Study on growth mechanism of low-temperature prepared microcrystalline Si thin films

Microcrystalline silicon thin films at different growth stages were prepared by hot wire chemical vapor deposition. Atomic force microscopy has been applied to investigate the evolution of surface topography of these films. According to the fractal analysis I it was found that, the growth of Si film deposited on glass substrate is the zero-diffused stochastic deposition; while for the film on Si substrate, it is the finite diffused deposition on the initial growth stage, and transforms to the zero-diffused stochastic deposition when the film thickness reaches a certain value. The film thickness dependence of island density shows that a maximum of island density appears at the critical film thickness for both substrates. The data of Raman spectra approve that, on the glass substrate, the a-Si: H/mu c-Si:H transition is related to the critical film thickness. Different substrate materials directly affect the surface diffusion ability of radicals, resulting in the difference of growth modes on the earlier growth stage.

Effects of different modified underlayer surfaces on growth and optical properties of InGaN quantum dots

InGaN/GaN quantum dots were grown on the sapphire (0 0 0 1) substrate in a metalorganic chemical vapor deposition system. The morphologies of QDs deposited on different modified underlayer (GaN) surfaces, including naturally as grown, Ga-mediated, In-mediated, and air-passivated ones, were investigated by atomic force microscopy (AFM). Photo luminescence (PL) method is used to evaluate optical properties. It is shown that InGaN QDs can form directly on the natural GaN layer. However, both the size and distribution show obvious inhomogeneities. Such a heavy fluctuation in size leads to double peaks for QDs with short growth time, and broad peaks for QDs with long growth time in their low-temperature PL spectra. QDs grown on the Ga-mediated GaN underlayer tends to coalesce. Distinct transform takes place from 3D to 2D growth on the In-mediated ones, and thus the formation of QDs is prohibited. Those results clarify Ga and In's surfactant behavior. When the GaN underlayer is passivated in the air, and together with an additional low-temperature-grown seeding layer, however, the island growth mode is enhanced. Subsequently, grown InGaN QDs are characterized by a relatively high density and an improved Gaussian-like distribution in size. Short surface diffusion length at low growth temperature accounts for that result. It is concluded that reduced temperature favors QD's 3D growth and surface passivation can provide another promising way to obtain high-density QDs that especially suits MOCVD system. (c) 2004 Elsevier Ltd. All rights reserved.

Ordered InAs quantum dots with controllable periods grown on stripe-patterned GaAs substrates

GaAs (001) substrates are patterned by electron beam lithography and wet chemical etching to control the nucleation of InAs quantum dots (QDs). InAs dots are grown on the stripe-patterned substrates by solid source molecular beam epitaxy, A thick buffer layer is deposited on the strip pattern before the deposition of InAs. To enhance the surface diffusion length of the In atoms, InAs is deposited with low growth rate and low As pressure. The AFM images show that distinct one-dimensionally ordered InAs QDs with homogeneous size distribution are created, and the QDs preferentially nucleate along the trench. With the increasing amount of deposited InAs and the spacing of the trenches, a number of QDs are formed beside the trenches. The distribution of additional QDs is long-range ordered, always along the trenchs rather than across the spacing regions.

Atomic hydrogen induced step bunching and fabrication of quantum wire arrays on GaAs (311)A substrate by molecular beam epitaxy

Atomic hydrogen assisted molecular beam epitaxy (MBE) is a novel type of epitaxial growth of nanostructures. The GaAs (311)A surface naturally forms one-dimensional step arrays by step bunching along the direction of (-233) and the space period is around 40nm. The step arrays extend over several mum without displacement. The InGaAs quantum wire arrays are grown on the step arrays as the basis. Our results may prompt further development of more uniform quantum wire and quantum dot arrays.

Smaller Ge Quantum Dots Obtained by ArF Excimer Laser Annealing

Ge self-assembled quantum dots (SAQDs) are grown with a self-assembled UHV/CVD epitaxy system. Then,the as-grown Ge quantum dots are annealed by ArF excimer laser. In the ultra-shot laser pulse duration,～20ns, bulk diffusion is forbidden, and only surface diffusion occurs, resulting in a laser induced quantum dot (LIQD). The diameter of the LIQD is 20～25nm which is much smaller than the as-grown dot and the LIQD has a higher density of about 6 × 10~(10)cm~(-2). The surface morphology evolution is investigated by AFM.

Two- and three-dimensional Au nanoparticle/CoTMPyP self-assembled nanotructured materials: Film structure, tunable electrocatalytic activity, and plasmonic properties

Two- and three-dimensional Au nanoparticle/[tetrakis(N-methylpyridyl)porphyrinato]cobalt (CoTMPyP) nanostructured materials were prepared by "bottom-up" self-assembly. The electrocatalytic and plasmonic properties of the Au nanoparticle/CoTMPyP self-assembled nanostructured materials (abbreviated as Au/CoTMPyP SANMs) are tunable by controlled self-assembly of the An nanoparticles and CoTMPyP on indium tin oxide (ITO) electrode. The electrocatalytic activity of the Au/CoTMPyP SANMs can be tuned in two ways. One way is that citrate-stabilized An nanoparticles are positioned first on ITO surface with tunable number density, and then positively charged CoTMPyP ions are planted selectively on these gold sites. The other way is that An nanoparticles and CoTMPyP are deposited by virtue of layer-by-layer assembly, which can also tune the amount of the as-deposited electrocatalysts. FE-SEM studies showed that three-dimensional SANMs grow in the lateral expansion mode, and thermal annealing resulted in both surface diffusion of nanoparticles and atomic rearrangement to generate larger gold nanostructures with predominant (I 11) facets.

In-situ FT-IR spectroscopic studies of fuel cell electro-catalysis: From single-crystal to nanoparticle surfaces

The work presented in this article shows the power of the variable temperature, in-situ FT-IR spectroscopy system developed in Newcastle with respect to the investigation of fuel cell electro-catalysis. On the Ru(0001) electrode surface, CO co-adsorbs with the oxygen-containing adlayers to form mixed [CO+(2x2)-O(H)] domains. The electro-oxidation of the Ru(0001) surface leads to the formation of active (1x1)-O(H) domains, and the oxidation of adsorbed CO then takes place at the perimeter of these domains. At 20 degrees C, the adsorbed CO is present as rather compact islands. In contrast, at 60 degrees C, the COads is present as a relatively looser and weaker adlayer. Higher temperature was also found to facilitate the surface diffusion and oxidation of COads. No dissociation or electro-oxidation of methanol was observed at potentials below approximately 950mV; however, the Ru(0001) surface at high anodic potentials was observed to be very active. On both Pt and PtRu nanoparticle surfaces, only one linear bond CO adsorbate was formed from methanol adsorption, and the PtRu surface significantly promoted both methanol dissociative adsorption to CO and its further oxidation to CO2. Increasing temperature from 20 to 60 degrees C significantly facilitates the methanol turnover to CO2.

Caracterização de novas membranas de titanossilicatos microporosos por ensaios de permeabilidade

O interesse crescente das membranas inorgânicas deve-se à potencial aplicação em novas áreas de investigação e da indústria, e em alternativa a operações mais convencionais. Em particular, as membranas de titanossilicatos oferecem vantagens importantes sobre as de zeólitos, pois podem ser sintetizadas sem agentes estruturantes orgânicos, para evitar a calcinação subsequente usualmente responsável por defeitos irreversíveis, exibem novas possibilidades de substituição isomórfica da matriz, permitindo um ajuste mais fino das propriedades catalíticas e de adsorção, e são capazes de separar misturas com base em diferenças de afinidade e tamanho molecular (efeito de peneiro). Os objectivos principais deste trabalho foram: i) a caracterização dinâmica de membranas do tipo zeolítico sintetizadas no Laboratório Associado CICECO, realizando-se experiências de permeação com gases puros e misturas; ii) o desenvolvimento e validação de novos modelos para a transferência de massa multicomponente através de membranas porosas pela abordagem de Maxwell-Stefan, tendo em conta os mecanismos específicos encontrados, particularmente a contribuição por difusão superficial; e iii) a modelação dos pontos experimentais medidos, bem como dados compilados da literatura. De forma a realizar os ensaios de permeação, desenhou-se, montou-se e testou-se uma instalação experimental. Para gases puros, os objectivos principais foram a medição de permeâncias a temperatura constante, por variação da pressão transmembranar r ( ΔP ), e de permeâncias a temperatura programada, conduzidas a ΔP constante. Seguidamente, calcularam-se as selectividades ideais. Em relação a misturas, a determinação de selectividades reais requer as fracções molares no permeado e no retido. Na globalidade, estudaram-se três suportes diferentes (aço inoxidável e α − alumina) e dezanove membranas de AM-3, ETS-10, ZSM-5 e zeólito 4A, utilizando-se H2, He, N2, CO2, e O2. A primeira avaliação exploratória da qualidade das membranas foi feita permeando azoto à temperatura ambiente. Assim, permeâncias superiores a 10−6 mol/m2s.Pa evidenciavam defeitos grosseiros, levando-nos a efectuar cristalizações adicionais sobre as primeiras camadas. Este procedimento foi implementado com oito membranas. Um trabalho experimental mais detalhado foi conduzido com cinco membranas. Membranas com curvas permeância-temperatura ( Π −T ) decrescentes indicam tipicamente transporte viscoso e de Knudsen, i.e. meso e macrodefeitos. Por exemplo, a membrana nº 3 de AM-3 exibiu este comportamento com H2, He, N2 e CO2 puros. A contribuição de Knudsen foi confirmada pela relação linear encontrada entre as permeâncias e o inverso da raiz quadrada da massa molar. O mecanismo viscoso foi também identificado, pois as permeâncias eram inversamente proporcionais à viscosidade do gás ou, atendendo a equações do tipo de Chapman-Enskog, directamente proporcionais a 2 0.5 k d M (onde k d é o diâmetro cinético e M a massa molar). Um comportamento de permeação distinto observou-se com a membrana nº 5 de AM-3. As permeâncias registadas a temperatura programada eram aproximadamente constantes para o N2, CO2 e O2, enquanto com o H2 cresciam significativamente. Conjuntamente elas evidenciam a ocorrência de macro, meso e microdefeitos intercristalinos. O transporte gasoso activado através dos microporos compensa o impacto diminuidor dos meso e macroporos. Ao contrário do N2, CO2 e O2, o pequeno diâmetro do hidrogénio torna-lhe possível permear através dos microporos intracristalinos, o que lhe adiciona um mecanismo de transferência responsável por esse crescimento. No que respeita à difusão superficial, o sistema CO2/ZSM-5 pode ser tomado como um exemplo paradigmático. Uma vez que este zeólito adsorve o CO2, as permeâncias diminuem com o crescimento de ΔP , em virtude de as concentrações no sólido aumentarem de forma não linear e tenderem para a saturação. Os resultados contrastantes obtidos com azoto realçam ainda mais o mecanismo superficial, pois o N2 não é adsorvido e as permeâncias medidas são constantes. Globalmente, as selectividades ideais calculadas ( α* ) variam de cerca de 1 a 4.2. Este parâmetro foi também utilizado para discriminar as melhores membranas, uma vez que baixos valores de α* denotam o escoamento viscoso não-selectivo típico de macrodefeitos. Por exemplo, o H2/CO2 na membrana nº 3 de AM-3 apresentou α* = 3.6 − 4.2 para 40–120ºC, enquanto que na membrana nº 5 de AM-3 originou α* = 2.6 − 3.1. Estes resultados corroboraram as observações anteriores, segundo as quais a membrana nº 5 era melhor do que a nº 3. Alguns ensaios foram realizados com membranas saturadas com água para aumentar a selectividade: as medições mostraram claramente uma melhoria inicial seguida de uma redução consistente de α* com o aumento da temperatura, devido à remoção das moléculas de água responsáveis pela obstrução de alguns poros. Em relação às selectividades reais de misturas contendo hidrogénio, devem ser realizadas mais experiências e a quantificação do hidrogénio deve ser melhorada. No que concerne à modelação, novos factores termodinâmicos de Maxwell- Stefan foram derivados para as isotérmicas mono e multicomponente de Nitta, Langmuir-Freundlich e Toth, tendo sido testadas com dados de equilíbrio e de permeação da literatura. (É importante realçar que só estão publicadas equações para Langmuir e Dual-Site Langmuir de componentes puros e misturas). O procedimento de validação adoptado foi exigente: i) as isotérmicas multicomponente foram previstas a partir das de gás puro; ii) os parâmetros de difusão dos componentes puros foram ajustados a dados de permeação de cada gás; iii) depois, as difusividades cruzadas de Maxwell- Stefan foram estimadas pela relação de Vignes; finalmente, v) as novas equações foram testadas usando-se estes parâmetros, tendo sido capazes de estimar com sucesso fluxos binários. Paralelamente ao enfoque principal do trabalho, derivou-se um novo modelo para permuta iónica em materiais microporosos baseado nas equações de Maxwell-Stefan. Este foi validado com dados experimentais de remoção de Hg2+ e Cd2+ de soluções aquosas usando ETS-4. A sua capacidade preditiva foi também avaliada, sendo possível concluir que se comporta muito bem. Com efeito, conseguiram-se boas previsões com parâmetros optimizados a partir de conjuntos de dados independentes. Este comportamento pode ser atribuído aos princípios físicos sólidos da teoria de Maxwell-Stefan.

New insights on growth mechanisms of protein clusters at surfaces: an AFM and simulation study

Despite its relevance to a wide range of technological and fundamental areas, a quantitative understanding of protein surface clustering dynamics is often lacking. In inorganic crystal growth, surface clustering of adatoms is well described by diffusion-aggregation models. In such models, the statistical properties of the aggregate arrays often reveal the molecular scale aggregation processes. We investigate the potential of these theories to reveal hitherto hidden facets of protein clustering by carrying out concomitant observations of lysozyme adsorption onto mica surfaces, using atomic force microscopy. and Monte Carlo simulations of cluster nucleation and growth. We find that lysozyme clusters diffuse across the substrate at a rate that varies inversely with size. This result suggests which molecular scale mechanisms are responsible for the mobility of the proteins on the substrate. In addition the surface diffusion coefficient of the monomer can also be extracted from the comparison between experiments and simulations. While concentrating on a model system of lysozyme-on-mica, this 'proof of concept' study successfully demonstrates the potential of our approach to understand and influence more biomedically applicable protein-substrate couples.

Carbon nanotubes formed in graphite after mechanical grinding and thermal annealing

Multi-walled carbon nanotubes with cylindrical and bamboo-type structures are produced in a graphite sample after mechanical milling at ambient temperature and subsequent thermal annealing up to 1400 °C. The ball milling produces a precursor structure and the thermal annealing activates the nanotube growth. Different nanotubular structures indicate different formation mechanisms: multi-wall cylindrical carbon nanotubes are probably formed upon micropores and the bamboo tubes are produced because of the metal catalysts. A two-dimensional growth governed by surface diffusion is believed to be one important factor for the nanotube growth. A potential industrial production method is demonstrated with advantages of large production quantity and low cost.

Growth and structure of prismatic boron nitride nanorods

Prismatic boron nitride nanorods have been grown on single crystal silicon substrates by mechanical ball-milling followed by annealing at 1300 °C. Growth takes place by rapid surface diffusion of BN molecules, and follows heterogeneous nucleation at catalytic particles of an Fe/Si alloy. Lattice imaging transmission electron microscopy studies reveal a central axial row of rather small truncated pyramidal nanovoids on each nanorod, surrounded by three basal planar BN domains which, with successive deposition of epitaxial layers adapt to the void geometry by crystallographic faceting. The bulk strain in the nanorods is taken up by the presence of what appear to be simple nanostacking faults in the external, near-surface domains which, like the nanovoids are regularly repetitive along the nanorod length. Growth terminates with a clear cuneiform tip for each nanorod. Lateral nanorod dimensions are essentially determined by the size of the catalytic particle, which remains as a foundation essentially responsible for base growth. Growth, structure, and dominating facets are shown to be consistent with a system which seeks lowest bulk and surface energies according to the well-known thermodynamics of the capillarity of solids.

A novel approach for real mass transformation from V2O5 particles to nanorods

A solid-state, mass-quantity transformation from V2O5 powders to nanorods has been realized via a two-step approach. The nanorods were formed through a controlled nanoscale growth from the nanocrystalline V2O5 phase created by a ball milling treatment. The nanorods grow along the [010] direction and are dominated by {001} surfaces. Surface energy minimization and surface diffusion play important roles in their growth mechanism. Real large quantity production can be achieved when the annealing process is conducted in a fluidized bed which can treat large quantities of the milled materials at once. The crystal orientation of nanorods provides an improved cycling stability for lithium intercalation.

One-dimensional growth of TiO2 nanorods from ilmenite sands

Growth mechanisms of TiO₂ nanorods synthesized from mineral ilmenite using ball milling and annealing method have been systematically investigated. Two annealing processes are needed to grow the nanorods. The heating rate and gaseous environment in the first annealing step are critical to the formation of intermediate phases; these and the annealing atmosphere in the second heating play very important roles in nanorod growth. One-dimensional growth of the nanorods induced by low-temperature annealing in nitrogen plus hydrogen is possibly driven by atom vacancy diffusion in addition to surface diffusion.

Síntese e caracterização de membranas zeolíticas tipo mfi e aplicação em separação de aromáticos

The synthesis of MFI-type zeolite membranes was carried by the process in situ or hydrothermal crystallization. We studied the homogenization time of the room temperature and gel filtration just before the crystallization step performed out in an oven, thus obtaining a more uniform zeolite film. The powder synthesized zeolite (structure type MFI, Silicalite) was characterized by several complementary techniques such as Xray diffraction (XRD), scanning electron microscopy (SEM), thermal analysis, temperature programmed desorption (TPD), Fourier Transform infrared spectroscopy (FTIR) and textural analysis by nitrogen adsorption (specific surface area). For the purpose of evaluating the quality of the layer supported on the ceramic support, N2 permeation tests were carried starting from room temperature to 600 °C, where values were observed values more appropriate permeation from 200 °C. With the data obtained, it was made into a graph of temperature versus permeation function, the curve of surface diffusion was found. For scanning electron microscopy, we observed the formation of homogeneous crystals and the zeolite film showed no fissures or cracks, indicating that the process of synthesis and subsequent treatments not damaged the zeolite layer on the support. Carried permeation studies were found values ranging from 3.64x10-6 to 3.78x10-6, 4.71x10-6 to 5.02x10-6, to pressures 20 and 25 psi, respectively. And the mixture xylenes/N2 values were between 5.39x10-6 to 5.67x10-6 and 8.13x10-6 to 8.36x10-6, also for pressures of 20 and 25 psi. The values found for the separation factor were 15.22 at 400 °C in the first experiment and 1.64 for the second experiment at a temperature of 150 °C. It is concluded that the Silicalite membrane was successfully synthesized and that it is effective in the separation of binary mixtures of xylenes