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Laser-Induced Chemical Vapour Deposition of Silicon Carbonitride 激光诱导化学气相沉积碳氮化硅
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:19955112
W. Besling, P. Put, J. Schoonman
Laser-induced Chemical Vapour Deposition of silicon carbonitride coatings and powders has been investigated using hexamethyldisilazane (HMDS) and ammonia as reactants. An industrial CW CO 2 -laser in parallel configuration has been used to heat up the reactant gases. HMDS dissociates in the laser beam and reactive radicals are formed which increase rapidly in molecular weight by an addition mechanism. Dense polymer-like silicon carbonitride thin films and nanosized powders are formed depending on process conditions. Powder particles are deposited on a substrate by means of a thermal gradient. The primary particle size is about 30 nm. The particles are agglomerated. Depositions are characterized with spectroscopic and chemical analysis and correlated to some important laser process parameters. The powder deposit and the thin film consist of Si-N, Si-C and Si-O bonds according to FTIR-spectroscopy and X-ray Photo-Electron Spectroscopy. A residual amount of hydrogen is present. The material is amorphous (XRD) and has a polymer-like structure. The overall composition varies around Si 0.4 C 0.1 N 0.3 O 0.2 . The nitrogen content increases significantly by adding ammonia to the reactant gas flow. The high amount of oxygen is caused by hydrolysis and is a result of being exposed to air.
以六甲基二矽氮烷(HMDS)和氨为反应物,研究了激光诱导化学气相沉积碳氮化硅涂层和粉末。采用平行配置的工业连续co2激光器对反应物气体进行了加热。HMDS在激光束中解离,形成反应性自由基,并通过加成机制迅速增加分子量。根据不同的工艺条件,可以形成致密的类聚合物碳氮化硅薄膜和纳米级粉末。粉末颗粒通过热梯度沉积在衬底上。主要粒径约为30 nm。颗粒聚集在一起。用光谱和化学分析对沉积进行了表征,并与一些重要的激光工艺参数相关联。ftir光谱和x射线光电子能谱分析表明,粉末沉积物和薄膜由Si-N、Si-C和Si-O键组成。有残余的氢存在。该材料是无定形的(XRD),具有类似聚合物的结构。整体组成在Si 0.4 C 0.1 N 0.3 O 0.2左右变化。在反应物气流中加入氨气,氮含量显著增加。大量的氧气是由水解引起的,是暴露在空气中的结果。
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引用次数: 3
OMCVD on Fluidized Divided Substrates : a Potential Method for the Preparation of Catalysts 流化分离基质上的OMCVD:一种有潜力的催化剂制备方法
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:19955122
R. Feurer, A. Reynes, P. Serp, P. Kalck, R. Morancho
The OMCVD method has been used to deposit highly pure metal particles on porous divided substrates in order to prepare metal supported catalysts. A fluidized bed reactor has been especially designed and the requirements of CVD and fluidization have been taken into account to select convenient experimental conditions. Three organometallic compounds of rhodium have been selected and their thermal decomposition under He and He/H2 mixtures studied by infrared spectroscopy and on-line mass spectrometry analyses. The deposition are carried out at a total pressure of 100 Torr and substrate temperatures as low as 100°C. The solid deposits have been characterized by XPS, the size and dispersion of the particules have been determined by chemisorption methods or measured by TEM. These catalysts can be used without further treatment and their performances have been compared to those of conventionally prepared ones.
利用OMCVD方法在多孔分割的衬底上沉积高纯度的金属颗粒,制备了金属负载催化剂。特别设计了流化床反应器,考虑了气相沉积和流态化的要求,选择了方便的实验条件。选择了三种铑的金属有机化合物,用红外光谱和在线质谱分析研究了它们在He和He/H2混合物下的热分解。沉积是在总压力为100托和衬底温度低至100°C下进行的。用XPS对固体沉积物进行了表征,用化学吸附法和透射电镜测定了颗粒的大小和分散性。这些催化剂无需进一步处理即可使用,并与常规制备的催化剂进行了性能比较。
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引用次数: 0
Mechanism of Thermal Decomposition of Palladium β-Diketonates Vapour on Hot surface 钯β-二酮酸酯蒸气热表面热分解机理研究
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:1995523
P. P. Semyannikov, V. Grankin, I. Igumenov, A. Bykov
The processes of thermal decomposition of palladium(II) β-diketonate complexes were investigated by a high-temperature mass spectrometric method with the use of a high-temperature molecular beam source. It was established that decomposition of the palladium complexes in gas phase processes proceeds by a radical mechanism and depends on temperature. For an additional proof of the existence of the radical particles the spin trap method was applied with a mass spectrometric identification of adducts. The following order of thermal stability of the complexes in gas phase was established: Pd(hfac) 2 > Pd(tfac) 2 > Pd(dpm) 2 > Pd(acac) 2 . This order is reverse to the thermal stability in a solid state. The thermal decomposition of Pd(aa) 2 and Pd(hfa) 2 complexes in deuterium showed that the deuterium presence strongly accelerates the decomposition processes.
采用高温分子束源,用高温质谱法研究了钯(II) β-二酮酸配合物的热分解过程。确定了钯配合物在气相过程中的分解是由自由基机制进行的,并依赖于温度。为了进一步证明自由基粒子的存在,用自旋阱法对加合物进行了质谱鉴定。配合物的气相热稳定性顺序为:Pd(hfac) 2 > Pd(tfac) 2 > Pd(dpm) 2 > Pd(acac) 2。这个顺序与固态的热稳定性相反。Pd(aa) 2和Pd(hfa) 2配合物在氘中的热分解表明,氘的存在强烈地加速了分解过程。
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引用次数: 6
Direct Deposition of Metal Film Patterns Using Nitrogen Laser 氮激光直接沉积金属薄膜图案
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:1995582
E. Reznikova, V. V. Chesnokov, G. I. Zharkova, I. Igumenov
Rhenium, gold and platinum film micropatterns were obtained by the LCVD method on the surface of silicon and glass substrates from vapors of Re 2 (CO) 10 , (CH 3 ) 2 Au(dpm), Pt(hfa) 2 , respectively. The heated reaction chamber at atmospheric pressure with a flow of an inert gas-carrier was used. The high marginal sharpness and the thickness uniformity of deposited films was provided by the use of a powerful nanosecond pulse nitrogen laser (λ=337 nm), a projective system for delineation of the irradiation zone and by laser beam microscanning in the limits of the projective mask window. The metal pattern replicating the configuration of the projective mask window with a uniform 0.1-1 μm thickness was formed during 1-10 s. The writing rate of the straight metal lines was limited by the size of the irradiation zone and by the pulse repetition frequency and made of 150 μm/s. The smooth Re films were obtained with a good adhesion to the substrate and a surface resistivity of about 1 Ω/square. The films of Au and Pt were deposited as layers of microdrops whose coupling with one another and with the contact ground determined the film resistivity. The melting of Au and Pt films occurs during the laser-induced deposition process and influences the film growth dynamics and the film-to-substrate adhesion.
用LCVD法在硅和玻璃衬底表面分别用re2 (CO) 10、(ch3) 2、Au(dpm)、Pt(hfa) 2的蒸气制备了铼、金和铂薄膜微图案。在常压下加热反应室,用惰性气体载体流动。利用强大的纳秒脉冲氮激光器(λ=337 nm)、用于划定辐照区的投影系统以及在投影掩膜窗口的极限内进行激光束微扫描,提供了高边缘锐度和厚度均匀性的沉积膜。在1 ~ 10 s的时间内,形成了均匀厚度为0.1 ~ 1 μm、与投影掩模窗结构相似的金属图案。直线金属线的写入速率受辐照区大小和脉冲重复频率的限制,写入速率为150 μm/s。得到了光滑的Re膜,与衬底的附着力良好,表面电阻率约为1 Ω/平方。Au和Pt薄膜以微滴的形式沉积,它们之间的耦合以及与接触面的耦合决定了薄膜的电阻率。在激光诱导沉积过程中,Au和Pt薄膜的熔化影响了薄膜的生长动力学和薄膜与衬底的粘附性。
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引用次数: 0
Chemical Vapor Deposition of Hyperpure Polysilicon on Industrial Scale 工业规模超纯多晶硅的化学气相沉积
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:19955129
M. Domenici
The worldwide production of semiconductor grade polysilicon for electronic application has reached nowadays the amount of 10,000 T/y. The material is produced universally by CVD of extremely purified (chloro)silanes reacting with hydrogen. A modern plant will be described operating under conditions which are optimized for energy saving and ecological purposes (closed-loop operation). Other CVD applications in use for electronic materials are described, namely polysilicon deposition on wafer back, for gettering purposes, and epitaxial layer deposition on wafer front. Last one accounts for an annual production of more than 450 MSQI (million square inches).
目前,全球电子用半导体级多晶硅产量已达10000吨/年。该材料普遍采用极纯氯硅烷与氢反应的气相沉积法生产。一个现代化的工厂将在节能和生态目的优化的条件下运行(闭环运行)。描述了用于电子材料的其他CVD应用,即在晶圆背面沉积多晶硅,用于吸光目的,以及在晶圆正面沉积外延层。最后一个占年产量超过450 MSQI(百万平方英寸)。
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引用次数: 0
Atomic layer-by-layer MOCVD of oxide superconductors 氧化物超导体的原子逐层MOCVD
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:1995545
S. Oda, Shuu'ichirou Yamamoto, A. Kawaguchi
A very smooth surface film of c-axis oriented YBa 2 Cu 3 Ox (YBCO) with roughness of less than monomolecular layer over 10μmx10μm, free of precipitates, has been obtained by atomic layer-by-layer metalorganic chemical vapor deposition (MOCVD) on a SrTiO 3 substrate at 650°C. A very large terrace length of 0.3-0.5μm may be due to the enhanced migration of growing species on the surface. The result of an attempt to prepare YBCO films with a larger terrace width surface using NdGaO 3 substrates is discussed. The correlation between boulder formation and dislocations in the substrate is clarified and methods for eliminating boulders are proposed. Very high superconductivity critical current densities of 3x10 7 A/cm 2 at 4.2K and 3x10 6 A/cm 2 at 77K have been obtained.
采用原子逐层金属有机化学气相沉积(MOCVD)技术,在650℃的srtio3衬底上制备了一层无析出物、粗糙度小于10μmx10μm的C轴取向YBa 2 Cu 3 Ox (YBCO)薄膜。梯田的长度很大(0.3 ~ 0.5μm),这可能是由于生长物种在地表的迁移增强所致。讨论了利用NdGaO 3衬底制备具有较大台阶宽度表面的YBCO薄膜的结果。阐明了岩石形成与基底位错之间的关系,并提出了消除岩石的方法。在4.2K和77K下分别获得了3 × 10 7 A/ cm2和3 × 10 6 A/ cm2的超高超导临界电流密度。
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引用次数: 1
Mass Spectrometric Study of the Gas Phase During Chemical Vapor Deposition of Pyrolytic Carbon 热解碳化学气相沉积气相质谱研究
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:1995508
F. Fau-Canillac, F. Carrere, A. Reynes, C. Vahlas, F. Maury
The pyrolysis of CH 4 , of C 3 H 8 and of the mixture 20C 3 H 8 /80CH 4 was investigated in a hot wall CVD reactor by mass spectrometry. Experiments were conducted as a function of temperature and of surface-to-volume (S/V) ratio of the substrate. The main by-products of the pyrolysis were identified and reaction mechanisms were proposed taking into account homogenous decomposition/formation reactions. Cyclic species are possibly involved in the formation mechanism of pyrocarbon.
采用质谱法在热壁CVD反应器中研究了ch4、c3h8和20c3h8 / 80ch4混合物的热解过程。实验以温度和衬底的表面体积比(S/V)为函数进行。确定了热解的主要副产物,并结合均相分解/生成反应提出了反应机理。环状物质可能参与了热解碳的形成机制。
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引用次数: 2
A study by In Situ FTIR Spectroscopy of the Decomposition of Precursors for the MOCVD of High Temperature Superconductors 高温超导体MOCVD前驱体分解的原位FTIR光谱研究
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:1995542
A. Kovalgin, Francoise Chabert-Rocabois, M. Hitchman, S. H. Shamlian, S. Alexandrov
In this paper we report on a study by FTIR spectroscopy of the gas phase thermal decomposition of [Y(TMHD) 3 ], [Cu(TMHD) 2 ] and [Ba(TDFND) 2 .tetraglyme] under a total pressure of 10 Torr, for a temperature range 200 - 650°C, and in the absence and presence of oxygen. The variation of the decomposition characteristics for each of the complexes as a function of temperature, and as shown by changes in the absorption coefficients, are related to the molecular structures.
本文用红外光谱法研究了[Y(TMHD) 3]、[Cu(TMHD) 2]和[Ba(TDFND) 2 .四胺]在总压力为10托、温度范围为200 ~ 650℃、无氧和有氧条件下的气相热分解。每一种配合物的分解特性随温度的变化以及吸收系数的变化都与分子结构有关。
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引用次数: 2
Chemical Vapor Deposition of ZrO2 Thin Films Using Zr(NEt2)4 as Precursor 以Zr(NEt2)4为前驱体的化学气相沉积ZrO2薄膜
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:1995561
A. Bastianini, G. Battiston, R. Gerbasi, M. Porchia, S. Daolio
By using tetrakis(diethylamido) zirconium [Zr(NEt 2 ) 4 ], excellent quality ZrO 2 thin films were deposited with high growth rates on alumina and glass substrates by chemical vapor deposition. The depositions were carried out in a hot wall reactor at reduced pressure (200 Pa) in the temperature range 500-580°C and in the presence of oxygen. The as-grown films are colourless, smooth and well-adherent to the substrates. SIMS analysis evidenced pure ZrO 2 with a slight superficial contamination of hydrocarbons and nitrogen. The films have a tapered polycrystalline columnar structure well visible in SEM micrographs. From X-ray diffraction analysis. the monoclinic phase resulted as the major phase together with a small variable amount of tetragonal zirconia. Under 550°C the as-grown films resulted highly textured and were dominated by the (020) orientation. The films were annealed in the range 600-1000°C and the effect of annealing on the texture and on the phase and dimensions of the crystallites have been studied.
以四(二乙基酰胺)锆[Zr(NEt 2) 4]为材料,采用化学气相沉积法在氧化铝和玻璃基底上沉积了高生长速率的优质ZrO 2薄膜。沉积在热壁反应器中进行,减压(200 Pa),温度范围为500-580°C,并在氧气存在下进行。生长后的薄膜是无色的,光滑的,能很好地附着在基材上。SIMS分析证实为纯ZrO 2,表面有轻微的碳氢化合物和氮污染。薄膜具有锥形多晶柱状结构,在SEM显微照片中很明显。来自x射线衍射分析。以单斜相为主,外加少量的四方氧化锆。在550℃下,生长的薄膜具有高度织构,并且以(020)取向为主。在600 ~ 1000℃范围内退火,研究了退火对薄膜织构、晶相和晶粒尺寸的影响。
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引用次数: 22
Chemical Vapour Deposition of AIN-Si3N4 Codeposits 化学气相沉积AIN-Si3N4共沉积层
Pub Date : 1995-06-01 DOI: 10.1051/JPHYSCOL:1995593
F. Henry, B. Armas, C. Combescure, D. Thenegal, R. Flamand
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引用次数: 0
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Le Journal De Physique Colloques
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