Implementation of the time-modulated process to produce diamond films using microwave-plasma and hot-filament CVD systems

A newly developed process called time-modulated chemical vapour deposition (TMCVD) was employed to deposit smooth polycrystalline diamond films onto silicon substrates using both microwave plasma CVD (MPCVD) and hot-filament CVD (HFCVD) systems. The distinctive feature of the TMCVD process, which separates it from the conventional diamond CVD process, is that it pulses methane (CH₄) at different flow rates for different time durations into the vacuum reactor during the entire diamond CVD process. Generally, both MPCVD and HFCVD systems produced results that displayed similar trends, except that the growth rate results obtained using the two CVD systems were conflicting. In comparison to the conventional CVD diamond films, the time-modulated films, deposited using both MPCVD and HFCVD techniques, were generally found to be (i) smoother, (ii) consisted of smaller diamond crystallites and (iii) displayed approx. similar film quality. The diamond-carbon phase purity of the as-grown films was assessed using Raman spectroscopy. In addition, the surface roughness, Ra, values of the deposited films were obtained using surface profilometry.     

高品质金刚石膜微波等离子体CVD技术的发展现状

金刚石膜拥有许多优异的性能。在制备金刚石膜的各种方法之中,高功率微波等离子体化学气相沉积(MPCVD)法因其产生的等离子体密度高,同时金刚石膜沉积过程的可控性和洁净性好,因而一直是制备高品质金刚石膜的首选方法。在世界范围内,美、英、德、日、法等先进国家均已掌握了以高功率MPCVD法沉积高品质金刚石膜的技术。但在我国国内,高功率MPCVD装备落后一直是困扰我国高品质金刚石膜制备技术发展的主要障碍。首先综述国际上高功率MPCVD装备和高品质金刚石膜制备技术的发展现状,包括各种高功率MPCVD装置的特点。其后,回顾了我国金刚石膜MPCVD技术的发展历史,并介绍北京科技大学近年来在发展高功率MPCVD装备和高品质金刚石膜制备技术方面取得的新进展。     

Chemical bath deposition and characterization of CdSe thin films for optoelectronic applications

Cadmium selenide (CdSe) thin films of high crystalline quality on glass substrate have been prepared by chemical bath deposition technique from an aqueous bath containing tetramine cadmium and sodium selenosulphate. Structural analysis using XRD shows that the film is single phase, crystallized in hexagonal structure with preferred growth in (111) direction. The energy band gap calculated from the absorption spectra of unannealed CdSe thin films shows an optical band gap of 1.8 eV and absorption coefficient near band edge (α)—0.58 × 10⁵ cm⁻¹. The conductivity of CdSe thin films is n-type.     

分体圆柱谐振腔法用于金刚石膜微波介电性能测试的研究

针对金刚石膜微波介电损耗低、厚度薄带来的微波介电性能测试难点, 研制了一台分体圆柱谐振腔式微波介电性能测试装置。利用不同直径的蓝宝石单晶样品, 用上述装置对低损耗薄膜类样品微波介电性能的测试能力及样品直径对测试结果的影响进行了实验研究。在此基础上, 使用分体圆柱谐振腔式微波介电性能测试装置对微波等离子体化学气相沉积法和直流电弧等离子体喷射法制备的高品质金刚石膜在Ka波段的微波介电性能进行了测试比较。测试结果表明, 由Raman光谱、紫外-可见光谱等分析证明品质较优的微波等离子体化学气相沉积法制备的金刚石膜具有更高的微波介电性能, 其相对介电常数和微波介电损耗值均低于直流电弧等离子体喷射法制备的金刚石膜。     

Effects of the grain size of CVD diamond films on the detector performance

Although the unique properties of CVD diamond films have made it a candidate material for radiation detectors, the detector performance is strongly dependent on the film quality. In this paper, three CVD diamond films with different grain size were grown by using a hot-filament chemical vapor deposition (HFCVD) technique and the ratio of the grain size to the film thickness is high to 50%. 5.9 keV ⁵⁵Fe X-rays measured the photocurrents and the pulse height distributions (PHDs) of these CVD diamond detectors. The detector performance is improved with the grain size increasing. The dark-current of 16.0 nA and the photocurrent of 15.9 nA are obtained at an electrical field of 50 kV⋅cm⁻¹ and the PHD peak is well separated from the noise pedestal.     

Crystalline β-C3N4 synthesized by MPCVD

Carbon nitride films were grown on Si and Pt substrates by microwave plasma chemical vapor deposition (MPCVD) method. Scanning electron microscope (SEM) observations show that the films deposited on Si substrates consisted of densely populated hexagonal crystalline rods. Energy dispersive X-ray (EDX) analyses show that N/C ratios of the rods were in the range of 1.0 to 2.0 depending on deposition condition. X-ray diffraction experiments show that the films consisted of crystalline phase -C₃N₄. Comparison with films grown on Pt substrate show that the main X-ray diffraction peaks of -C₃N₄ are existed in films deposited on both substrate. XPS study showed that carbon and nitride atoms are covalent bounded to each other. IR results show that the film is predominantly C-N bonded. Raman measurement showed characteristic peaks of -C₃N₄ in the low wave number region. Temperature dependent growth experiments show that the amount of Si₃N₄ in the films grown on Si substrates can be significantly reduced to negligible amount by controlling the substrate temperature.     

Epitaxial growth of SrRuO3 thin films by RF sputtering and study of surface morphology

We report on the epitaxial growth of SrRuO₃ (SRO) thin films on Pt (111)/γ-Al₂O₃ (111) nSi (111) substrates. The grown thin films are crystalline and epitaxial as suggested by RHEED and XRD experiments. With the use of γ-Al₂O₃ (001)/nSi (001) and γ-Al₂O₃ (111)/nSi (111) substrates, crystalline but not epitaxial films have grown successfully. This result implies that lattice mismatch between nSi and SRO prevents the epitaxial growth of SRO film directly on nSi. However, the buffer Pt (111) layer mitigates lattice mismatch that provides to grow epitaxial film on nSi of quality. Morphological study shows a good surface with moderate roughness. Film grown at 700°C is smoother than the film grown at 750°C, but the variation of temperature does not affect significantly on the epitaxial nature of the films.     

微波等离子体化学气相沉积——一种制备金刚石膜的理想方法

综述了微波等离子体化学气相沉积(MPCVD)法制备金刚石膜技术,表明MPCVD是高速、大面积、高质量制备金刚石膜的首选方法。介绍了几种常用的MPCVD装置类型,从MPCVD装置的结构特点可以看到,用该类型装置在生长CVD金刚石膜时显示出独特的优越性和灵活性。用MPCVD法制备出的金刚石膜其性能接近甚至超过天然金刚石,并在多个领域得到广泛应用。     

Annealing temperature effect on structural and morphological properties of nano photonic LiNbO<Subscript>3</Subscript>

In this work, thermal annealing processes was depended in order to prepare (Δ) phase LiNbO₃ and the properties of nanostructure films was characterized. The sol–gel method was used to grow and deposit high purity Lithium-Niobate Nano and Micro-structure on a quartz substrate, at three different annealing temperatures. The structural, morphological, and optical properties of grown films have been investigated using X-ray diffraction, scanning electron microscopy, atomic force microscopy, optical study through Raman spectroscopy, UV–Vis and Photoluminescence. The measurements showed that the structure was crystalline in nature and the grains are regularly distributed within the film as a result of increasing the annealing temperature. This observation is typically used in optical waveguides and other optoelectronics applications.     

ZnO ultra-fine powders and films: hydrothermal synthesis,luminescence and UV lasing at room temperature

Zinc oxide ultra-fine crystalline powders and polycrystalline films of high optical quality were synthesized under soft hydrothermal conditions. The phase composition, crystal morphology, and luminescent properties of submicron ZnO powders and films were studied depending on synthesis conditions (system composition, precursor kind, solvent type and concentration, temperature). For the systems containing metallic zinc, the ZnO growth mechanism was suggested. The most intensive UV luminescence and the highest values of I_UV/I_VIS were observed for polycrystalline films grown on Zn substrates. Low-threshold UV lasing at room temperature was found for ZnO-films, grown in hydrothermal systems with hydroxide or halide solutions as solvents, E _th = 1–5 MW/cm². The lowest threshold was observed on the ZnO films grown using LiOH as a solvent and zinc nitrate as ZnO-precursor. Clear mode structures with line-width 0.3 nm are characteristic of the lasing spectra.     

The effects of temperature on the molecular orientation of zinc phthalocyanine films

Phthalocyanine compounds have been widely investigated as candidate materials for technological applications, which is mainly due to their thermal stability and possibility of processing in the form of thin films. In most applications, the controlled growth of thin films with high crystalline quality is essential. In this study, zinc phthalocyanine (ZnPc) thin films were prepared by evaporation on glass and Au-coated glass substrates with subsequent annealing at different temperatures in ambient atmosphere. The morphological and structural features of 80 nm thick zinc phthalocyanine films were investigated, evidencing an α → β phase transformation after annealing the films at 200 °C, as indicated by UV–Vis spectroscopy and FTIR analyses. A better uniformity of the annealed films was also evidenced via AFM analysis, which may be of importance for applications where film homogeneity and excellent optical quality are required.     

Simultaneous fabrication of nanocrystalline and {100} textured large-grained diamond films

In this work, we report the simultaneous synthesis of both nanocrystalline and {100} textured large-grained diamond films in one deposition run performed in a 5-kW microwave plasma chemical vapor deposition (MPCVD) reactor. This was achieved by employing the coupled effect of nitrogen addition in the gas phase and substrate temperature on the growth of diamond films. In one deposition run, different substrate surface temperatures were obtained by a novel substrate arrangement, nanocrystalline diamond of high growth rate around 3 μm/h was formed at low temperature, while {100} textured large-grained diamond of much higher growth rate about 11 μm/h was grown at high temperature. This new method opens way for mechanical and tribological applications of both nano-diamond and {100} textured diamond in industrial level. This result indicates that distinct growth modes or growth mechanisms were involved at different substrate temperatures with a certain amount of nitrogen addition. The coupled effect of nitrogen addition and temperature on the growth of CVD diamond films and the involved growth mechanism is briefly discussed from the point of view of gas phase chemistry and surface reactions.     

无支撑、光学级MPCVD金刚石膜的研制

利用引进的6 kW微波等离子体化学气相沉积设备,进行了无支撑金刚石膜工艺的初步研究。在800~1050℃的基片温度范围内,金刚石膜都呈(111)择优取向;基片相对位置对沉积较大面积、光学级金刚石膜至关重要。制出0.25 mm厚Φ50 mm的无支撑金刚石膜。拉曼光谱和X射线衍射分析表明,合成的金刚石膜晶体结构完整,sp2含量极低;透过率测试结果说明了优良的光学性能:截止波长225 nm,光学透过率(λ≥2.5μm)≥70%。     

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.     

Effects of disk rotation rate on the growth of ZnO films by low-pressure metal-organic chemical vapor deposition

ZnO films were grown at low pressure in a vertical metal-organic vapor deposition (MOCVD) reactor with a rotating disk. The structural and morphological properties of the ZnO films grown at different disk rotation rate (DRR) were investigated. The growth rate increases with the increase of DRR. The ZnO film grown at the DRR of 450 revolutions per minute (rpm) has the lowest X-ray rocking curve full width at half maximum and shows the best crystalline quality and morphology. In addition, the crystalline quality and morphology are improved as the DRR increased but both are degraded when the DRR is higher than 450 rpm. These results can help improve in understanding the rotation effects on the ZnO films grown by MOCVD.     

不同等离子体体系中纳米金刚石薄膜制备的研究

利用微波等离子体化学气相沉积（MPCVD）法分别在CH4／H2／Ar体系、CH4／H2／O2体系和C2H5OH／H2体系中进行纳米金刚石（NCD）薄膜的制备研究。采用原子力显微镜（AFM）和激光拉曼光谱（Raman）等方法对不同体系中制备得到的NCD薄膜的表面形貌及其质量进行了检测。结果表明：在CH4／H2体系中添加O2对于促进高平整度NCD薄膜的效果明显优于添加At;C2H5OH／H2体系更有利于制备颗粒更细、金刚石相含量更高的NCD薄膜。利用等离子体CVD技术的相关理论对上述结论进行了理论分析。     

Thermal properties of semiconductor zinc oxide nanostructures

A combination of two methods — laser modulation and 3ω — has been used to determine the heat capacity, heat conductivity, and heat diffusivity of zinc oxide nanostructures. A significant difference between the thermal parameters of zinc oxide nanostructures grown by different technological methods has been revealed. It has been shown that the relatively low heat conductivity and heat diffusivity values of oxide zinc nanostructures are due to both the internal defects and the contact resistance between the film and its base — the substrate.     

Two-step growth of HFCVD diamond films over large areas

This paper reports the results of a two-step hot filament chemical vapor deposition method to improve the quality of diamond films. Diamond films were deposited on a Si(100) substrate having an area of 45 cm² and a thickness of 60 μm, employing a HFCVD system. The first step is the growth of CVD diamond in the HFCVD reactor. In the second step, the samples were treated in a saturated solution of H₂SO₄:CrO₃ and rinsed in a (1:1) solution of H₂O₂:NH₄OH. After this procedure, a second diamond layer was deposited. The diamond films were analyzed by Raman scattering spectroscopy (RSS), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The films showed a high degree of purity with a thickness of 60 μm, presenting uniform characteristics over a large area.     

Growth and characterization of YBa2Cu3Ox and NdBa2Cu3Ox superconducting thin films by mist microwave-plasma chemical vapor deposition using a CeO2 buffer layer

Superconducting thin films of YBa₂Cu₃O_x (YBaCuO) and NdBa₂Cu₃O_x (NdBaCuO) were grown by mist microwave-plasma chemical vapor deposition (MPCVD) using a CeO₂ buffer layer on a MgO (001) substrate. In this method, the CeO₂ buffer layer was deposited on the MgO (001) substrate at 1173 K by MPCVD. YBaCuO and NdBaCuO films were then grown at 1073 K and 1223 K, respectively. The T_c (zero resistance) values of the YBaCuO and NdBaCuO films obtained with a CeO₂ buffer layer were 90.1 K and 94.1 K, respectively, about 10 K higher than those without a CeO₂ buffer layer. The surface roughness of the films was less than 5 nm in each case. The interface between the substrate and the grown layer was confirmed to be extremely sharp by Auger profile analysis.     

Annealing effect on structural, optical and electrical properties of pure and Mg doped tin oxide thin films

This study describes the effect of annealing at different temperatures (400–600 °C) on structural, optical and electrical behaviors of pure and Mg doped tin oxide thin films grown on the glass substrate by electron beam evaporation technique. The transformation of tetragonal to orthorhombic form due to annealing, introduced a change in the optical and electrical properties of pure and Mg doped tin oxide thin films. X-ray diffraction studies or analysis revealed the phase transformation and change in the crystalline size with increase in the annealing temperature. The morphology and roughness of the thin films were studied by Atomic force microscopy. Optical band gap increased with annealing temperature confirms the improvements of crystallinity. The quality of thin films transparency was investigated by UV/Vis-spectroscopy. Photoluminescence of pure and Mg doped tin oxide thin films shows two extra peaks one at 486 nm and other at 538 nm is due to the crystal defect created as a result of annealing temperature. These peaks became stronger and shifted to longer wavelength with increasing the annealing temperature. The complex plot (Nyquist plot) showed the data point laying on two semicircles and the resistance of grains and grain boundaries increases with the increase in annealing temperature for both pure and Mg doped tin oxide thin films.