Organometallic chemical vapor deposition using allyl precursors

Homoleptic allyl derivatives of many Main-Group and transition metals, M(C₃H₅)_n, are readily available through one-pot syntheses using metal halides and allyl Grignard reagents or by alkylation of alkali-metal salts. The relatively low molecular weight of a C₃H₅ ligand contributes to high vapor pressures whilst the stability of the allyl radical is predicted to reduce decomposition temperatures. These compounds represent a class of volatile precursors for organometallic chemical vapor deposition (OMCVD) of thin films. Film growth studies using iridium, molybdenum, palladium, platinum, rhodium, selenium, tellurium and tungsten compounds are reviewed and the relationships between pyrolysis pathways and film purity are discussed.     

Metallization of a thiol-terminated organic surface using chemical vapor deposition

The deposition and the subsequent decomposition of an organometallic precursor, (eta (3)-allyl)(eta (5)-cyclopentadienyl)palladium [Cp(allyl)Pd], on an organic surface exposed by self-assembled monolayers (SAM) was studied using X-ray photoelectron spectroscopy (XPS) and infrared reflection absorption spectroscopy (IRRAS). The interfacial chemical reactions of the vapor-deposited metal precursor with the pendant thiol group of the SAMs made from oligophenyldithiols, which are either prepared directly (terphenyldimethyldithiol, TPDMT) or by a deprotection route from SAMs formed by a monoacylated derivative of biphenyldimethyldithiol (dep. BPDMAc-1) have been studied in detail. When the TPDMT-SAMs were exposed to Cp(allyl)Pd vapor, a Pd (2+)/allyl-terminated SAM surface was obtained (to a lower extent this was also the case for dep. BPDMAc-1 SAMs), which was stable against exposure to H 2 gas. Reduction to Pd (0) by H 2 was only observed when small amounts of Pd (0) were already present, for example, after prolonged exposure to the precursor. The catalytic activity of the small Pd (0) particles also caused a decomposition of the SAMs upon exposure to air.     

Fabrication of a thin palladium membrane supported in a porous ceramic substrate by chemical vapor deposition

A thin, gas-tight palladium (Pd) membrane was prepared by the counter-diffusion chemical vapor deposition (CVD) process employing palladium chloride (PdCl₂) vapor and H₂ as Pd precursors. A disk-shaped, two-layer porous ceramic membrane consisting of a fine-pore γ-Al₂O₃ top layer and a coarse-pore -Al₂O₃ substrate was used as Pd membrane support. A 0.5–1 μm thick metallic membrane was deposited in the γ-Al₂O₃ top layer very close to its surface, as verified by XRD and SEM with a backscattered electron detector. The most important parameters that affected the CVD process were reaction temperature, reactants concentrations and top layer quality. Deposition of Pd in the γ-Al₂O₃ top layer resulted in a 100- to 1000-fold reduction in He permeance of the porous substrate. The H₂ permeation flux of these membranes was in the range 0.5–1.0 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ at 350–450°C. The H₂ permeation data suggest that surface reaction steps are rate-limiting for H₂ transport through such thin membranes in the temperature range studied.     

On-wafer thermomechanical characterization of a thin film polyimide formed by vapor deposition polymerization for through-silicon via applications: Comparison to plasma-enhanced chemical vapor deposition SiO2

Thin-film polyimides were prepared by solvent-less vapor deposition polymerization (VDP) from pyromellitic dianhydride and 4,4′-oxydianiline at 200 °C for liner dielectric formation of vertical interconnects called through-silicon vias (TSVs) used in three-dimensionally stacked integrated circuit (3DICs). FTIR, synchrotron XPS, and TDS were employed for determining the imidization ratio, and in addition, the mechanical properties, coefficient of thermal expansion and Young's modulus, of the VDP polyimide were characterized on Si wafers. The VDP polyimide exhibited extremely high conformality, beyond 75%, toward high-aspect-ratio deep Si holes, compared with conventional SiO₂ prepared by plasma-enhanced chemical vapor deposition. The adhesion between the VDP polyimide and Si wafer was enhanced by an Al-chelate promotor. Remarkably, the VDP polyimide TSV liner dielectrics showed much less thermomechanical stresses applied to the Si surrounding the TSVs than the plasma-chemical vapor deposition SiO₂. The small keep-out zone is expected for scaling down highly reliable 3DICs for the upcoming real artificial intelligence society.     

Characterization of amorphous hydrogenated carbon formed by low-pressure inductively coupled plasma enhanced chemical vapor deposition using multiple low-inductance antenna units

Three-dimensional plasma enhanced chemical vapor deposition (CVD) of hydrogenated amorphous carbon (a-C:H) has been demonstrated using a new type high-density volumetric plasma source with multiple low-inductance antenna system. The plasma density in the volume of phi 200 mm x 100 mm is 5.1 x 10(10) cm(-3) within +/-5% in the lateral directions and 5.2 x 10(10)cm(-3) within +/-10% in the axial direction for argon plasma under the pressure of 0.1 Pa and the total power as low as 400 W. The uniformity of the thickness and refractive index is within +/-3.5% and +/-1%, respectively, for the a-C:H films deposited on the substrates placed on the six side walls, the top of the phi 60 mm x 80 mm hexagonal substrate holder in the pure toluene plasma under the pressure is as low as 0.04 Pa, and the total power is as low as 300 W. It is also found that precisely controlled ion bombardment by pulse biasing led to the explicit observation in Raman and IR spectra of the transition from polymer-like structure to diamond-like structure accompanied by dehydrogenation due to ion bombardment. Moreover, it is also concluded that the pulse biasing technique is effective for stress reduction without a significant degradation of hardness. The stress of 0.6 GPa and the hardness of 15 GPa have been obtained for 2.0 microm thick films deposited with the optimized deposition conditions. The films are durable for the tribology test with a high load of 20 N up to more than 20,000 cycles, showing the specific wear rate and the friction coefficient were 1.2 x 10(-7) mm3/Nm and 0.04, respectively.     

硅纳米线的化学气相沉积法合成

硅纳米线是近十几年来在纳米科学与技术领域快速发展的一种重要材料．通过精细的结构设计与材料合成,硅纳米线在生物传感、锂离子电池、太阳能电池和光电化学等领域展示出良好的应用前景．化学气相沉积（CVD）法是一大类重要的自下而上合成硅纳米线方法．本文简介了CVD法合成硅纳米线的主要进展,包括具有单一结构和复合结构的硅纳米线的合成．其中,单一结构的硅纳米包括本征（无掺杂）、掺杂和超长的硅纳米线;复合结构的硅纳米线包括轴向异质结、径向异质结、转折结构和树枝状结构的硅纳米线．     

Photoinitiated chemical vapor deposition of polymeric thin films using a volatile photoinitiator

Photoinitiated chemical vapor deposition (piCVD) is an evolutionary CVD technique for depositing polymeric thin films in one step without using any solvents. The technique requires no pre- or post-treatment and uses a volatile photoinitiator to initiate free-radical polymerization of gaseous monomers under UV irradiation. Glycidyl methacrylate (GMA) was used as a test monomer for its ability to undergo free-radical polymerization, and 2,2'-azobis(2-methylpropane) (ABMP) was used as the photoinitiator, as it is known to produce radicals when excited by photons. GMA and ABMP vapors were fed into a vacuum chamber in which film growth was observed on a substrate exposed to UV irradiation. The resulting poly(glycidyl methacrylate) (PGMA) thin films were comprised of linear chains and had high structural resemblance to conventionally polymerized PGMA, as shown by the high solubility in tetrahydrofuran and the infrared and X-ray photoelectron spectroscopy measurements. The introduction of ABMP into the vacuum chamber significantly increased growth rates. The maximum growth rate achieved was approximately 140 nm/min and represents a 7-fold enhancement over the case without ABMP. The molecular weight was found to increase with increasing monomer-to-initiator (M/I) feed ratio, and the polydispersity indexes (PDIs) of the samples were between 1.8 and 2.2, lower than the values obtained in conventional batch polymerization but in agreement with the theoretical expressions developed for low-conversion solution-phase polymerization, which are applicable to continuous processes such as piCVD. Molecular-weight distributions can be narrowed by filtering out wavelengths shorter than 300 nm, which induce branching and/or cross-linking. The strong dependence of the molecular weight on the M/I ratio, the rate enhancement due to the use of a radical photoinitiator, the good agreement between the experimental, and the theoretical PDIs provide evidence of a free-radical mechanism in piCVD. The clear films obtained in this work had number-average molecular weights between 12 500 and 97 000 g/mol. The similarities in growth conditions, growth rates, and molecular weights between the initiated CVD, a previously reported thermal process able to synthesize a wide range of polymers, and the piCVD of PGMA suggest that piCVD can also be used to produce those polymers and potentially others whose monomers undergo free-radical mechanisms. This paper serves as an introduction to the technique by demonstrating piCVD's ability in synthesizing high-molecular-weight PGMA thin films with narrow molecular-weight distributions from vapors of GMA and ABMP in a single, dry step under UV irradiation.     

Synthesis, characterization and gas permeation properties of a silica membrane prepared by high-pressure chemical vapor deposition

Cylindrical silica membranes with dead-end structure were prepared by an extended counter-diffusion chemical vapor deposition (CVD) method, in which a tetramethylorthosilicate (TMOS) silica source was fed from the outside of a cylindrical membrane support with γ-alumina interlayer (the membrane side), and oxygen gas was fed from the inside (the support side). Extended counter-diffusion CVD is a method of depositing silica films under highly pressurized conditions applied to the membrane side where TMOS is supplied. Two silica membranes were deposited for 10 h at 573 K under differential pressures of 0.1 MPa and 0.0 MPa applied between the cylindrical membranes. The hydrogen permeances for these silica membranes were unaffected (5 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹ at 573 K), although the methane and carbon dioxide permeances were greatly reduced for dense silica films prepared by high-pressure CVD (HPCVD). Therefore, the selectivity of hydrogen over methane and carbon dioxide was 24,000, and 1200, respectively. It is suggested from energy dispersive X-ray microanalysis (EDX) observations in scanning electron microscopy (SEM) and scanning probe microscopy (SPM) results that this high selectivity was due to the reduced number of defects and/or pinholes formed in the dense silica membranes by HPCVD.     

Ti-Si-N films prepared by plasma-enhanced chemical vapor deposition

Ti-Si-N thin films were deposited on HSS substrates at 560°C using plasmaenhanced chemical vapor deposition. Feed gases used were TiCl₄, SiCl₄, N₂, and H₂. The composition of the films could be controlled well through adjustment of the mixing ratio of the chlorides in the feed gases. The Si content in the film varied in the range of O to 40 at. %. It was jbund that a small addition of Si to a TiN film improved the morphology significantlv, showing dense and glasslike structure. Also a much smootherand more homogeneous interface between thefilm and the substrate was obtained. The Ti-Si- N films containing 10–15 at. % Si showed the maximal microhardness value of about 6350 kgf/mm², much higher than that of TiN films.     

Plasma chemical vapor deposition of TiN

Experiments indicate that the temperature in chemical vapor deposition (CVD) of TiN can be decreased from about 1000°C in conventional CVD to about 500°C by the application of a D.C. nonequilibrium plasma. The hardness of the TiN film is greater than 2000 kg/mm² (Vickers). The effect of pressure, ratio of gas mixture, and discharge parameters on the film deposition rate, its hardness, and microstructures has been studied.     

Epitaxial polymerization of 1,3-butadiyne by chemical vapor deposition

1,3-Butadiyne was epitaxially polymerized on the graphite basal plane by chemical vapor deposition to form a homogeneous thin film. The film thickness varied from 100 to 3000 Å depending on the polymerization condition. The films on the graphite showed a variety of interference colors such as blue, purple, or gold depending on the film thickness. Raman spectra revealed that the polymerized film was mainly composed of ? C?C? bonds. Electron diffraction pattern and the ESCA spectrum of the film were quite similar to those of graphite, suggesting that butadiyne was polymerized in an epitaxial manner.     

Metallic Li in carbonaceous nanotubes grown by metalorganic chemical vapor deposition from a metalorganic precursor

Metallic Li in carbonaceous nanostructures was obtained in high concentration (as much as 33.4%) through metalorganic chemical vapor deposition involving certain lithium–aminoalkyl moieties, which are formed in situ , by decomposition of a precursor containing both cobalt and lithium. The bimetallic complex containing both lithium and cobalt was characterized by IR spectroscopy, mass spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis and thermogravimetric analysis. X‐ray photoelectron spectroscopy measurements performed on the as‐grown films demonstrate that lithium can be stable in metallic form in such a film. Results of X‐ray photoelectron spectroscopic analysis of the as‐grown films are presented as direct evidence of the formation and stabilization of metallic lithium in carbon nanotubes. Carbon nanotubes, encapsulating metallic lithium, can potentially act as a miniaturized nanobattery. Such a battery would be potentially useful in the next generation of communication and remote sensing devices, where a pulse of current is required for their operation. In addition, with metallic lithium, having an effective nuclear magnetic moment, such materials can be envisioned to show potential applications in devices based on nuclear magnetic resonances. Copyright © 2008 John Wiley & Sons, Ltd.     

n型金刚石薄膜催化生长碳纳米管

研究了n型金刚石薄膜作为催化剂生长碳纳米管的方法.首先采用丙酮裂解化学气相沉积(CVD)法制备均匀的n型金刚石薄膜,然后采用乙醇为碳源的CVD法,在850、900和950℃下,分别在n型金刚石薄膜上制备了碳球、竹节状碳管和多壁碳纳米管.所得产物用扫描电子显微镜、透射电子显微镜、拉曼光谱和X射线光电子能谱表征.实验结果表明产物的形貌与反应温度有关.我们还提出了与金刚石催化生长碳纳米管结果相符的实验机理.     

Polymerization of 2,4-hexadiyn-1,6-diol by chemical vapor deposition

2,4-Hexadiyn-1,6-diol (HDO) was polymerized on glass and silicon plates by chemical vapor deposition without transition metal catalysis to form homogeneous thin films. Structural properties of the films were investigated by FT-IR, UV-visible, Raman, x-ray diffraction, and XPS spectroscopic analyses. The structure of CVD-polymerized HDO (CVD-PHDO) films was different from that of metathesis polymerized HDO (metathesis-PHDO), showing a polyacene-based structure but no polyene structure with acetylenic side groups. © 1996 John Wiley & Sons, Inc.     

Synthesis of molybdenum disulfide particles by aerosol-assisted chemical vapor deposition

It was shown that dimethylformamide can be, in principle, used as a solvent of ammonium thiomolybdate for obtaining molybdenum disulfide particles by the aerosol-assisted chemical vapor deposition method. IR Fourier spectroscopy was used to examine (NH₄)₂MoS₄–C₃H₇NO liquid solutions and the thermal stability of dimethylformamide and ammonium thiomolybdate vapors. It was demonstrated that pyrolysis at temperatures of 700–900°C yields spherical molybdenum disulfide microparticles with average diameters in the range 0.6–1 µm and “onion” structure.     

Seedless growth of free-standing copper nanowires by chemical vapor deposition

Free-standing copper nanowires were synthesized by a chemical vapor deposition process at low substrate temperatures using Cu(etac)[P(OEt)3]2 as a precursor. The process requires neither templates nor catalysts to produce copper nanowires of 70-100 nm in diameter, which exhibited high purity and crystallinity with [111] orientation. The grain structures of the films deposited from a series of Cu(I) alkyl 3-oxobutanoate complexes indicated that the high precursor stability was responsible for the columnar growth of the grains, which was evolved to the nanowires eventually.     

Fabrication of graphene with CuO islands by chemical vapor deposition

Graphene prepared on Cu foil by chemical vapor deposition was studied as a function of post growth cooling conditions. CuO islands embedded in the graphene film were discovered and studied by scanning electron microscopy, atomic force microscopy, and X-ray photoemission spectroscopy. It is shown that nanostructured holes can be formed within a graphene film by reduction using hydrogen cooling immediately after film growth. We also observe the formation of symmetrical oxide islands in these holes. This study provides an easy way to fabricate a graphene + CuO composite, and the method may be extended to other graphene based structures.     

Synthesis of helical and straight carbon nanofibers by chemical vapor deposition using alkali chloride catalysts

Microchimica Acta - Carbon nanofibers were synthesized by chemical vapor deposition using alkali chloride catalysts at a temperature range from 500 to 700 °C. Depending on the...