Seeded growth of TPA-MFI films using the fluoride route

The fluoride route in combination with surface seeding was used for the preparation of TPA-MFI films on dense amorphous silica glass supports. The use of F⁻ as mineralizing agent allowed the crystallization of TPA-MFI at near-neutral pH (6.7 ± 0.1). The supports were seeded with colloidal TPA-MFI crystals and hydrothermally treated in a synthesis gel at 100 °C for various durations (24–192 h). The synthesis products were characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRPD). A film growth rate of about 9 nm/h was found. The crystals in these films exhibit a preferred orientation, with the (1 0 1) planes of the crystals parallel or near parallel to the support surface. Film growth in the near-neutral synthesis gel was also attempted on seeded porous -alumina supports. However, epitaxial growth of the seed crystals was inhibited by the formation of a uniform layer of colloidal silica particle which covered the seed crystals even in an early stage of hydrothermal treatment. Continuous films could only be prepared by increasing the pH of the initial synthesis mixture from 6.7 to 9.6, thus using both OH⁻ and F⁻ as mineralizing agents. These films are composed of a columnar layer on top of a layer built up of small grains. Such microstructure has previously been reported in the literature for TPA-MFI films grown in conventional synthesis mixtures.     

厚度对掺铝氧化锌透明导电薄膜性质的影响

采用紫外光助溶胶一凝胶法在玻璃基底上制备了掺铝氧化锌薄膜。研究了厚度对薄膜性质的影响,结果表明：所有薄膜均由具有c轴优先生长取向的六角纤锌矿结构的ZnO晶体构成,晶体的粒径随厚度的增加而先增大,达到最大值后,不再随厚度的增加而改变;薄膜的方阻随厚度的增加先减小,在达刮最小值2．1×10^2Ω／口后,随厚度的增加又略有增大;而所有薄膜均是透明的,在可见光区的透光率〉80％。     

Preparation of Tetragonal Barium Titanate Thin Film on Titanium Metal Substrate by Hydrothermal Method

Tetragonal BaTiO₃ thin films were prepared directly on Ti metal substrates in Ba(OH)₂ solutions by a hydrothermal method at temperatures 400° to 800°C for 5 to 240 min. The film thickness estimated from weight gain of Ti plate was in the range from 0.5 to 2.5 μm, and it increased with increasing treatment temperature, treatment time, and Ba(OH)₂ concentration. Rectangular crystals having {100} and {001} faces grew idiomorphically with approximate crystal size of 0.3 to 2.0 μm. The tetragonality of the BaTiO₃ films became apparent when the average crystal size exceeded about 1 μm. Lattice parameters of the films were a = 3.994 Å, c = 4.035 Å, and c/a = 1.010. The films formed above 600°C had preferred orientation showing stronger XRD peaks of h 00 and 00 l than the other peaks.     

Use of Transmission Electron Microscopy for the Characterization of Rapid Thermally Annealed, Solution-Gel, Lead Zirconate Titanate Films

The microstructure and preferred orientations of rapid thermally annealed Pb(Zr_0.53,Ti_0.47)O₃ films, deposited on Pt/Ti/SiO₂/Si electrode/substrates by solution-gel spinning, have been investigated using analytical and high-resolution electron microscopy and X-ray diffraction. The temperature of pyrolysis of the PZT films was found to influence the preferred orientation of the film: lower temperatures (350°C) favored a (111) orientation, whereas higher temperatures (420°C) favored a (100) orientation. Excess Pb was used to control the A-site stoichiometry of the film particularly at the film surface where Pb-deficient crystals could often be observed. The absence of these crystals was shown to be correlated with an improvement in the dielectric response.     

Oriented Lead Titanate Film Growth at Lower Temperatures by the Sol-Gel Method on Particle-Seeded Substrates

An approach to fabricate lead titanate (PbTiO₃) films with preferred orientation on arbitrary substrates by a sol-gel method was developed. To ensure a preferred crystallographic orientation on the substrates with different crystal structure, well-defined platelet PbTiO₃ particles were used as seeds. Because the basal plane of the platelet-shaped particles was the (001) plane, the particles aligned with the c-axis perpendicular to the substrates. During crystallization of the sol-gel PbTiO₃ films on the particle-seeded substrate, preferential nucleation occurred on seeded particles with the same crystallographic orientation as the particles at a much lower temperature. In the current study, (100) and (001) textured PbTiO₃ films have been produced on various substrate materials such as silicon, silicate glass, indium tin oxide (ITO) glass, and titanium metal at temperatures as low as 275°C. The microstructure of the films was examined by scanning electron microscopy and atomic force microscopy. Limited ferroelectric properties also were determined, to underscore the preferred orientation that was produced in these materials.     

A study on the crystallization behavior of poly(β-hydroxybutyrate) thin films on Si wafers

The exact molecular chain orientation of poly(β-hydroxybutyrate) (PHB) in ultrathin films was successfully probed using surface-sensitive, grazing incidence X-ray diffraction techniques. The crystal orientation of spin-coated PHB films was very sensitive to free surface and thermal annealing. In pristine films, the free surface easily exerted its influence on PHB crystallization and caused lamellar orientation with the b-axis perpendicular to the film surface. The effect of the buried interface increased with temperature. With the increase in thermal annealing temperature, the lamellar orientation changed from the b-axis being perpendicular to the film surface to the c-axis becoming perpendicular to the film surface. As film thickness increased, the temperature, at which the lamellae with the b-axes oriented normal to the film surface disappeared, increased. The thickness and temperature dependence of the crystallization behavior of PHB in an ultrathin film could be attributed to the competition between the effects of the free surface and the buried interface.     

Facile solution deposition of ZnIn2S4 nanosheet films on FTO substrates for photoelectric application

In this paper, ZnIn(2)S(4) perpendicular nanosheet films have been directly deposited on FTO substrates by a facile hydrothermal method and investigated as the electrode materials for solar cells. The crystal structure, morphology, and optical properties of the obtained ZnIn(2)S(4) films were characterized by measurements such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive spectrum (EDS), X-ray photoelectron spectrum (XPS) and UV-vis spectra. The results revealed a uniform perpendicular ZnIn(2)S(4) film with thickness of 4 μm and with an average nanosheet thickness of about 30 nm on FTO substrate, along with the band gap of 2.35 eV. The reaction conditions influencing the formation of ZnIn(2)S(4) films, such as the substrate treatment and reaction time were investigated. A possible mechanism for the formation of ZnIn(2)S(4) films on FTO substrates under hydrothermal conditions has been proposed. Furthermore, after heat treatment, the ZnIn(2)S(4) film electrode exhibited a photoelectrical conversion efficiency of 0.23% in FTO/ZnIn(2)S(4)/polysulfide/Au liquid-junction solar cell under AM 1.5 (100 mW cm(-2)).     

Thermal conductivity of nanocrystalline carbon films studied by pulsed photothermal reflectance

The effect of nanocrystals with preferred orientation on the thermal conductivity of carbon films is studied. During graphitization, the presence of biaxial compressive stress results in the formation of preferred orientation in the microstructure of graphitic nanocrystals if the corresponding activation energy is supplied. This formation of preferred orientation leads to the orientation of graphitic basal planes perpendicular to the substrate. Due to the high thermal conductivity of graphite in the basal planes, there is a significant increase in thermal conductivity of textured nanocrystalline films compared to amorphous film.     

Lamellar arrangements of linear polyethylene in ultrathin films

The crystal orientations of linear polyethylene films on silicon substrates are investigated using grazing incidence X‐ray diffraction and atomic force microscopy. From diffraction analysis, we can identify the structural arrangement of PE crystals in ultrathin film. The orientation of lamellar crystal in PE films changes from edge‐on to flat‐on with the decrease of film thickness in the film thickness below ～ 100 nm. The slightly inclined lamellae relative to the substrate are found to coexist with the flat‐on lamellae in thin PE films that we have investigated. We find that the crystal orientation and structures is governed by the constraint imposed by film thickness rather than enthalpy gain as the film got thinner especially in the thickness below 200 nm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(caprolactone) thin film preparation,morphology, and surface texture

The properties and surface uniformity of poly‐ (caprolactone) (PCL) thin films were measured. Thin films were prepared using a spin‐coating technique. Film thickness and roughness were correlated with variation in solution concentration, spinning speed and spinning time. Differential scanning calorimetry (DSC) was used to investigate the crystallization and melting processes. The enthalpy of melting variation correlated with the film thickness, while melting temperature was independent of film thickness. In addition, surface roughness was found to be a function of PCL thickness. Film thickness and roughness showed a progressive decrease when spinning speed was increased, while spinning time provided no significant influence on film thickness. PCL thickness and roughness significantly increased when PCL solution concentration increased. Hot stage optical microscopy showed that larger spherulitic crystals were present in thin films, and the smaller crystals present in thicker films had a coarser texture consistent with increased surface roughness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1287–1294, 2007     

在玻璃上合成有取向的silicalite-1分子筛膜及其生长机理

引言 分子筛膜具有规则的微孔结构、良好的化学和热稳定性,在气体分离、催化膜反应器、化学传感器以及分子筛改性电极等方面有广泛的应用前景[1-2],是催化和分离新材料领域的研究热点之一.     

Origin of Orientation in Sol-Gel-Derived Lead Titanate Films

The origin of orientation in sol-gel-derived PbTiO₃ films is investigated in detail. Aging of the solution is found to promote (100) orientation of the films. Characterizing the solution by viscometry indicates that the preferred orientation might be attributable to the change of molecular size in the solution. The substrate also influences the film orientation: more strongly (100)-oriented film forms on Pt-coated Si than on fused quartz. Highly c -axis-oriented films with azimuthal orientation are grown on a (100) SrTiO₃ single-crystal disk.     

Preparation of Thin Mullite Films

Aluminosilicate glass films having compositions approximately that of mullite produced by reactive sputtering of aluminum-silicon alloys are discussed. Data are given on the speed of deposition under certain conditions for a variety of metal and ceramic substrates. Mullite crystals with the needle habit are formed from the initial amorphous film by subsequent heat treatment of about 1 hour at temperatures of 1100° to 1400°C. The number and size of the crystals are affected by firing conditions, composition, and thickness of the film and by nucleating agents such as carbon on the surface of the film as indicated by transmission electron micrographs of unsupported films. The reaction of the oxide films with some supporting ceramic substrates has also been studied.     

Model of morphology evolution in the growth of polycrystalline β-SiC films

The growth of β-SiC films via chemical vapor deposition (CVD) has been under intensive investigation because this is viewed to be an enabling material for a variety of new semiconductor devices in areas where silicon cannot effectively compete. However, the difficulty in achieving single-crystal or highly textured surface morphology in films with low bulk defect density has limited the use of β-SiC films in electronic devices. Although several researchers have reported results relating the morphology of β-SiC films to deposition parameters, including substrate temperature and gas composition, detailed knowledge of the effects of deposition parameters on film morphology and crystallographic texture is still lacking. If these relationships between deposition parameters and film morphology can be quantified, then it may be possible to obtain optimal β-SiC film morphologies via CVD for specific applications such as high-power electronic devices.The purpose of this study is to predict the dependence of the surface morphology of β-SiC films grown by CVD on substrate temperature and inlet atom ratio of Si:C, and to model the morphological evolution of the growing polycrystalline film. The Si:C ratio is determined by the composition of the reactant gases, propane (C₃H₈) and silane (SiH₄). A two-dimensional numerical model based on growth rate parameters has been developed to predict the evolution of the surface morphology. The model calculates the texture, surface roughness, and grain size of continuous polycrystalline β-SiC films resulting from growth competition between nucleated seed crystals of known orientation. Crystals with the fastest growth direction perpendicular to the substrate surface are allowed to overgrow all other crystal orientations. When a continuous polycrystalline film is formed, the facet orientations of crystals are represented on the surface. In the model, the growth parameter α_2D, the ratio of the growth rates of the {10} and {11} faces, determines the crystal shapes and, thus, the facet orientations of crystals. The growth rate parameter α_2D used in the model has been derived empirically from the textures of continuous β-SiC films reported in the literature.     

An investigation of optical clarity and crystalline orientation in polyethylene tubular film

A study of the crystalline orientation, light transmission, and surface roughness of polyethylene tubular film prepared in our laboratories is presented. The present studies were primarily carried out on low-density (LDPE) and linear-low-density (LLDPE) polyethylene films. The optical properties of a few films of high-density polyethylene (HDPE) prepared for a previous study of morphology were characterized for comparison to the LDPE and LLDPE films. Wide angle X-ray diffraction and birefringence were used to characterize orientation. Both the LDPE and LLDPE films exhibited crystalline texture in which the b-axes tended to be perpendicular to the film surface and the a-axes had some tendency to align with the machine direction. The c-axes tended to be concentrated in the plane of the film with nearly equal biaxial orientation with respect to the machine and transverse directions. Little variation in the crystalline orientation was found with changes of process conditions in the range studied. Birefringence results indicate that the amorphous regions developed an orientation in which the chains tend to be normal to the film surface. The majority of light scattering from these films and a series of HDPE films was from the surface and not from the film interior. The transmission coefficient for the surface contribution was found to be a monotonic decreasing function of the standard deviation of the surface height obtained from surface profiles measured by profilometer. The surface asperites were largest for the HDPE and smallest for the LDPE samples. The intensity of both the surface and interior contributions to the scattering increased with increasing frostline height, i.e., a slower cooling rate. As draw-down ratio and blow-up ratio increase the scattering contribution from the film interior decreases but the contribution from the surface increases somewhat. These effects are discussed in terms of the changes in crystalline morphology and surface roughness produced by flow defects generated during extrusion.     

New Experimental Approaches for the Study of Polymer/Metal Interphases

In this short review we present recent experiments which can be used to infer the structural parameters of ultrathin polyimide and polyamide acid films as a function of distance from the substrate surface. The polyimide films are prepared by the Langmuir-Blodgett technique in a layer-by-layer fashion, and the orientation of the pyromellitic imide unit in the polyimide macromolecules is determined as a function of film thickness by Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. Subsequent delamination experiments on these Langmuir-Blodgett (LG) deposited polyimide films reveal that the locus of failure does not occur in a “weak boundary-layer” adjacent to the silicon substrate as expected from delamination experiments with macroscopically thick films.

As a non-destructive method to study the orientation of polymer molecules during film growth, second harmonic generation (SHG) experiments on the deposition of polyamide acid (PAA) on gold and silver surfaces will be briefly described. In this particular case, the experiments reveal an influence on the interfacial chemical bond on the film structure up to a total thickness of 60-100 mm.     

In situ growth of AlPO4-5 molecular sieve on stainless steel support

A continuous coating on stainless steel mesh with AFI-type molecular sieve was achieved by a simple one-step in situ synthesis. AlPO₄-5 crystals have been grown directly on the surface of the substrate. Influences of composition of the staring reaction solution and crystallization temperature on the morphology and the orientation of crystals on the support were investigated. It was shown that the crystals in the coating grew along their one-dimensional channel perpendicular to the substrate when using the synthesis solution with the molar ratio of Al₂O₃:1.3P₂O₅:1.2TrEA:200H₂O. Stainless steel slice was also used as the substrate to study the growth of molecular sieve AlPO₄-5 film at similar synthesis conditions. A competitive growth model was implied to explain the formation of c-axis oriented film based on the observations. The supported coatings were characterized by scanning electron microscopy and X-ray diffractions.     

Synthesis and evaluation of ZSM-5 films on cordierite monoliths

Well-defined ZSM-5 films were prepared on cordierite monoliths using the seed film method. The monoliths were seeded with silicalite-1 seeds and hydrothermally treated either at 75 or at 150 °C in a single or several steps. By adding sodium hydroxide to the solution, the aluminum concentration in the zeolite increased. Consequently, films with different Si/Al ratios were prepared. The film thickness could be controlled from 110 nm to 9 μm. Multi-step synthesis was used to prevent bulk crystallization and ultrasound treatment was found to be beneficial (in order) to remove sedimented crystals on the top of the coatings. The zeolite-coated monoliths were active for p-xylene isomerization, and the test results indicated that the films became less deactivated than the films prepared on alumina beads.     

Effects of atomic layer deposition conditions on the formation of thin ZnO films and their photocatalytic characteristics

The use of photocatalysts in water treatment systems is regarded as an advanced technology. To ensure efficiency and stability, the optimization of photocatalyst immobilization is essential for application in water treatment processes. In this study, we investigated the effect of atomic layer deposition (ALD) conditions on the development of highly photocatalytically active thin ZnO films. Three different temperatures and three ALD cycles were employed to evaluate the photocatalytic activity of thin ZnO films (represented by the production rate of reactive oxygen species and the degradation rate of methylene blue). We found that the surface properties of the thin ZnO films, such as grain size and homogeneity, exerted a dominant influence on the photocatalytic activity. At a low temperature (50 °C), nanograins were not formed properly, while various nanograin shapes were obtained at a high temperature (250 °C). The optimized grain had a grain size of 20 nm and a (002)/(101) crystalline orientation ratio of 2.2. The UV light absorption increased in proportion to the film thickness, and a minimum film thickness (50 nm) was necessary to ensure high photocatalytic activity at the film surface. In addition, the increase in the photocatalytic activity was not significant as the thickness increased beyond the optimum thickness. These results will provide useful guidelines for the fabrication of thin ZnO films with excellent photocatalytic activity for water treatment.     

Effect of TiO2 thin film thickness and specific surface area by low-pressure metal–organic chemical vapor deposition on photocatalytic activities

TiO₂ photocatalyst films having an anatase crystal structure with different thickness were prepared by the low-pressure metal–organic chemical vapor deposition (LPMOCVD) to examine the effect of growth conditions on photocatalytic activity. Film thickness was linearly proportional to the deposition time. Structure of the film was strongly dependent on the deposition time. In early stage of deposition, fine particles deposit on the substrate. As increasing the deposition time, crystal orientation is gradually selected following the Kolmogorov model and c-axis oriented columnar crystals become dominant. The photocatalytic activity strongly depends on the film deposition time (or film thickness) in nonlinear way. The optimum thickness of TiO₂ catalyst film grown by LPMOCVD may locate between 3 and 5 μm.