UV irradiation, graphite was selectively oxidized and partially removed without oxidation of diamond, indicating that the strong reaction of ozone (O₃) and atomic oxygen (O·) produced by the UV irradiation oxidized the graphite, even at room temperature, without the need of an additional heating source. The oxidation of graphite was best observed after 2 days of UV treatment. A sensible improvement in the diamond film quality was obtained after 2 days of irradiation, as revealed by the sharpening of the corresponding Raman band.     

大面积高质量金刚石自支撑膜热导率的影响因素研究

通过Raman、XRD、SEM分析方法分别对大面积高质量金刚石自支撑膜的质量、晶体结构、晶粒尺寸进行研究,分析它们对金刚石自支撑膜热导率的影响.研究结果表明,金刚石自支撑膜的质量对热导率的影响较大,质量越好,热导率越接近于天然金刚石的热导率;并且金刚石自支撑膜中晶体[220]取向度越高,热导率越高.形核面晶粒尺寸越大,晶粒间的晶界就减少,有利于提高金刚石自支撑膜的热导率.     

Effects of substrate temperature and post-annealing on microstructure and properties of (AlCrNbSiTiV)N coatings

AlCrNbSiTiV nitride films were deposited by reactive radio-frequency magnetron sputtering from an AlCrNbSiTiV equimolar target. Effects of substrate temperatures from 100 °C to 500 °C and post-annealing on the chemical composition, microstructure and mechanical properties of the films were investigated. Experimental results indicate that all nitride films have a single face-centered cubic (NaCl-type) structure with the stoichiometric nitride ratio approximately as Al₈Cr₈Nb₇Si₉Ti₉V₈N₅₀. Increasing the substrate temperature increases the grain size and the compressive residual stress, but decreases the lattice constant. The highest hardness of (AlCrNbSiTiV)N nitride films is 41 GPa, corresponding to the super-hard grade. Even annealing in a vacuum at 900 °C for 5 h caused no notable change in the crystalline structure, lattice parameter, grain size or hardness. The super-hard level and thermal stability of these multi-component coatings are discussed.     

Raman spectroscopy of diamond and doped diamond

The optimization of diamond films as valuable engineering materials for a wide variety of applications has required the development of robust methods for their characterization. Of the many methods used, Raman microscopy is perhaps the most valuable because it provides readily distinguishable signatures of each of the different forms of carbon (e.g. diamond, graphite, buckyballs). In addition it is non-destructive, requires little or no specimen preparation, is performed in air and can produce spatially resolved maps of the different forms of carbon within a specimen. This article begins by reviewing the strengths (and some of the pitfalls) of the Raman technique for the analysis of diamond and diamond films and surveys some of the latest developments (for example, surface-enhanced Raman and ultraviolet Raman spectroscopy) which hold the promise of providing a more profound understanding of the outstanding properties of these materials. The remainder of the article is devoted to the uses of Raman spectroscopy in diamond science and technology. Topics covered include using Raman spectroscopy to assess stress, crystalline perfection, phase purity, crystallite size, point defects and doping in diamond and diamond films.     

The Influence of Nitrogen and Boron Implant into Silicon Substrate on the Phase and Internal Stress of c-BN Films

Cubic boron nitride(c-BN) film was deposited on a Si (100) substrate by the RF-magnetron sputtering.The mainly problems for fabrication of c-BN films are the low purity and high intrinsic compressive stress. In order to solve the two problems, the c-BN film with the buffer interlayer was deposited on the substrate which had been implanted with nitrogen and/or boron ions. The results show: the implantation of nitrogen ions can obviously increase c-BN content and reduce the internal stress slightly; while the implantation of boron shows no obvious improvement to the content of c-BN, which can reduce the internal stress in the film obviously. In addition, it is suggested that the implantation of nitrogen and boron shows the best result, which not only can increase the content of c-BN, but also reduce the internal stress in the c-BN film obviously.