立方氮化硼薄膜沉积过程的相变研究

从能量和结构两个角度分析了BN四种相的转变过程，以及杂质和缺陷对立方氮化硼(c-BN)薄膜制备的影响.研究了从六角氮化硼(h-BN)到c-BN转变的一个可能的过程，即h-BN→菱形氮化硼(r-BN)→c-BN过程.对纯的h-BN到r-BN的转变需要克服一个很高的能量势垒，在实验室条件下很难能够提供能量来越过这个势垒.而从r-BN到c-BN的转变只需要克服一个很低的能量势垒.这个能量势垒要低于从h-BN到纤锌矿氮化硼(w-BN)转变所需要克服的能量势垒.c-BN薄膜的制备过程中，薄膜在高能粒子轰击下，会产生大量的缺陷，这些缺陷对立方相的形成起到了重要的作用，缺陷和杂质的存在大大降低了从h-BN到r-BN转变的能量势垒.根据这个理论模型，在两步法制备c-BN薄膜的基础上，调整实验参数，形成三步法制备高质量c-BN薄膜.主要研究了三步法中第一步的时间和衬底负偏压对c-BN薄膜制备的影响，找到合适的沉积时间和衬底负偏压分别为5min和-180V.采用三步法制备薄膜，可以重复得到高立方相体积分数(立方相体积分数超过80%)的BN薄膜，并且实验重复性达到70%以上. 关键词： 立方氮化硼 能量势垒 缺陷 衬底偏压     

立方氮化硼薄膜的光学带隙

用射频溅射法在p型Si(100)衬底上沉积立方氮化硼(c-BN)薄膜,薄膜的成分由傅里叶变换红外谱标识,用紫外-可见分光光度计测量了c-BN薄膜的反射光谱,利用K-K(Kramers-Kroning)关系从反射谱计算出c-BN薄膜的光吸收系数,进而确定c-BN薄膜的光学带隙.对于立方相含量为55.4%的c-BN薄膜,光学带隙为5.38eV. 关键词： 立方氮化硼薄膜 光学带隙 K-K关系     

衬底材料对制备立方氮化硼薄膜的影响

较系统地研究了不同衬底材料对制备氮化硼薄膜的影响。用热丝增强射频等离子体CVD法,以NH3,B2H6和H2为反应气体,在Si,Ni,Co和不锈钢等衬底材料上,成功生长出高质量的立方氮化硼薄膜,还用13.56MHz的射频溅射系统将c-BN薄膜沉积在Si衬底上,靶材为h-BN(纯度为99.99％）,溅射气体为氩气和氮气的混合气体,所得到的氮化硼薄膜中立方相含量高于90%,用X射线衍射谱和傅里叶变换红谱对样品进行了分析表明,衬底材料与c-BN的晶格匹配情况,对于CVD生长立方氮化硼薄膜影响很大,而对溅射生长立方氮化硼薄膜影响不大。     

高质量宽带隙立方氮化硼薄膜的研究进展

文章着重介绍了最近研制出的高质量宽带隙立方氮化硼薄膜的三种制备方法和结构特性 :(1)用射频溅射法在Si衬底上制备出立方相含量在 90 %以上 ,Eg>6 .0eV的c-BN薄膜 ;(2 )用离子束辅助的化学气相沉积法(CVD) ,在金刚石上外延生长出立方含量达 10 0 %的单晶c -BN薄膜 ;(3)用微波电子回旋共振CVD法 (MW -ECR-CVD)在金刚石上外延生长出高纯c-BN薄膜 .这些高纯c -BN薄膜 ,可应用于制作各种半导体 (主要是高温、高频大功率 )电子器件 .     

立方氮化硼薄膜的生长特性与粘附性研究

用X射线衍射技术、红外吸收光谱、扫描电子显微镜、X射线光电子能谱对热丝辅助射频等离子体化学汽相沉积法制备的立方氮化硼(c-BN)薄膜的生长特性和粘附性进行了研究.改变生长条件，在Si、不锈钢和Ni衬底上沉积c-BN薄膜，进而研究了c-BN薄膜的质量和生长条件与衬底之间的关系.实验发现，Ni衬底上生长的薄膜c-BN含量较高，且粘附性好.当Si衬底上溅射一层Ni过渡层，再生长c-BN薄膜，薄膜中c-BN含量提高，与Si衬底的粘附性也显著增强. 关键词：     

脉冲直流偏压增强的高质量立方氮化硼薄膜的合成

采用磁增强活性反应离子镀系统成功地合成了立方氮化硼薄膜.通过给基片施加脉冲直流偏压以代替传统的射频偏压,增强了立方氮化硼的成膜稳定性,研究了基片的直流脉冲偏压、等离子体放电电流、通入气体流量比(Ar/N₂)和基片温度沉积参数对立方氮化硼薄膜形成的影响规律.结果表明:随着基片负偏压和放电电流的增大,薄膜中立方氮化硼的纯度提高,当基片负偏压为155V,放电电流为15A时,可获得几乎单相的立方氮化硼薄膜.基片温度为500℃和Ar/N₂流量比为10时,最有利于立方氮化硼 关键词： 立方氮化硼 活性反应离子镀 脉冲偏压     

用气相沉积方法在低气压下制备BN的高压相：E-BN、c-BN、w-BN

 用射频磁控溅射方法得到了低应力立方氮化硼薄膜。红外光谱结果表明,薄膜具有很好的附着力,且含有少量的E-BN和w-BN。电子衍射谱表明薄膜表层是纯立方相。同时利用此方法得到了E-BN薄膜。认为在薄膜生长过程中可能经历了一个从E-BN到c-BN的相转变过程。     

立方氮化硼薄膜生长过程中的界面控制

在立方氮化硼薄膜气相生长过程中生成的无定形初期层和乱层结构氮化硼中间层，一直是阻碍立方氮化硼薄膜外延生长的主要原因.系统地分析了硅衬底预处理对立方氮化硼薄膜中无定形初期层成分的影响，发现在等离子体化学气相生长法制备薄膜时，硅衬底上形成无定形初期层的可能原因有氧的存在、离子轰击以及高温下硅的氮化物的形成.在H₂气氛中1200K热处理硅衬底可以有效地减少真空室中残留氧浓度，除去硅表面的自然氧化层，保持硅衬底表面晶体结构.控制衬底温度不超过900 K，就能防止硅的氮化物的形成，成功地除去无 关键词： 立方氮化硼薄膜 等离子体化学气相生长 界面 电子显微镜     

氮化硼薄膜的红外光谱研究

用磁控溅射法制备六角氮化硼薄膜,在衬底温度、衬底偏压、工作气压等条件一定的情况下改变工作气体(氮气+氩气)中氮气的比例,以制备高质量的六角氮化硼薄膜,薄膜以红外吸收光谱标识。实验结果表明,工作气体中氮气的比例对制得的六角氮化硼薄膜有很大影响,在氮气比例为20%时得到理想的六角氮化硼薄膜。     

偏压磁控溅射法在水冷柔性衬底上制备ITO透明导电膜

通过对衬底施加负偏压吸引等离子体中的阳离子对衬底轰击,从而用射频磁控溅射法在水冷透明绦纶聚脂胶片上制备出相对透过率为80%左右、最小电阻率为63×10^-4Ωcm、附着良好的ITO(Indium Tin Oxide)透明导电膜.SnO₂最佳掺杂浓度为7.5%—10%(w.t.),最佳氩分压为0.5—1Pa.当衬底负偏压为20—40V时,晶粒平均尺寸最大,制备出的薄膜的电阻率有最小值.薄膜为多晶纤锌矿结构,垂直于衬底的c轴具有［222］方向的择优取向,随衬底负偏压 关键词：     

Heteroepitaxial growth of cubic boron nitride films on single-crystalline (001) diamond substrates

Heteroepitaxial cubic boron nitride (c-BN) films of significantly improved crystalline quality have successfully been deposited on (001) diamond single crystals using an ion beam assisted preparation method. The results of various characterization techniques prove that films containing 100% pure c-BN phase were nucleated directly on top of diamond without any intermediate hexagonal BN layer. Epitaxially grown, 500-nm-thick c-BN films are mechanically stable even under ambient conditions, though they still exhibit a compressive stress of 5 GPa. Their rocking angles of 0.2°, as observed by X-ray diffraction, point to a hitherto unprecedented quality of the films. Their surface smoothness, the magnitude of their Youngs modulus as well as their ultrahardness corroborate the outstanding quality of these epitaxially grown c-BN films on single-crystalline diamond. PACS 68.55.Jk; 81.15.Jj; 62.20.Qp; 81.05.Je     

Preparation of super-hard coatings by pulsed laser deposition

Amorphous diamond-like carbon (DLC) films and nanocrystalline cubic boron nitride (c-BN) films were prepared by pulsed laser deposition. DLC films with 80 to 85% sp³ bonds prepared at a laser fluence above 6 J/cm² and a substrate temperature below 100 °C show high compressive stresses in the range of 8 to 10 GPa. Those stresses can be completely removed by means of pulsed laser annealing, allowing the preparation of DLC films with several-micrometre thickness. c-BN films were prepared with additional ion-beam bombardment at a substrate temperature of 250 °C. The properties of DLC and c-BN films deposited at high growth rates up to 100 nm/min are presented . PACS 81.15.Fg; 68.60.Bs: 62.40.+i     

Infrared Spectroscopy Investigation of Cubic Boron Nitride Films

Abstract

FT-IR Spectroscopy have been used for identifying both the structure of BN and the intensity of the compressive stress in cubic boron nitride (c-BN) film prepared by a unbalanced of (13.56 MHz) magnetron sputtering of a hexagonal boron nitride target in a mixture argon and nitride discharge. A T(temperature) - V(negative bias) phase diagram was obtained using the phase structure identify by IR spectra. Comparing the reflection infrared spectra (RIR) with the transmission infrared spectra (TIR) measured from same c-BN film, it is firstly found that RIR peak position of c-BN is lower than TIR peak position of c-BN, this means that the compressive stress on the surface layer of c-BN film is smaller than that inside c-BN film, may be this is the reason why thicker c-BN film can not be synthesized. A higher IR peak position of 1064 cm^?1 and a lower peak position 1004.7 cm^?1 were detected from a broken and partly peeled off c-BN film. The peak position of 1064 cm^?1 agrees with that of bulk c-BN at 1065 cm^?1 which was synthesized at high temperature and high pressure, while the peak position of 1004.7 cm^?1 accords well with the result calculated (1004 cm^?1) by Wentzcovitch and it may be closes to that of the stress free value of c-BN. Using the result measured by Ulrich, the shift rate of IR peak position of c-BN in the films is about 3.8 cm^?1/Gpa to be obtained.     

THE INFLUENCE OF COMPRESSIVE STRESS ON THE FORMATION OF CUBIC BORON NITRIDE THIN FILM

The elastic strain energy and Gibbs free energy of cubic BN (cBN) thin film in biaxial stress field are calculated. The results show that the stress in cBN thin films has an impact on the formation of cubic phase. It is concluded that the high compressive stress in the cBN thin films is not the cause of cBN formation. This conclusion is different from that predicted by compressive stress model; however, it could well account for the experimental results. At a given substrate temperature, there is a compressive stress threshold, below which cBN phase is thermodynamically stable and above which hexagonal BN(hBN) phase is thermodynamically stable. At room temperature the compressive stress threshold is calculated to be 9.5 GPa.     

Surface properties of cubic boron nitride thin films

Studying the surface properties of cubic boron nitride (c-BN) thin films is very important to making it clear that its formation mechanism and application. In this paper, c-BN thin films were deposited on Si substrates by radio frequency sputter. The influence of working gas pressure on the formation of cBN thin film was studied. The surface of c-BN films was analyzed by X-ray photoelectron spectroscopy (XPS), and the results showed that the surface of c-BN thin films contained C and O elements besides B and N. Value of N/B of c-BN thin films that contained cubic phase of boron nitride was very close to 1. The calculation based on XPS showed that the thickness of hexagonal boron nitride (h-BN) on the surface of c-BN films is approximately 0.8 nm.     

Phase transformation in BN films by nitrogen-protected annealing at atmospheric pressure

Two groups of RF-sputtered BN films (pure hexagonal phase and approximately 27.5% cubic content, respectively) were annealed at 600 to 1000 °C under nitrogen at atmospheric pressure after deposition. FTIR spectroscopy indicates a reversible transformation from hexagonal phase to cubic phase, and again hexagonal phase. The most effective temperature for h-BN converting to cubic zincblende (c-BN) is 900 °C. Further, the indirectly stepwise transformation from hexagonal (h-BN) to explosive BN (E-BN) and then to c-BN employing metastable E-BN as an intermedium was observed. In addition, we tentatively put forward that the existence of defective h-BN and the N defects plays a key role on h-BN to c-BN transformation.     

Thick c-BN films deposited by radio frequency magnetron sputtering in argon/nitrogen gas mixture with additional hydrogen gas

The excellent physical and chemical properties of cubic boron nitride(c-BN) film make it a promising candidate for various industry applications. However, the c-BN film thickness restricts its practical applications in many cases. Thus, it is indispensable to develop an economic, simple and environment-friend way to synthesize high-quality thick, stable c-BN films. High-cubic-content BN films are prepared on silicon(100) substrates by radio frequency(RF) magnetron sputtering from an h-BN target at low substrate temperature. Adhesions of the c-BN films are greatly improved by adding hydrogen to the argon/nitrogen gas mixture, allowing the deposition of a film up to 5-μm thick. The compositions and the microstructure morphologies of the c-BN films grown at different substrate temperatures are systematically investigated with respect to the ratio of H_2 gas content to total working gas. In addition, a primary mechanism for the deposition of thick c-BN film is proposed.