微波化学气相沉积中气压对金刚石薄膜生长速率和质量的影响

研究了微波化学气相沉积中沉积气压对金刚石薄膜生长速率和质量的影响.研究表明，金刚石薄膜的生长速率随沉积气压的提高而增大，生长速率与沉积气压为线性关系.在高沉积气压下生长的金刚石薄膜晶形完整，拉曼谱测量可得到锐利的金刚石相的峰，但电压-电流测量表明，随着制备时沉积气压的提高，金刚石薄膜的暗电流增大，膜的电学质量下降. 关键词： 金刚石薄膜 生长速率 沉积气压     

Effect of freon flow rate on tin oxide thin films deposited by chemical vapor deposition

High quality fluorine-doped tin oxide (SnO₂:F) films on glass substrates were been prepared using chemical vapor deposition (CVD) method. The electrical properties, surface morphologies, structural properties and optical properties of the films were studied by varying the freon flow rates. The structure was analyzed by X-ray diffraction (XRD). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to study the morphology. Energy-dispersive spectroscopy (EDS) was conducted to understand the surface fluorine composition of the film. The results showed that crystalline structure of the film had a have cassiterite-like diffraction patterns with a preferred orientation of (1 1 0). Surface roughness was evaluated by atomic force microscopy, characterized by root mean square (RMS) and average value (Ra). The SnO₂:F resistivity decreased as the freon flow rate increased. The films had a uniform thickness and a transmittance of 80–90% within the visible region of the spectrum.     

On the structure, morphology, and optical properties of chemical bath deposited Sb2S3 thin films

In the present paper, we have reported the room temperature growth of antimony sulphide (Sb₂S₃) thin films by chemical bath deposition and detailed characterization of these films. The films were deposited from a chemical bath containing SbCl₃ and Na₂S₂O₃ at 27 °C. We have analysed the structure, morphology, composition and optical properties of as deposited Sb₂S₃ films as well as those subjected to annealing in nitrogen atmosphere or in air. As-deposited films are amorphous to X-ray diffraction (XRD). However, the diffused rings in the electron diffraction pattern revealed the existence of nanocrystalline grains in these films. XRD analysis showed that upon annealing in nitrogen atmosphere these films transformed into polycrystalline with orthorhombic structure. Also, we have observed that during heating in air, Sb₂S₃ first converts into orthorhombic form and then further heating results in the formation of Sb₂O₃ crystallites. Optical bandgap energy of as deposited and annealed films was evaluated from UV-vis absorption spectra. The values obtained were 2.57 and 1.73 eV for the as-deposited and the annealed films respectively.     

Effect of hydrogen on the growth and morphology of single wall carbon nanotubes synthesized on a FeMo/MgO catalytic system

Single wall carbon nanotubes were synthesized from thermal pyrolysis of methane on a FeMo/MgO catalyst by radio frequency catalytic chemical vapor deposition (RF-CVD) using argon as a carrier gas. Controlled amounts of hydrogen (H₂/CH₄=0-1 v/v) were introduced in separate experiments along with the carbon source. The properties and morphology of the synthesized single wall carbon nanotubes were monitored by transmission electron microscopy, Raman scattering, and thermogravimetric analysis. The nanotubes with the highest crystallinity were obtained with H₂/CH₄=0.6. By monitoring the Radial Breathing Modes present in the Raman spectra of the single-wall carbon nanotube samples, the variation of the structural and morphological properties of the carbon nanotubes with the flow level of hydrogen, reflect changes of the catalyst systems induced by the presence of hydrogen.     

Crystallization and grain growth characteristics of yttria-stabilized zirconia thin films grown by pulsed laser deposition

Knowledge about the crystallization and grain growth characteristics of metal oxide thin films is essential for effective microstructural engineering by thermal post-annealing and the integration to Si-based miniaturized electroceramic devices. Finite size and interface effects may cause fundamentally different behavior compared to three dimensional macroscopic systems. This work presents a comprehensive investigation of the crystallization kinetics and microstructural evolution upon thermal post-annealing of amorphous 200 nm and 1.2 μm thin films of 8 mol% yttria-stabilized zirconia grown by pulsed laser deposition (PLD) using ex- and in-situ X-ray diffraction, Raman spectroscopy, and electron microscopy techniques. The layers exhibit a remarkably low crystallization temperature of 200-250 °C while exposure to energetic electrons induces the formation of randomly dispersed ~ 20 nm sized crystallites already at ambient temperature. The isothermal amorphous to crystalline phase transformation kinetics can be described quantitatively by the Johnson-Mehl-Avrami-Kolmogorov model. They reveal characteristics of a three dimensional growth under cation bulk diffusion control with heterogeneous nucleation that changes from continuous to instantaneous initial seeding at temperatures above 300 °C. Large (> 100 nm) equiaxed grains are formed rapidly without a stabilization of transient nanocrystals during the thermally induced phase transformation. A stagnation of normal grain growth resulting in a logarithmic normal size distribution is observed once the average grain dimensions approach the film thickness. The results on the crystallization and grain growth of the PLD-grown YSZ films are evaluated with regards to the fabrication of YSZ solid electrolyte membranes for Si-supported micro solid oxide fuel cells and gas sensors.     

The morphology and structural properties of InP thin films deposited by spray pyrolysis method

InP film samples were prepared by spray pyrolysis technique using aqueous solutions of InCl₃ and Na₂HPO₄, which were atomized with compressed air as carrier gas onto glass substrates at 500 °C with different thicknesses of the films. The structural properties of the samples have been determined by using X-ray diffraction (XRD). It was found that the crystal structure of the InP films is polycrystalline hexagonal. The orientations for all the obtained films are along the c-axis perpendicular to the substrate. It is observed that the crystallite sizes of the films increase with the thickness of the film up to 616 nm. The changes observed in the morphology and structural phases related to the film thickness have been discussed in detail.     

Synthesis and characterization of GaN nanowires by a catalyst assisted chemical vapor deposition

GaN nanowires have been fabricated on Si(1 1 1) substrates by chemical vapor deposition (CVD) method with NiCl₂ as catalyst and their compositions, microstructures, morphologies and light emitting properties were characterized by X-ray diffraction (XRD), FT-IR spectrophotometer (FTIR), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), Raman spectroscopy and photoluminescence (PL). The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure and high crystalline quality, having the size of 20-50 nm in diameter and several tens of microns in length with some nano-droplets on their tips, which reveals that the growth mechanism of GaN nanowires agrees with vapor-liquid-solid (VLS) process. Five first-order Raman active phonon bands move to low shift and A₁(TO), E₁(TO), and E₂ (high) bands are overlapped and broaden, which is caused by uncertainty in the phonon wave vector. Five non-first-order active Raman phonons also appear, which is caused by the small dimension and high surface disorder degree. A blue-shift of the band-gap emission occurs due to quantum confinement effect.     

Structural,photoluminescent, and dielectric properties of Eu3+-doped Ba0.7Sr0.3TiO3 thin films

Eu³⁺-doped Ba_0.7Sr_0.3TiO₃ thin films were prepared by a chemical solution deposition method and characterized by X-ray diffraction, field emission scanning electron microscopy, photoluminescence and dielectric measurements. The thin films were well crystallized with a pure perovskite structure. A contraction of the unit cell was observed upon incorporation of Eu³⁺ ions below 2 mol%, while an expansion occurred as the Eu³⁺ concentration was further increased above 2 mol%, indicating that Eu³⁺ ions with different concentrations occupied different lattice sites. Photoluminescence spectra showed two prominent transitions of Eu³⁺ ions at 594 nm (⁵D₀ → ⁷F₁) and 618 nm (⁵D₀ → ⁷F₂) upon excitation at 395 nm (⁷F₀ → ⁵L₆). There existed two quenching concentrations at 2 mol% and 4 mol% due to different lattice sites of the Eu³⁺ ions. We also investigated the dielectric properties of the thin films. Our study suggests that Eu³⁺-doped Ba_0.7Sr_0.3TiO₃ thin films have potential applications in multifunctional optoelectronic devices.     

Investigations of morphology, purity and crystal defects of the InN pillar crystals prepared by means of halide chemical vapor deposition under atmospheric pressure

Indium nitride prepared under atmospheric pressure using a halide chemical vapor deposition method has been examined by means of a variety of analytical techniques. Scanning electron microscopic observations showed that the crystals deposited onto a Si(100) substrate have hexagonal pillar structure. Based on the X-ray diffraction and X-ray pole-figure analyses, it was deduced that each InN pillar crystal grows with a different rotation angle around the 〈001〉 axis. Transmission electron diffraction showed that they are of single-like form. This was also confirmed by the selected area electron diffraction image as well.     

Growth of crystalline quartz films with AT-cut plane by means of catalyst-enhanced vapor-phase epitaxy under atmospheric pressure

Crystalline quartz films with an AT-cut plane have been grown by catalyst-enhanced vapor-phase epitaxy, at atmospheric pressure, using two quartz buffer layers on a sapphire (110) substrate. In this method, the first quartz buffer layer was deposited on the sapphire (110) substrate at 773 K. After annealing at 823 K, the second buffer layer was deposited at 723 K. The crystal quartz epitaxial layer was then grown at 843 K. The X-ray full-width-at-half-maximum (FWHM) value of the crystalline quartz film obtained was smaller than that of crystalline quartz prepared using a hydrothermal process. The crystalline quality of the quartz films was dependent on the thickness of the buffer layers. Furthermore, it was found that angle control of the cut plane depended on the film thickness of the second buffer layer. The quartz films grown by vapor phase epitaxy show good oscillation characteristics at room temperature.     

Heat treatment effects on the structural and electrical properties of thermally deposited AgIn5S8 thin films

The heat treatment effects on structural and electrical properties of thermally deposited AgIn₅S₈ thin films have been investigated. By increasing the annealing temperature of the sample from 450 to 500 K, we observed a change in the crystallization direction from (420) to (311). Further annealing of the AgIn₅S₈ films at 550, 600 and 650 K resulted in larger grain size in the (311) preferred direction. The room temperature electrical resistivity, Hall coefficient and Hall mobility were significantly influenced by higher annealing temperatures. Three impurity levels at 230, 150, and 78 meV were detected for samples annealed at 350 K. The electrical resistivity decreased by four orders of magnitude when the sample annealing temperature was raised from 350 to 450 K. The temperature dependent electrical resistivity and carrier concentration of the thin film samples were studied in the temperature ranges of 25-300 K and 140-300 K, respectively. A degenerate-nondegenerate semiconductor transition at approximately 180 was observed for samples annealed at 450 and 500 K. Similar type of transition was observed at 240 K for samples annealed at 600 and 650 K.     

Ultra thin films of gadolinium deposited by evaporation in ultra high vacuum conditions: Composition, growth and morphology

Ultra-thin gadolinium films with thicknesses between 8 and 101 Å were deposited on AT-cut crystalline quartz substrates under ultra high vacuum conditions, and subsequently subjected to composition and morphologic characterization through X-ray photo-spectroscopy analysis and atomic force microscopy. Oxygen contamination is found on the samples, and its amount is estimated in terms of the thickness of an oxygen layer over the gadolinium films after subtracting the contribution to the XPS spectra of the underlying background. Atomic force microscope pictures provide evidence of having metal island films, with two growing regimes: the Volmer-Weber mode for the thinner films considered and the Stranski-Krastanov growing mode for the thicker ones. From evaluation of the sticking coefficient, the shape of the islands is approximated in terms of oblate spheroid caps and variation of the contact angle with film mass thickness is reported.     

A study of structural, compositional and optical properties of spray-deposited non-stoichiometric (Zn,Fe)S thin films

Non-stoichiometric ternary chalcogenides (Zn,Fe)S were prepared in the film form by pyrolytic spray deposition technique, using air/nitrogen as the carrier gas. The precursor solution comprised of ZnCl₂, FeCl₂ and thiourea. The depositions were carried out under optimum conditions of experimental parameters viz. carrier gas (air/nitrogen) flow rate, concentration of precursor constituents, nozzle substrate distance and temperature of quartz substrate. The deposited thin films were later sintered in argon at 1073 K for 120 min.The structural, compositional and optical properties of the sintered thin films were studied. X-ray diffraction studies of the thin films indicated the presence of (Zn,Fe)S solid solution with prominent cubic sphalerite phase while surface morphology as determined by scanning electron microscopy (SEM) revealed a granular structure.The chemical composition of the resulting thin films as analyzed by energy dispersive X-ray analysis (EDAX) reflected the composition of the precursor solutions from which the depositions were carried out with Fe at% values ranging from 0.4 up to 33.SEM micrographs of thin films reveal that the grain sizes of the thin films prepared using air as carrier gas and N₂ as carrier gas are in the vicinity of 300 and 150 nm, respectively.The diffuse transmittance measurements for thin films, as a function of wavelength reveal the dependence of direct optical band gap on Fe content and type of phase.     

Mechanisms of CVD diamond nucleation and growth on mechanically scratched Si(100) surfaces

The diamond nucleation has been studied on scratched Si(100) both by surface analyses (XPS, AES, ELS) and microstructural probes (AFM, SEM). Two pathways for diamond formation and growth are detected: A seeding pathway occurs by direct growth from part of diamond seeds left by the mechanical pretreatment. Not all of these seeds however are prone to diamond growth as they can be either dissolved or carburized. A nucleation pathway occurs through a stepwise process including the formation of extrinsic (pretreatment) or intrinsic (in situ) nucleation sites, followed by formation of carbon-based precursors. It is believed that nucleation sites could be either grooves of scratching lines or protrusions produced by etching-redeposition. The size of these protrusions is not larger than 100 nm. On top of these protrusions as well as on the bare substrate, a thin layer of silicon carbide rapidly forms and DLC carbon likely. This complex process on top of protrusions may constitute carbon-based embryos for further diamond nucleation. Received 21 December 1998     

Structural and optical properties of chemically synthesized monodispersed CdCr2S4 films

Alkaline chemical synthesis of amorphous CdCr₂S₄ (CCS) thin films of different thicknesses using cadmium chloride, chromic acid, disodium salt of ethylenediaminetetra acetic acid and thiourea precursors is reported, and the structural and surface morphological properties of CCS using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM) techniques are discussed. Films of aggregated grains with some void spaces are obtained. Change in band gap energy and electrical resistivity of CCS films are discussed as a function of film thickness. n-type conductivity is confirmed from the sign of thermally generated voltage across the cold and hot junctions.     

Microstructure and surface morphology of YSZ thin films deposited by e-beam technique

In present study yttrium-stabilized zirconia (YSZ) thin films were deposited on optical quartz (amorphous SiO₂), porous Ni-YSZ and crystalline Alloy 600 (Fe-Ni-Cr) substrates using e-beam deposition technique and controlling technological parameters: substrate temperature and electron gun power which influence thin-film deposition mechanism. X-ray diffraction, scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used to investigate how thin-film structure and surface morphology depend on these parameters. It was found that the crystallite size, roughness and growth mechanism of YSZ thin films are influenced by electron gun power. To clarify the experimental results, YSZ thin-film formation as well evolution of surface roughness at its initial growing stages were analyzed. The evolution of surface roughness could be explained by the processes of surface mobility of adatoms and coalescence of islands. The analysis of these experimental results explain that surface roughness dependence on substrate temperature and electron gun power non-monotonous which could result from diffusivity of adatoms and the amount of atomic clusters in the gas stream of evaporated material.     

A novel continuous process for synthesis of carbon nanotubes using iron floating catalyst and MgO particles for CVD of methane in a fluidized bed reactor

A novel continuous process is used for production of carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CVD) of methane on iron floating catalyst in situ deposited on MgO in a fluidized bed reactor. In the hot zone of the reactor, sublimed ferrocene vapors were contacted with MgO powder fluidized by methane feed to produce Fe/MgO catalyst in situ. An annular tube was used to enhance the ferrocene and MgO contacting efficiency. Multi-wall as well as single-wall CNTs was grown on the Fe/MgO catalyst while falling down the reactor. The CNTs were continuously collected at the bottom of the reactor, only when MgO powder was used. The annular tube enhanced the contacting efficiency and improved both the quality and quantity of CNTs.The SEM and TEM micrographs of the products reveal that the CNTs are mostly entangled bundles with diameters of about 10-20 nm. Raman spectra show that the CNTs have low amount of amorphous/defected carbon with I_G/I_D ratios as high as 10.2 for synthesis at 900 °C. The RBM Raman peaks indicate formation of single-walled carbon nanotubes (SWNTs) of 1.0-1.2 nm diameter.     

Structure, morphology and optical properties of SiO2−x thin films prepared by plasma-assisted pulsed laser deposition

The amorphous silicon oxide SiO_2−x thin films were prepared by the plasma-assisted pulsed laser deposition (PLD) method. X-ray diffraction spectrometry (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-VIS-NIR scanning spectrophotometry and ellipsometry were used to characterize the crystallinity, microscopic morphology and optical properties of obtained thin films. The influences of substrate temperatures, oxygen partial pressures and oxygen plasma assistance on the compositions of silicon oxide (SiO_2−x) thin films were investigated. Results show that the deposited thin films are amorphous and have high surface quality. Stoichiometric silicon dioxide (SiO₂) thin film can be obtained at elevated temperature of 200 °C in an oxygen plasma-assisted atmosphere. Using normal incidence transmittance, a novel and simple method has been proposed to evaluate the value of x in transparent SiO_2−x thin films on a non-absorbing flat substrate.     

Origin,characteristics, and suppression of residual nitrogen in MPCVD diamond growth reactor

Unintentional nitrogen incorporation has been observed in a set of microwave plasma chemical vapor deposition (MPCVD)-grown samples. No abnormality has been detected on the apparatus especially the base pressure and feeding gas purity. By a comprehensive investigation including the analysis of the plasma composition, we found that a minor leakage of the system could be significantly magnified by the thermal effect, resulting in a considerable residual nitrogen in the diamond material. Moreover, the doping mechanism of leaked air is different to pure nitrogen doping. The dosage of several ppm of pure nitrogen can lead to efficient nitrogen incorporation in diamond, while at least thousands ppm of leaked air is required for detecting obvious residual nitrogen. The difference of the dosage has been ascribed to the suppression effect of oxygen that consumes nitrogen. As the unintentional impurity is basically detrimental to the controllable fabrication of diamond for electronic application, we have provided an effective way to suppress the residual nitrogen in a slightly leaked system by modifying the susceptor geometry. This study indicates that even if a normal base pressure can be reached, the nitrogen residing in the chamber can be activated by the thermal effect and thus be incorporated in diamond material grown by a MPCVD reactor.     

Luminescence properties of Tb and Eu-doped alumina films prepared by sol-gel method under various conditions and sensitized luminescence

Rare earth ion (Tb³⁺ and Eu³⁺)-doped alumina films were prepared by the aqueous sol-gel method under various conditions. The influences of the OH groups (phonon relaxation) and rare earth ion concentration (cross-relaxation) on luminescence were examined. In regard to the former relaxation, at treatment temperature above 600°C, reciprocal lifetime decreased with OH concentration, and below 500°C, decreased markedly and nonlinearly. On the other hand, in regard to the latter relaxation, there was negligible effect on luminescence for these doped films. The quantitative treatment was tried to lifetime considering these influences. Tb³⁺ and Eu³⁺ co-doped alumina films showed enhanced Eu³⁺ luminescence by the energy transfer from Tb³⁺ to Eu³⁺. Eu³⁺ luminescence intensity increased with a greater Tb³⁺ concentration.