Free-standing boron doped CVD diamond films grown on partially stabilized zirconia substrates

Boron doped diamond films have been grown adhered to silicon substrates by chemical vapor deposition using boron containing gases. In this work it was shown that it is possible to grow free-standing boron doped CVD diamond films on partially stabilized zirconia substrates using boron powder as the source for doping. Results from Raman spectroscopy confirmed the boron incorporation with concentration up to ∼10²⁰ cm⁻³. X-ray diffraction and scanning electron microscopy showed that the effect of boron incorporation in the microstructure of the diamond film is negligible. The measurement of the resistivity as a function of temperature confirmed the semiconductor behavior, as expected for p-type diamond.     

Diamond synthesis by DC thermal plasma CVD at 1 atm

Diamond crystals and films have been success full y synthesized by DC thermal plasma jet CVD at a pressure of I atrn. A novel triple torch plasma reactor has been used to generate a convergent plasma volume to entrain the participating gases. Three coalescing plasma jets produces! by this reactor direct the dissociated and ionized gaseous species onto ( 100) silicon wafer substrates where the diamond grows. In a typical 10-min run, depending on the method of .substrate preparation, either microcrystals with sizes up to 8 m or continuous films with thicknesses of 1–2 m have been obtained. X-ray diffraction, scanning electron microscopy, and Raman spectroscopy have been used for the characterization of the crystals and of the films.     

Study of the Interface Microstructures of CVD Diamond Films by TEM

 The characteristics of the interface microstructures between a CVD diamond film and the silicon substrate have been studied by transmission electron microscopy and electron energy loss spectroscopy. The investigations are performed on plan-view TEM specimens which were intentionally thinned only from the film surface side allowing the overall microstructural features of the interface to be studied. A prominent interfacial layer with amorphous-like features has been directly observed for CVD diamond films that shows a highly twinned defective diamond surface morphology. Similar interfacial layers have also been observed on films with a <100> growth texture but having the {100} crystal faces randomly oriented on the silicon substrate. These interfacial layers have been unambiguously identified as diamond phase carbon by both electron diffraction and electron energy loss spectroscopy. For the CVD diamond films that exhibit heteroepitaxial growth features, with the {100} crystal faces aligned crystallographically on the silicon substrate, such an interfacial layer was not observed. This is consistent with the expectation that the epitaxial growth of CVD diamond films requires diamond crystals to directly nucleate and grow on the substrate surface or on an epitaxial interface layer that has a small lattice misfit to both the substrate and the thin film material.     

Simultaneous growth of diamond and nanostructured graphite thin films by hot-filament chemical vapor deposition

Diamond and graphite films on silicon wafer were simultaneously synthesized at 850 °C without any additional catalyst. The synthesis was achieved in hot-filament chemical vapor deposition reactor by changing distance among filaments in traditional gas mixture. The inter-wire distance for diamond and graphite deposition was kept 5 and 15 mm, whereas kept constant from the substrate. The Raman spectroscopic analyses show that film deposited at 5 mm is good quality diamond and at 15 mm is nanostructured graphite and respective growths confirm by scanning auger electron microscopy. The scanning electron microscope results exhibit that black soot graphite is composed of needle-like nanostructures, whereas diamond with pyramidal featured structure. Transformation of diamond into graphite mainly attributes lacking in atomic hydrogen. The present study develops new trend in the field of carbon based coatings, where single substrate incorporate dual application can be utilized.     

Three-dimensional nano-foam of few-layer graphene grown by CVD for DSSC

We report a robust and direct route to fabricate a three-dimensional nano-foam of few-layer graphene (3D-NFG) with large area coverage via a chemical vapor deposition (CVD) technique. Pyrolysis of polymer/nickel precursor film under a hydrogen environment, simply prepared by spin-coating, leads to the creation of nano-foam in the film and the reduction process of nickel ions. Carbonized-C and the nickel nano-frame formed from the pyrolysis are used as a solid carbon source and as a catalyst for the growth of graphene under CVD conditions, respectively. We investigate the use of 3D-NFG, with the advantage of large surface area and high conductivity, as an alternative to the Pt counter electrode material in dye sensitized solar cells. The excellent properties of 3D-NFG, fabricated in this simple and direct manner, suggest a great potential for interconnected graphene networks in electronic devices and photocatalytic sensors as well as in energy-related materials.     

Scanning Probe Microscopy and Spectroscopy of CVD Diamond Films

 The surface morphology and electronic properties of as-deposited CVD diamond films and the diamond films which have been subjected to boron ion implantation or hydrogen plasma etching have been systematically studied by high resolution scanning probe microscopy and spectroscopy techniques. AFM and STM image observations have shown that (a) both the as-deposited CVD diamond films and the boron ion implanted films exhibit similar hillock morphologies on (100) crystal faces and these surface features are formed during the deposition process; (b) boron ion implantation does not cause a discernible increase in surface roughness; (c) atomic flatness can be achieved on crystal faces by hydrogen plasma etching of the film surface. Scanning tunnelling spectroscopy analysis has indicated that (a) the as-deposited diamond films and the hydrogen plasma etched diamond films possess typical p-type semiconductor surface electronic properties; (b) the as-deposited diamond films subjected to boron implantation exhibit surface electronic properties which change from p-type semiconducting behaviour to metallic behaviour; (c) the damage in the boron implanted diamond films is restricted to the surface layers since the electronic properties revert to p-type on depth profiling.     

PCVD法制备ZrO~2和YSZ薄膜

以金属β-二酮类有机螯合物Zr(DPM)~4和Y(DPM)~3为挥发性源物质, 采用微波等离子体化学气相淀积法于较低的温度下(420～560℃)成功地在多孔α-Al~2O~3陶瓷,非晶玻璃等衬底上制备出致密的ZrO~2和YSZ薄膜材料.XRD分析结果表明,纯ZrO~2薄膜中除了单斜相外还存在着亚稳态的四方相.当掺入的Y~2O~3 摩尔百分含量大于或等于7%时,ZrO~2完全被稳定成立方相.SEM观察表明, 在等离子体内的不同区域中生成的薄膜形貌有所不同.XPS检测了YSZ薄膜中Zr3d~5~/~2和Zr3d~3~/~2 的电子结合能,发现较ZrO~2的标准值低0.7eV.由TEM观察和由XRD衍射峰半宽度计算, 所制备的ZrO~2和YSZ薄膜中微晶粒径在10nm左右     

NIR- and VIS-raman spectroscopy of CVD diamond films

Raman spectroscopy is a widely used method for the analysis of CVD diamond layers, because it enables to distinguish between different carbon phases, such as diamond, graphite, amorphous carbon and nanocrystalline carbon, which are all commonly present in CVD diamond films. A comparison of visible Raman spectroscopy and near-infrared Raman spectroscopy applied to CVD diamond layers on various substrates (Si, SiAlON, Au, Pd, Mo, W and cemented carbides) has been carried out with the result that visible Raman spectroscopy can be preferably used for characterizing the diamond quality, but for the detection of non-diamond carbon phases NIR-Raman spectroscopy exhibits certain advantages. The NIR-Raman spectra of diamond on silicon substrates are interfered by thermal activation of the Si.Dedicated to Professor Dr. Dr. h.c. mult. J.F.K. Huber on the occasion of his 70th birthday     

Nucleation and morphology control in semiconductor AIBIIIX2VI type crystals grown by closed-tube CVD

Crystals of A^IB^IIIX₂^VI compounds can be successfully grown by chemical vapour deposition. By using this crystal growth method it is very important to reduce both primary nucleation and dendritic patterns. With this in mind two possible methods were described which are expected to give the best results. A discussion is further reported on some criteria for reducing the dendritic formations due to instability of the solid-vapour interface during the growth process. On the basis of these conclusions some improvements in the growth apparatus are proposed.     

Quantitative investigation of boron incorporation in polycrystalline CVD diamond films by SIMS

Polycrystalline diamond films have been produced on pre-treated silicon substrate by CVD hot filament method, with B(C₂H₅)₃ added to the gas phase. However, under identical surface conditions, boron incorporation is not homogeneous. In {111} growth sectors, the boron concentration is found to be about 5 times higher than in {100} growth sectors. Moreover, a marked increase in contaminating elements such as aluminium and sodium in regions with higher boron concentrations is detected. Under SIMS fine focus conditions it can be shown that the interface between these two different facet regions is smaller than 0.5?μm. With 3D-depth profile images it can also be shown that the carbon distribution in the diamond layer is not totally homogeneous.     

Quantitative investigation of boron incorporation in polycrystalline CVD diamond films by SIMS

Polycrystalline diamond films have been produced on pre-treated silicon substrate by CVD hot filament method, with B(C₂H₅)₃ added to the gas phase. However, under identical surface conditions, boron incorporation is not homogeneous. In {111} growth sectors, the boron concentration is found to be about 5 times higher than in {100} growth sectors. Moreover, a marked increase in contaminating elements such as aluminium and sodium in regions with higher boron concentrations is detected. Under SIMS fine focus conditions it can be shown that the interface between these two different facet regions is smaller than 0.5 μm. With 3D-depth profile images it can also be shown that the carbon distribution in the diamond layer is not totally homogeneous.     

High-quality free-standing and oriented periodic mesoporous organosilica films grown without a solid substrate at the air-water interface

In this communication, we report the first synthesis of high-quality free-standing and oriented periodic mesoporous organosilica (PMO) films grown without a solid substrate, by surfactant templating at the air-water interface.     

Wetting of CVD carbon films by polar and nonpolar liquids and implications for carbon nanopipes

The handling, dispersion, manipulation, and functionalization of carbon nanotubes and nanopipes often require the use of solvents. Therefore, a good understanding of the wetting properties of the carbon nanotubes is needed. Such knowledge is also essential for the design of nanotube-based nanofluidic devices, which hold the promise of revolutionizing chemical analysis, separation, drug delivery, filtration, and sensing. In this work, we investigated the wetting behavior of individual nanopipes produced by the chemical vapor deposition (CVD) of carbon in porous alumina templates and of thin carbon films produced by the same technique. The carbon pipes and films have the same chemistry and structure as determined by Raman and infrared spectroscopies and, when similarly treated, demonstrate the same qualitative wetting behavior, as determined by optical microscopy. Thus, measurements conducted on the carbon film surface are relevant to the nanopipes. In the case of the nanopipes, filling with various liquids was monitored. Contact angle experiments with both polar (water, glycerol, ethylene glycol, ethanol, tetra-hydro furan, and 2-propanol alcohol) and nonpolar liquids (cyclohexane, hexadecane, poly(dimethylsiloxane), and a fluoro-silicone) were conducted on films using the sessile drop method. The contact angles on the CVD carbon films ranged from 0 to 79 degrees. The exposure of the carbon films to a NaOH solution, typically used to dissolve the alumina template, led to a significant decrease of the contact angle, especially in the case of polar liquids.     

Thermoelectric properties of photo- and thermal CVD boron and boron phosphide films

The electrical properties of n-BP films newly prepared by thermal CVD in the B₂H₆-PH₃-H₂ system were improved by a deuterium lamp excitation. High-temperature electrical conductivity and thermoelectric power of amorphous boron and polycrystalline boron phosphide films grown on silica glass were measured to evaluate the thermoelectric figure-of-merit (Z). In particular, the Z-value for photo-thermal BP films was higher (10⁻⁴/K) than that of boron films, indicating that they are promising for high-temperature thermoelectric materials.     

Photoluminescent carbon nitride films grown by vapor transport of carbon nitride powders

The thermal vapor transport of nitrogen-rich carbon nitride powders produces carbon nitride films on substrates that retain significant nitrogen content, have conjugated bond character, and show blue photoluminescent emission near 450 nm.     

Nanocrystals grown in amorphous Cr and CrNi thin films

The structure of vacuum annealed amorphous sputtered Cr and CrNi (55:45) thin films has been studied by transmission electron microscopy (TEM) and electron diffraction (TED). The thin films with thicknesses ranging from 150 to 600 Å were annealed while still on their alkali halide substrates under high vacuum at temperatures ranging from 200 to 370°C. The TEM and TED data permitted to establish the annealing conditions (temperature, duration), which lead to the nucleation and growth of nanosized crystals in the Cr and CrNi icosahedral glasses.     

Structure and optical properties of CVD molybdenum oxide films for electrochromic application

Vibrational and optical properties of MoO₃ thin films have been studied by Raman and infrared spectroscopy. The films were deposited onto Si substrates at a temperature of 150 °C by chemical vapor deposition of Mo(CO)₆ at atmospheric pressure and different amounts of oxygen in the reactor. The Raman and IR spectral analyses show that the as-deposited films are in general amorphous. Post-deposition annealing at 300 and 400 °C leads to crystallization and the MoO₃ film structure is a mixture of orthorhombic and monoclinic MoO₃ modifications. Transformation of the monoclinic crystallographic modification to a thoroughly orthorhombic layered structure is observed for films heated at temperatures above 400 °C. Electronic Publication     

Combined laser and magnetic field treatment of YFeO<Subscript>3</Subscript>—containing films grown by spray-pyrolysis

Thin films (50–1200 nm) of YFeO₃ were deposited on fused silica substrates by spray-pyrolysis using ethylene glycol solution of Y-Fe(III) citric complexes. The films were post deposition annealed at 750°C in static air for 2 h. Films obtained in this way were afterwards irradiated by a burst mode operated Nd-YAG laser (pulse energy 650 mJ, pulse duration 700 μs, energy density 110 mJ/cm²). The laser’s onset was synchronized with that of a magnetic field pulse of nearly square shape (magnetic induction 0.5 T, pulse duration 900 μs). The samples were placed normally to the direction of the magnetic field. The treatment does not affect the phase composition of the film but significantly increases the crystallite sizes of the phases presenting in the sample. The saturation magnetization of the films decreases as a result of the laser and magnetic field treatment and the coercive force increases by 50%.     

Polymorphism and phase control in titanyl phthalocyanine thin films grown by supersonic molecular beam deposition

Polymorphism in the growth of titanyl phthalocyanine films on dielectric substrates has been systematically studied by UV absorption and micro-Raman analyses, correlating structure and optical properties. We explored different growth regimes as a function of substrate temperature and growth rate using hyperthermal seeded supersonic beams. We identify and discuss specific signatures in micro-Raman spectra specifically correlated to the different phases and demonstrate the unprecedented ability of growing crystalline films and controlling the relative abundance of the different phases (amorphous, phase I, and phase II) by the beam parameters. We envisage the very promising perspective of controlling polymorphism at low temperatures via supersonic beam growth, paving the way for better performing devices.