Chemical vapor deposition of amorphous ruthenium-phosphorus alloy films

Chemical vapor deposition growth of amorphous ruthenium-phosphorus films on SiO₂ containing ∼ 15% phosphorus is reported. cis-Ruthenium(II)dihydridotetrakis-(trimethylphosphine), cis-RuH₂(PMe₃)₄ (Me = CH₃) was used at growth temperatures ranging from 525 to 575 K. Both Ru and P are zero-valent. The films are metastable, becoming increasingly more polycrystalline upon annealing to 775 and 975 K. Surface studies illustrate that demethylation is quite efficient near 560 K. Precursor adsorption at 135 K or 210 K and heating reveal the precursor undergoes a complex decomposition process in which the hydride and trimethylphosphine ligands are lost at temperatures as low at 280 K. Phosphorus and its manner of incorporation appear responsible for the amorphous-like character. Molecular dynamics simulations are presented to suggest the local structure in the films and the causes for phosphorus stabilizing the amorphous phase.     

Low-temperature growth and orientational control in RuO2 thin films by metal-organic chemical vapor deposition

For growth temperatures in the range of 275°C to 425°C, highly conductive RuO₂ thin films with either (110)- or (101)-textured orientations have been grown by metal-organic chemical vapor deposition (MOCVD) on both SiO₂/Si(001) and Pt/Ti/SiO₂/Si(001) substrates. Both the growth temperature and growth rate were used to control the type and degree of orientational texture of the RuO₂ films. In the upper part of this growth temperature range ( 350°C) and at a low growth rate (< 3.0 nm/min.), the RuO₂ films favored a (110)-textured orientation. In contrast, at the lower part of this growth temperature range ( 300°C) and at a high growth rate (> 3.0 nm/min.), the RuO₂ films favored a (101)-textured orientation. In contrast, higher growth temperatures (> 425°C) always produced randomly-oriented polycrystalline films. For either of these low-temperature growth processes, the films produced were crack-free, well-adhered to the substrates, and had smooth, specular surfaces. Atomic force microscopy showed that the films had a dense microstructure with an average grain size of 50–80 nm and a rms. surface roughness of 3–10 nm. Four-probe electrical transport measurements showed that the films were highly conductive with resistivities of 34–40 μΩ-cm (at 25°C).     

Crosslinking of copolymer thin films by initiated chemical vapor deposition for hydrogel applications

The ability of initiated chemical vapor deposition to finely tune crosslinking densities in copolymer thin films has been used to develop a functional, reactive hydrogel system. The system consists of poly[maleic anhydride-co-dimethyl acrylamide-co-di(ethylene glycol) divinyl ether] films covalently attached to silicon substrates using the coupling agent 3-aminopropylethoxydimethylsilane. The swelling of the films in water is pH-dependent, with a maximum swelling ratio of 11 at pH = 8. The hydrogel was also functionalized with 0.1 M cysteamine solutions in 2-propanol for 30 min to convert 97% of the anhydride functional groups to carboxylic acid and amide functionalities, confirmed by XPS and Fourier transform infrared spectroscopy. The functionalization yielded free thiol groups at the surface, which were used to attach CdSe/ZnS core-shell semiconductor nanoparticles to the hydrogels.     

Thin molybdenum oxide films produced by molybdenum pentacarbonyl 1-methylbutylisonitrile with plasma-assisted chemical vapor deposition

Molybdenum oxide thin films were prepared by plasma-enhanced chemical vapor deposition of molybdenum pentacarbonyl 1-methylbutylisonitrile. This precursor is an interesting alternative for the commonly used molybdenum hexacarbonyl, because the substance is liquid at room temperature, offers sufficient volatility and stability to air and water. The film growth was monitored in situ by a soft X-ray reflectivity measurement. The films were deposited with different plasma gases (hydrogen and oxygen) under different conditions and analysed by Auger electron spectroscopy, X-ray diffraction and spectral ellipsometry.     

Hot-wire chemical vapor deposition and characterization of polycrystalline silicon thin films using a two-step growth method

A two-step growth method was proposed to reduce the amorphous incubation layer in the initial growth of polycrystalline silicon (poly-Si) films prepared by hot-wire chemical vapor deposition (HWCVD). In the two-step growth process, a thin seed layer was first grown on the glass substrate under high hydrogen dilution ratios (φ ≥ 0.9), and then a thick overlayer was subsequently deposited upon the seed layer at a lower φ value. The effect of various deposition parameters on the structural properties of poly-Si films was investigated by Raman spectroscopy and transmission electron microscopy. Moreover, the electrical properties, such as dark and photo conductivities, of poly-Si films were also measured. It was found that the Si incubation layer could be suppressed greatly in the initial growth of poly-Si with the two-step growth method. In the subsequent poly-Si film thickening, a lower φ value of the reactant gases can be applied to enhance the deposition rate. Therefore, a high-quality poly-Si film can be fabricated via a two-step growth method with a sufficient growth rate using HWCVD.     

Magnetic behavior of cobalt oxide films prepared by pulsed liquid injection chemical vapor deposition from a metal-organic precursor

Thin films of cobalt oxide were prepared by the pulsed liquid injection chemical vapor deposition technique from metal-organic precursor. By using a β-diketonate complex of cobalt, namely cobalt (II) acetylacetonate (Co(acac)₂) as the precursor, oxygen as the reactant and argon as the carrier gas, cobalt oxide films 100 nm in thick were deposited onto Si (100) substrates at 650 °C in about 40 min. According to the characterization by X-ray diffraction and atomic force microscopy, smooth and polycrystalline films, consisting exclusively of the Co₃O₄ phase, were deposited. Magnetic properties, such as saturation magnetization, the remanence, the coercivity, the squareness ratio and the switching field distribution, were extracted from the hysteresis loop. Cobalt oxide films with coercivities of 6.61 mT, squareness ratio of 0.2607 and saturation magnetization of 12.17 nA m², corresponding to a soft magnetic material, were achieved.     

Effect of HCl addition on the crystalline fraction in silicon thin films prepared by hot-wire chemical vapor deposition

In an effort to increase the crystalline fraction of silicon films directly deposited on a glass substrate by hot-wire chemical vapor deposition, the effect of HCl addition was studied. The silicon film was deposited on a glass substrate at 320 °C under a reactor pressure of 1333 Pa at the wire temperature of 1600 °C with 10%SiH₄–90%He at a fixed flow rate 100 standard cubic centimeter per minute (sccm) and HCl varied at 0, 10, 16 and 28 sccm. With increasing HCl, the crystalline fraction of silicon was increased as revealed by Raman spectra but the growth rate was decreased.     

二氧化铈对准晶真空蒸镀薄膜的影响

采用DMD-450真空镀膜仪将Al65Cu20Fe15准晶粉末沉积在Q235钢表面制备薄膜。研究了二氧化铈对薄膜的组织和结构的影响。采用透射电镜（TEM）、扫描电镜（SEM）、X射线衍射仪（XRD）等分析了薄膜的组织结构和表面形貌。利用纳米压痕仪（MTS）测试了薄膜的显微硬度和弹性模量。结果表明：通过准晶粉末真空蒸镀可以形成准晶薄膜。其组成相有CuAl2，A1Cu3 and I（Al65Cu20Fe15）相等。薄膜的成分取决于制备工艺。二氧化铈对薄膜的结构没有产生明显的影响。但是薄膜的显微硬度和弹性模量随二氧化铈添加量的增加而提高。当二氧化铈添加量为5％（质量分数）时，薄膜的显微硬度达到9．0GPa，弹性模量最高达到190GPa。此外，二氧化铈的添加明显增加了薄膜的耐蚀性能。     

气相沉积技术制备TiN类硬质膜

硬质膜由于具有良好的耐磨、耐蚀和耐热等特点,所以在航天、化工和机械等领域获得了日益广泛的应用,而硬质膜的组成和制备工艺也随之得到不断发展.本文综述了TiN类硬质膜的应用和制备硬质膜常用的气相沉积方法、工艺参数及其优缺点.阐明了制备工艺正向着以三束(电子束、离子束和激光束)为基础多种工艺复合的方向发展.而硬质膜正向着多元膜、梯度膜和纳米复合膜方向发展.     

BiFeO3 thin films prepared using metalorganic chemical vapor deposition

BiFeO₃ thin films were grown on (001) SrTiO₃ and (001) ZrO₂(Y₂O₃) substrates by single source metalorganic chemical vapor deposition in the temperature range T = 500 ÷ 800 °C using Fe(thd)₃ and Bi(C₆H₅)₃ as volatile precursors. X-ray diffraction analysis shows cube-on-cube epitaxial growth of BiFeO₃ on (001) SrTiO₃. The strongly reduced bismuth transfer into the film due to the high thermal stability of Bi(C₆H₅)₃ was counterbalanced by the increase of the total pressure as well as of the residence time of the precursor flow in the reactor; the Bi/Fe ratio in the film thus becomes close to that in the precursor mixture. Optical second harmonic generation measurements have evidenced the ferroelectric ordering in BiFeO₃ films and the apparent decrease of the Curie temperature of the strained films as compared to BiFeO₃ single crystal.     

Large-scale initiated chemical vapor deposition of poly(glycidyl methacrylate) thin films

The initiated chemical vapor deposition (iCVD) of poly(glycidyl methacrylate) (PGMA) was scaled up using dimensionless analysis. In the first stage, PGMA was deposited onto a large stationary substrate and a deposition rate as high as 85 nm/min was achieved. It was found that the deposition rate increases with increasing filament temperature, whereas the deposition rate and the number-average molecular weight decrease with increasing substrate temperature. In the second stage, PGMA was deposited onto a moving substrate. At speeds between 20 mm/min and 60 mm/min, the deposition rate on the moving substrate was found to be equal to the deposition rate on the stationary substrate. Fourier transform infrared spectroscopy showed that the epoxide functionality of the PGMA films was retained during the iCVD process. Since the iCVD polymerization of different vinyl monomers all use similar parameters, this scale up can be applied to the scale up of other vinyl monomers such as 2-hydroxyethyl methacrylate and perfluoroalkyl ethyl methacrylate.     

The process window for diamond deposition from the vapor phase with sulfur in the C–H–O feed gas mixtures

Theoretical predictions using a modified radical species ternary diagram for C–H–O system indicate that addition of sulfur expands the C–H–O gas phase compositional window for diamond deposition. Sulfur addition to no-growth domain increases the carbon super-saturation by binding the oxygen and the addition of sulfur to the non-diamond domain reduces the heavy carbon super-saturation by decreasing C_nH_m species concentration in the gas phase. The overall effect of sulfur addition to gas phase mixtures is characterized as that of oxygen addition to the C–H system, i.e. expansion of the compositional window over which diamond can be deposited from the gas phase. In addition, the increasing sulfur concentration to diamond domain feed gases beyond 2000 ppm did not affect the steady state gas phase composition but the quality of diamond was reduced.     

Chemical vapor deposition of aluminum from methylpyrrolidine alane complex

Chemical vapor deposition of aluminum from a recently developed precursor, methylpyrrolidine alane complex, has been studied. Aluminum films deposited on conducting surfaces (titanium nitride, copper, gold), but not on insulating surfaces (silicon, silicon dioxide, glass) at low substrate temperatures, showing deposition selectivity, while the deposition selectivity was lost at high substrate temperatures (> 210 °C). Al deposition rates on TiN and Cu were very close, but much higher than on Au. Deposition rates on all conducting substrates increased with the temperature and reached maximum at 180 °C. Al films deposited on as-sputtered TiN or Cu have no preferred orientations. Al–Au alloys and intermetallics were observed in the films deposited on Au. Surface morphology observation revealed that the film growth on TiN or Cu is different from that on Au. The surface roughness of Al films increased with the deposition time or the film thickness.     

化学气相沉积与渗透过程中热解炭织态结构生成机理研究

为研究热解炭织态结构的生成规律，采用不同压强的甲烷为碳源，在1100℃条件下进行了化学气相沉积和化学气相渗透实验。化学气相沉积以具有不同表面积／自由体积比（[A／V]值）的直通方形多孔陶瓷为基体；化学气相渗透实验在直径为1mm细直孔内表面沉积和对炭纤维体积分数为7％的炭毡进行致密化。借助正交偏光显微镜（消光角）和透射电子显微镜（定向角）对在不同实验条件下制备的热解炭进行分析和定量表征。研究发现：热解炭的织态结构可以在两种不同的沉积条件下形成。当甲烷压强较低时为化学生长阶段；当甲烷压强较高时为物理形核阶段。在化学生长控制阶段，热解炭的织态结构可以利用之前提出的“颗粒填充模型（P-F模型）”加以解释。该模型假设高织构热解炭的沉积一定对应于气相中存在具有合适比例的芳香化合物（例如苯）和线性小分子（主要是C2H2），当二者的浓度比偏离该最优比（或者偏大，或者偏小），均将导致中织构甚至低织构热解炭的生成。在化学生成控制阶段，化学气相沉积和化学气相渗透对热解炭织态结构影响的差别，除了[A／V]值而外，还有氢气的作用。在化学气相渗透过程中，基体内部生成的氢气快速扩散至基体表面，使内外沉积速率和织态结构均发生较大变化。     

Graphite formation on Ni film by chemical vapor deposition

Thin film formation of graphite by chemical vapor deposition using 2-methyl-1,2′-naphthyl ketone as a starting material was carried out on Ni film substrates. On Ni films directly deposited on quartz glass, the graphite films were obtained when the Ni film thickness was above 1 000 Å and above 5 000 Å at 700 °C and 1 000 °C, respectively. Depositions on thinner Ni film substrates comprise amorphous carbon (a-C) or graphite tubes which was owing to the thermal coagulation of the Ni film into droplets. On the other hand, graphite film was obtained on the Ni film with thickness 10 Å when a-C was inserted between the Ni film and the quartz glass. The coagulation of the Ni film is considered to be avoided by inserting a-C layer.     

Tungsten chemical vapor deposition using tungsten hexacarbonyl: microstructure of as-deposited and annealed films

Tungsten (W) films were deposited on Si(100) from tungsten hexacarbonyl, [W(CO)₆], by low-pressure chemical vapor deposition (CVD) in an ultra-high vacuum (UHV)-compatible reactor. The chemical purity, resistivity, crystallographic phase, and morphology of the deposited films depend markedly on the substrate temperature. Films deposited at 375°C contain approximately 80 at.% tungsten, 15 at.% carbon and 5 at.% oxygen. These films are polycrystalline β-W with a strong (211) orientation and resistivities of >1000 μΩ cm. Vacuum annealing at 900°C converts the metastable β-W to polycrystalline -W, with a resistivity of approximately 19 μΩ cm. The resultant -W films are porous, with small randomly oriented grains and nanoscale (<100 nm) voids. Films deposited at 540°C are high-purity (>95 at.%) polycrystalline -W, with low resistivities (18–23 μΩ cm) and a tendency towards a (100) orientation. Vacuum annealing at 900°C reduces the resistivity to approximately 10 μΩ cm, and results in a columnar morphology with a very strong (100) orientation.     

Synthesis of carbon nanofiber films and nanofiber composite coatings by laser-assisted catalytic chemical vapor deposition

Uniform carbon nanofiber films and nanofiber composite coatings were synthesized from ethylene on nickel coated alumina substrates by laser-assisted catalytic chemical vapor deposition. Laser annealing of a 50 nm thick nickel film produced the catalytic nanoparticles. Thermal decomposition of ethylene over nickel nanoparticles was initiated and maintained by an argon ion laser operated at 488 nm. The films were examined by scanning electron microscopy and by transmission electron microscopy. Overall film uniformity and structure were assessed using micro-Raman spectroscopy. Film quality was related to the experimental parameters such as incident laser power density and irradiation time. For long irradiation times, carbon can be deposited by a thermal process rather than by a catalytic reaction directly over the nanofiber films to form carbon nanocomposite coatings. The process parameters leading to high quality nanofiber films free of amorphous carbon by-products as well as those leading to nanofiber composite coatings are presented.     

Stress reduction in GaN films on (111) silicon-on-insulator substrate grown by metal-organic chemical vapor deposition

The GaN film was grown on the (111) silicon-on-insulator (SOI) substrate by metal-organic chemical vapor deposition and then annealed in the deposition chamber. A multiple beam optical stress sensor was used for the in-situ stress measurement, and X-ray diffraction (XRD) and Raman spectroscopy were used for the characterization of GaN film. Comparing the characterization results of the GaN films on the bulk silicon and SOI substrates, we can see that the Raman spectra show the 3.0 cm^− 1 frequency shift of E₂(TO), and the full width at half maximum of XRD rocking curves for GaN (0002) decrease from 954 arc sec to 472 arc sec. The results show that the SOI substrates can reduce the tensile stress in the GaN film and improve the crystalline quality. The annealing process is helpful for the stress reduction of the GaN film. The SOI substrate with the thin top silicon film is more effective than the thick top silicon film SOI substrate for the stress reduction.     

Influence of technological conditions on electronic transitions in chemical vapor deposited poly(azomethine) thin films

Thin films of poly(1,4-phenylenemethilidynenitrilo-1,4-phenylenenitrilomethilidyne) (PPI) have been prepared by chemical vapor deposition in the horizontal geometry using gaseous argon as a transport agent. PPI thin films have been grown by polycondensation of para-phenylene diamine (PPDA) and terephtal aldehyde (TPA). Fourier Transform Infrared spectra confirm formation of PPI layers without end groups. The strongest absorption band with discernible vibronic progression has been found to be due to superposition of 2.64, 2.82 and 3.03 eV bands corresponding to interband transitions connecting electronic ground state and vibrational levels of electronic excited state. A feature seen at about 2.6 eV in the spectra of PPI films prepared at higher temperatures of PPDA and TPA sources are attributed to excitons connected with the π-π? gap. Shoulder at 3.31 eV is attributed to interband transitions between delocalized states, while a peak at 4.2 eV is attributed to excitons formed by localized holes and delocalized electrons and vice versa and interband transitions connecting delocalized and localized bands, with the binding energy of about 0.8 eV. Thin films prepared at low temperatures of monomers consist of randomly distributed PPI chains weakly bound together.     

Growth of epitaxial sodium-bismuth-titanate films by metal-organic chemical vapor phase deposition

The liquid-delivery spin metal-organic chemical vapor phase deposition method was used to grow epitaxial sodium-bismuth-titanate films of the system Bi₄Ti₃O₁₂ + xNa_0.5Bi_0.5TiO₃ on SrTiO₃(001) substrates. Na(thd), Ti(OⁱPr)₂(thd)₂ and Bi(thd)₃, solved in toluene, were applied as source materials. Depending on the substrate temperature and the Na/Bi ratio in the gas phase several structural phases of sodium-bismuth-titanate were detected. With increasing temperature and/or Na/Bi ratio, phase transitions from an Aurivillius phase with m = 3 to m = 4 via an interleaved state with m = 3.5, and, finally, to Na_0.5Bi_0.5TiO₃ with perovskite structure (m = ∞) were established. These phase transitions proceed at remarkably lower temperatures than in ceramics or bulk crystals for which they had been exclusively observed so far.