Incorporation of niobium in SAPO-11 materials: Synthesis and characterization

The present work concerns a new synthesis approach to prepare niobium based SAPO materials with AEL structure and the characterization ofNb species incorporated within the inorganic matrixes. The SAPO-11 materials were synthesized with or without the help of a small amine, methylamine (MA) as co-template, while Nb was added directly during the preparation of the initial gel. Structural, textural and acidic properties of the different supports were evaluated by XRD, TPR, UV-Vis spectroscopy, pyridine adsorption followed by IR spectroscopy and thermal analyses. Pure and well crystalline Nb based SAPO-11 materials were obtained, either with or without MA, using in the initial gel a low Si content of about 0.6. Increasing the Si content of the gel up to 0.9 led to an important decrease of the samples crystallinity. Niobium was found to incorporate the AEL pores support as small Nb2O5 oxide particles and also as extra framework cationic species (Nb5+), compensating the negative charges from the matrix and generating new Lewis acid sites. (C) 2011 Elsevier Inc. All rights reserved.

Estudo das alterações no comportamento catalítico do zeólito MCM-22 por modificação controlada da porosidade

Este trabalho experimental teve como objetivo o estudo da influência dos tratamentos de dessilicação e combinação do tratamento alcalino seguido de tratamento ácido aplicado ao zeólito MCM-22, utilizando duas concentrações diferentes de solução de NaOH. O zeólito MCM-22 sintetizado e todas as amostras modificadas foram caraterizadas por difração de raios-X, RMN de 29Si e 27Al, SEM, TEM e adsorção de azoto a baixa temperatura. O estudo da acidez das amostras foi realizado por adsorção de piridina seguida de espetroscopia de infravermelho e análise da região dos grupos hidroxilo. Para avaliar a influência dos tratamentos pós-síntese na acidez e porosidade recorreu-se à reação catalítica modelo de isomerização de m-xileno. O desenvolvimento de mesoporosidade foi conseguido por meio de tratamento alcalino com a solução de NaOH de 0,05 M, não tendo sido obtido nenhum ganho adicional com o uso da solução de concentração 0,1 M. Observa-se contudo que nestas condições experimentais a extração de Si é realizada juntamente com a de Al da rede que fica depositado, como espécies extra-rede. As amostras submetidas aos tratamentos alcalino e ácido sequenciais apresentam comportamentos distintos. Quando foi usada a solução alcalina de menor concentração não se observou nenhum efeito relevante nas propriedades texturais. Pelo contrário, quando o tratamento ácido foi realizado sobre a estrutura mais fragilizada, devido à dessilicação com a solução alcalina mais concentrada, a extração de Al a partir de ambos os sistemas porosos internos promoveu a sua interligação, evoluindo-se de uma estrutura 2-D para uma estrutura 3-D. Por outro lado, a deposição contínua de espécies de Al extra-rede no interior dos poros leva a um aumento de seletividade de forma, que se traduz na formação preferencial do isómero de xileno mais importante a nível comercial, o p-xileno.

Modifications of MCM-22 zeolite through sequential post-synthesis treatments. Implications on the acidic and catalytic behaviour

Desilication and a combination of alkaline followed by acid treatment were applied to MCM-22 zeolite using two different base concentrations. The samples were characterised by powder X-ray diffraction, Al-27 and Si-29 MAS-NMR spectroscopy, SEM, TEM and low temperature N-2 adsorption. The acidity of the samples was study through pyridine adsorption followed by FTIR spectroscopy and by the analyses of the hydroxyl region. The catalytic behaviour, anticipated by the effect of post-synthesis treatments on the acidity and space available inside the two internal pore systems was evaluated by using the model reaction of m-xylene transformation. The generation of mesoporosity was achieved upon alkaline treatment with 0.05 M NaOH solution and practically no additional gain was obtained when the more concentrate solution, 0.1 M, was used. Instead, Al extraction takes place along with Si, as shown by Si-29 and Al-27 MAS-NMR data, followed by Al deposition as extraframework species. Samples submitted to alkaline plus acid treatments present distinct behaviour. When the lowest NaOH solution was used no relevant effect was observed on the textural characteristics. Additionally, when the acid treatment was performed on an already fragilized MCM-22 structure, due to previous desilication with 0.1 M NaOH solution, the extraction of Al from both internal pore systems promotes their interconnection, evolving from a 2-D to a 3-D porous structure. This transformation has a marked effect in the catalytic behaviour, allowing an increase of m-xylene conversion as a consequence of an easier and faster molecular traffic in the 3-D structure. On the other hand, the continuous deposition of extraframework Al species inside the pores leads to a shape selective effect that privileges the formation of the more valuable isomer p-xylene.

n-Hexane hydroisomerisation over bifunctional Pt/MCM-22 catalysts. Influence of the mode of Pt introduction

Three different methods were used to introduce 1.0 wt.% of Pt in bifunctional Pt/MCM-22 zeolite catalysts: ion exchange with Pt(NH3)(4)(2+), incipient wetness impregnation with PtCl6H2 and mechanical mixture with Pt/Al2O3. The Pt dispersion was estimated by transmission electron microscopy and the hydrogenating activity with toluene hydrogenation at 110 degrees C. From these experiments, it can be concluded that with the ion exchanged sample, platinum was located within the inner micropores and on the outer surface, whereas with the impregnated one, platinum was essentially on the outer surface under the form of large particles. With all the samples there is a fast initial decrease in the activity for n-hexane hydroisomerisation at 250 degrees C. With exchanged and impregnated samples, this decrease is followed by a plateau, the activity value being then higher with impregnated sample. For the sample prepared by mechanical mixture a continuous decrease in activity can be observed. All these differences can be related with the distinct locations of Pt.

Field effect and light-assisted a-Si:H sensors for detection of ions in solution

In this paper we present an amorphous silicon device that can be used in two operation modes to measure the concentration of ions in solution. While crystalline devices present a higher sensitivity, their amorphous counterpart present a much lower fabrication cost, thus enabling the production of cheap disposable sensors for use, for example, in the food industry. The devices were fabricated on glass substrates by the PECVD technique in the top gate configuration, where the metallic gate is replaced by an electrolytic solution with an immersed Ag/AgCl reference electrode. Silicon nitride is used as gate dielectric enhancing the sensitivity and passivation layer used to avoid leakage and electrochemical reactions. In this article we report on the semiconductor unit, showing that the device can be operated in a light-assisted mode, where changes in the pH produce changes on the measured ac photocurrent. In alternative the device can be operated as a conventional ion selective field effect device where changes in the pH induce changes in the transistor's threshold voltage.

Phototransistor with nanocrystalline Si/amorphous Si bilayer channel

We report a field-effect phototransistor with a channel comprising a thin nanocrystalline silicon transport layer and a thicker hydrogenated amorphous silicon absorption layer. The semiconductor and dielectric layers were deposited by radio-frequency plasma enhanced chemical vapor deposition. The phototransistor with channel length of 24 microns and photosensitive area of 1.4 mm(2) shows an off-current of about 1 pA, and high photoconductive gain in the subthreshold region. Measurements of the quantum efficiency at different incident light intensities and biasing conditions, along with spectral-response characteristics, and threshold voltage stability characterization demonstrate the feasibility of the phototransistor for low light level detection.

Nanocrystalline p-layer for a-Si:H p-i-n solar cells and photodiodes

We report on structural, electronic, and optical properties of boron-doped, hydrogenated nanocrystalline silicon (nc-Si:H) thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) at a substrate temperature of 150 degrees C. Film properties were studied as a function of trimethylboron-to-silane ratio and film thickness. The absorption loss of 25% at a wavelength of 400 nm was measured for the 20 nm thick films on glass and glass/ZnO:Al substrates. By employing the p(+) nc-Si:H as a window layer, complete p-i-n structures were fabricated and characterized. Low leakage current and enhanced sensitivity in the UV/blue range were achieved by incorporating an a-SiC:H buffer between the p- and i-layers.

A 3-phase model for VIS/NIR mu C-Si : H p-i-n detectors

The spectral response and the photocurrent delivered by entirely microcrystalline p-i-n-Si:H detectors an analysed under different applied bias and light illumination conditions. The spectral response and the internal collection depend not only on the energy range but also on the illumination side. Under [p]- and [n]-side irradiation, the internal collection characteristics have an atypical shape. It is high for applied bias and lower than the open circuit voltage, shows a steep decrease near the open circuit voltage (higher under [n]-side illumination) and levels off for higher voltages. Additionally, the numerical modeling of the VIS/NIR detector, based on the band discontinuities near the grain boundaries and interfaces, complements the study and gives insight into the internal physical process.

Bias dependent photocurrent collection in p-i-n a-Si : EVSiC : H heterojunction

A series of large area single layers and heterojunction cells in the assembly glass/ZnO:Al/p (SixC1-x:H)/i (Si:H)/n (SixC1-x:H)/Al (0

Bias-dependent photocurrent collection in p-i-n a-Si : H/SiC : H heterojunction

A series of large area single layers and glass/ZnO:AVp(SixC1-x:H)/i(Si:H)/n(SixC1-x:H)/AI (0 < x < 1) heterojunction cells were produced by plasma-enhanced chemical vapour deposition (PE-CVD) at low temperature. Junction properties, carrier transport and photogeneration are investigated from dark and illuminated current-voltage (J-V) and capacitance-voltage (C-V) characteristics. For the heterojunction cells atypical J-V characteristics under different illumination conditions are observed leading to poor fill factors. High series resistances around 106 Q are also measured. These experimental results were used as a basis for the numerical simulation of the energy band diagram, and the electrical field distribution of the structures. Further comparison with the sensor performance gave satisfactory agreement. Results show that the conduction band offset is the most limiting parameter for the optimal collection of the photogenerated carriers. As the optical gap increases and the conductivity of the doped layers decreases, the transport mechanism changes from a drift to a diffusion-limited process.

Enhanced short wavelength response in laser-scanned-photodiode image sensor using an a-SiC : H/a-Si : H tandem structure

We report in this paper the recent advances we obtained in optimizing a color image sensor based on the laser-scanned-photodiode (LSP) technique. A novel device structure based on a a-SiC:H/a-Si:H pin/pin tandem structure has been tested for a proper color separation process that takes advantage on the different filtering properties due to the different light penetration depth at different wavelengths a-SM and a-SiC:H. While the green and the red images give, in comparison with previous tested structures, a weak response, this structure shows a very good recognition of blue color under reverse bias, leaving a good margin for future device optimization in order to achieve a complete and satisfactory RGB image mapping. Experimental results about the spectral collection efficiency are presented and discussed from the point of view of the color sensor applications. The physics behind the device functioning is explained by recurring to a numerical simulation of the internal electrical configuration of the device.

ITO/SiOx/Si optical sensor with internal gain

A visible/near-infrared optical sensor based on an ITO/SiOx/n-Si structure with internal gain is presented. This surface-barrier structure was fabricated by a low-temperature processing technique. The interface properties and carder transport were investigated from dark current-voltage and capacitance-voltage characteristics. Examination of the multiplication properties was performed under different light excitation and reverse bias conditions. The spectral and pulse response characteristics are analysed. The current amplification mechanism is interpreted by the control of electron current by the space charge of photogenerated holes near the SiOx/Si interface. The optical sensor output characteristics and some possible device applications are presented.

New p-i-n Si : H imager configuration for spatial resolution improvement

Amorphous glass/ZnO-Al/p(a-Si:H)/i(a-Si:H)/n(a-Si1-xCx:H)/Al imagers with different n-layer resistivities were produced by plasma enhanced chemical vapour deposition technique (PE-CVD). An image is projected onto the sensing element and leads to spatially confined depletion regions that can be readout by scanning the photodiode with a low-power modulated laser beam. The essence of the scheme is the analog readout, and the absence of semiconductor arrays or electrode potential manipulations to transfer the information coming from the transducer. The influence of the intensity of the optical image projected onto the sensor surface is correlated with the sensor output characteristics (sensitivity, linearity blooming, resolution and signal-to-noise ratio) are analysed for different material compositions (0.5 < x < 1). The results show that the responsivity and the spatial resolution are limited by the conductivity of the doped layers. An enhancement of one order of magnitude in the image intensity signal and on the spatial resolution are achieved at 0.2 mW cm(-2) light flux by decreasing the n-layer conductivity by the same amount. A physical model supported by electrical simulation gives insight into the image-sensing technique used.

Optical Transducers Based on Amorphous Si/SiC Photodiodes

Amorphous Si/SiC photodiodes working as photo-sensing or wavelength sensitive devices have been widely studied. In this paper single and stacked a-SiC:H p-i-n devices, in different geometries and configurations, are reviewed. Several readout techniques, depending on the desired applications (image sensor, color sensor, wavelength division multiplexer/demultiplexer device) are proposed. Physical models are presented and supported by electrical and numerical simulations of the output characteristics of the sensors.

Photodiode with nanocrystalline Si/amorphous Si absorber bilayer

This letter reports a near-ultraviolet/visible/near-infrared n(+)-n-i-delta(i)-p photodiode with an absorber comprising a nanocrystalline silicon n layer and a hydrogenated amorphous silicon i layer. Device modeling reveals that the dominant source of reverse dark current is deep defect states in the n layer, and its magnitude is controlled by the i layer thickness. The photodiode with the 900/400 nm thick n-i layers exhibits a reverse dark current density of 3nA/cm(2) at -1V. Donor concentration and diffusion length of holes in the n layer are estimated from the capacitance-voltage characteristics and from the bias dependence of long-wavelength response, respectively. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3660725]