A high resolution photoconductivity investigation of two 13 -3 photon magneto-absorption (TPMA) in n-InSb (n - 9 x 10 cm ) has been performed. This is the first time that two-photon absorption in a semiconductor has been studied with cw lasers only. With a stable cw CC>2 laser and a highly sensitive sampling and magnetic field modulation technique, a minimum of 4 2 transitions in the TPMA photoconductivity spectra can be observed. Most of these transitions are a result of the usual spherical approximation TPMA selections rules (An =0, ±2; As = 0 for e ⊥ B and Δn = 0; Δs = 0 for e || B) . However, some transitions, in particular several near the TPMA band edge, are not explained by these rules. The TPMA spectra have been found to depend upon crystallographic orientation. This has not been previously observed. The temperature variation of the fundamental energy gap Eg between 2 and 100° K is also obtained from TPMA experiments.

Indium antimonide (InSb) and gallium antimonide (GaSb) are technologically important III-V semiconductor materials used in infrared detector systems. Yet, the application of these materials is to a certain extent limited, in that the techniques currently used for their growth are both expensive and problematic. Semiconductor electrochemical deposition, which has been successfully applied to the generation of II-VI semiconductor materials, may offer the prospect of overcoming such limitations. This work presents results that represent a significant contribution to the development of electrochemical methods for both InSb and GaSb thin film growth. The direct electrochemical co-deposition of InSb was achieved via the potentiostatic electrolysis of aqueous halide/citric acid electrolyte solutions, and for the first time, non-aqueous (ethylene glycol) electrolyte solutions containing the halides and tetraethylammonium chloride. This choice of solvents allowed the compound's deposition to be studied over a wide range of temperatures (RT to 185 °C). A first report was also made of the direct potentiostatic co-deposition of GaSb from an aqueous solution containing Ga[2](SO[4])[3] and SbCl[3].An extensive study was carried out on the relationship between the technique's fundamental growth parameters (temperature, deposition potential, solution composition etc.) and the film's compositional, crystallographic and morphological properties. The material's characterisation showed that there was tendency for the films to be non-stoichiometric. X-Ray diffraction patterns obtained from InSb films deposited from aqueous electrolyte solutions showed them to generally consist of two phases, the compound and, depending mostly on deposition potential, one of the elements. Films containing three phases, the compound and both elements, were deposited on Ti substrates from aqueous solutions and on to ITO substrates from non-aqueous solutions. These results were interpreted from both thermodynamic and kinetic viewpoints. This led to the conclusion that kinetic barriers to the formation of InSb still existed, even at the highest temperature used (~185 °C). In respect of GaSb, the compound's formation was complicated by a side reaction involving the evolution of H[2].New studies involving Scanning Electron Microscopy of the electrodeposited materials showed that they exhibited a nodular morphology, which can be explained in terms of the film's limiting current growth conditions. Energy Dispersive X-Ray Analysis (EDX) and Glow Discharge Optical Emission Spectroscopy (GDOES) identified indium chloride as a major impurity in the InSb films, especially those deposited from non-aqueous solutions. A mechanism for the incorporation of indium chloride was proposed, based on the physical entrapment of a precipitate of the compound.

No description available.

The objectives of the research undertaken have been to investigate the properties of semiconductor lasers operating at around 1.3 mum. The aim of the investigation is to suggest modifications which give rise to improved operating characteristics especially in the high temperature (approaching 85 °C) range. The investigation can be divided into 2 sections: a theoretical approach and an experimental section. The theoretical study examined the performance of compressively strained InGaAsP/InP multiple quantum-well lasers emitting at 1.3 mum in order to investigate the important factors and trends in the threshold current density and differential gain with strain, well width and well number. Structures with a fixed compressive strain of 1% but variable well width, and also with a fixed well width but variable strain from 0% to 1.4% have been considered. It has been found that there is little benefit to having compressive strains greater than 1 %. For structures with a fixed 1% compressive strain and unstrained barriers, an optimum structure for lowest threshold current density and a high differential gain has been found to consist of six 35 A quantum-wells. In addition, compensated strain (CS) structures with compressive wells and tensile barriers have been examined. It is shown that the conduction band offset can be significantly increased and the valence band offset reduced in such structures, to give band-offset ratios comparable with aluminium based 1.3 mum devices. The gain calculations performed suggest that there is little degradation in the threshold carrier density or differential gain due to these alterations in the band offsets; and hence a better laser performance is expected due to a reduction in thermal leakage currents due to the improved electron confinement. The experimental study concentrates on looking at certain key design parameters to investigate their effect on the laser performance. These design parameters range from the number of quantum-wells to the device length. The experimental study confirms the conclusions drawn in the theoretical investigation that the optimum structure for a 1.3 mum InGaAsP laser for low threshold current, high efficiency and high characteristic temperature operation consists of six 1% compressively strained 50 A quantum-wells in a device of medium length (approx. 450 mum). The inclusion of a high reflection coating on one facet provides further improvement in the device performance, but increases the production cost dramatically. Also investigated in the experimental section is the effect of changing the device material from InGaAsP to InGaA1As. The results discussed do not offer firm evidence of any improvement in the device characteristics in switching from a P-based to an Al-based structure. This is mainly due to the added complication of switching to a RWG structure from a BH structure. Another explanation for the relatively poor performance of InGaAsP 1.3 mum lasers has been examined. That is leakage of the carriers out of the well region. Evidence of a leakage current has been seen primarily in devices with a low number of quantum-wells. A novel measurement technique has been demonstrated, which should prove useful for obtaining a numerical value for the leakage current in semiconductor lasers. The results presented suggest that leakage current is not significant for a 9 well device until operating at temperatures above around 373 K. This is supported by evidence supplied by the spontaneous emission spectra.

141 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-03-22T16:05:41Z No. of bitstreams: 1 Tese final Ednaldo Sousa.pdf: 2728911 bytes, checksum: ab82406a11153fd2c6032629dc6be132 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-06-04T14:33:45Z (GMT) No. of bitstreams: 1 Tese final Ednaldo Sousa.pdf: 2728911 bytes, checksum: ab82406a11153fd2c6032629dc6be132 (MD5) / Made available in DSpace on 2013-06-04T14:33:45Z (GMT). No. of bitstreams: 1 Tese final Ednaldo Sousa.pdf: 2728911 bytes, checksum: ab82406a11153fd2c6032629dc6be132 (MD5) Previous issue date: 2012 / CNPq / A emissão de poluentes atmosféricos, tais como, monóxido de carbono (CO), óxidos de enxofre (SOX) e óxidos de nitrogênio (NOX) é, atualmente, um dos maiores problemas encontrados em processos industriais. O óxido nítrico (NO) representa cerca de 95% de toda emissão de NOX para a atmosfera. Uma das principais fontes de emissão de NOX são as unidades de regeneração de catalisadores de craqueamento catalítico em leito fluidizado (FCC). Nesse trabalho, foram utilizados catalisadores de irídio suportados em aluminas (0,1-1,0%/Al2O3) e em aluminas modificadas com índio (0,1%Ir/InxAl2-xO3). Os catalisadores foram preparados pelo método de impregnação úmida, sendo que para os suportes foi utilizado o método da combustão. Os materiais obtidos foram avaliados cataliticamente na redução de NO com CO na presença de O2, H2O e SO2. Todos os catalisadores mostraram-se ativos e hidrotermicamente estáveis em toda região de temperatura investigada (250 – 600°C) operando sobre alta velocidade espacial. O s catalisadores que não continham In em suas formulações apresentaram uma pequena desativação na presença de SO2, enquanto que, para os que possuíam In a presença de SO2 no meio reacional aumentou a atividade dos catalisadores, comprovando o efeito promotor deste metal. Catalisadores com baixo teor de Ir mostraram-se mais ativos do que os com altos teores. A influência do O2 no meio reacional também foi investigada, onde foi verificada uma forte dependência da presença do mesmo para a atividade do catalisador. Na ausência de O2, os catalisadores investigados tiveram uma significativa redução da atividade tanto na redução de NO quanto na conversão de CO. Avaliando o efeito do pré-tratamento, verificou-se que as amostra préreduzidas tiveram um maior desempenho no teste catalítico do que as pré-oxidadas. Sugerindo assim, que o sítio ativo para a redução de NO com CO sobre catalisadores de irídio é o Ir0. Todos os catalisadores demonstraram alta conversão de CO e seletividade a CO2. / Salvador

In today's "silicon age" in which we live, field-effect transistors (FET) are the workhorse of virtually all modern-day electronic gadgets. Although silicon currently dominates most of these electronics, layered 2D transition metal dichalcogenides (TMDCs) have great potential in low power optoelectronic applications due to their indirect-to-direct band gap transition from bulk to few-layer and high on/off switching ratios. TMDC WSe2 is studied here, mechanically exfoliated from CVT-grown bulk WSe2 crystals, to create a few-layered ambipolar FET, which transitions from dominant p-type behavior to n-type behavior dominating as temperature decreases. A high electron mobility μ>150 cm2V-1s-1 was found in the low temperature region near 50 K. Temperature-dependent photoconduction measurements were also taken, revealing that both the application of negative gate bias and decreasing the temperature resulted in an increase of the responsivity of the WSe2 sample. Besides TMDCs, Group III-VI van der Waals structures also show promising anisotropic optical, electronic, and mechanical properties. In particular, mechanically exfoliated few-layered InSe is studied here for its indirect band gap of 1.4 eV, which should offer a broad spectral response. It was found that the steady state photoconduction slightly decreased with the application of positive gate bias, likely due to the desorption of adsorbates on the surface of the sample. A room temperature responsivity near 5 AW-1 and external quantum efficiency of 207% was found for the InSe FET. Both TMDC’s and group III-VI chalcogenides continue to be studied for their remarkably diverse properties that depend on their thickness and composition for their applications as transistors, sensors, and composite materials in photovoltaics and optoelectronics.

xiii, 84 p. ; ill. / This dissertation describes the deposition and characterization of an amorphous thin film with a composition near that of CuInSe 2 (CIS). The creation of an amorphous intermediate leads to a crystalline film at low annealing temperatures. Thin films were deposited from elemental sources in a custom built high vacuum chamber. Copper-selenium and indium-selenium binary layered samples were investigated to identify interfacial reactions that would form undesired binary intermediate compounds resulting in the need for high temperature annealing. Although the indium-selenium system did not form interfacial compounds on deposit, indium crystallized when the indium layer thickness exceeded 15 angstroms, disrupting the continuity of the elemental layers. Copper-selenium elemental layers with a repeat thickness of over 30 angstroms or compositions with less than 63% selenium formed CuSe on deposit. Several deposition schemes were investigated to identify the proper deposition pattern and thicknesses to form the CIS amorphous film. Simple co-deposition resulted in the nucleation of CIS. A simple stacking of the three elements in the older Se-In-Cu at a repeat thickness of 60 angstroms resulted in the nucleation of CuSe and sometimes CIS. The CIS most likely formed due to the disruption of the elemental layers by the growth of the CuSe. Reduction of the repeat thickness to 20 angstroms eliminated the nucleation of CuSe, as predicted by the study of the binary Cu-Se layered samples, but resulted in the nucleation of CIS, similar to the co-deposited samples. To eliminate both the thick Cu-Se region, and prevent the intermixing of all three elements, a more complex deposition pattern was initiated. The copper and selenium repeat thicknesses were reduced into a Se-Cu-Se-Cu-Se pattern followed by deposition of the indium layer at a total repeat thickness of 60 angstroms. At a Se:Cu ratio of 2:1 and the small repeat thickness, no Cu-Se phases nucleated. Additionally, the Cu-In interface was eliminated. For this deposition scheme, films with a selenium rich composition relative to CuInSez were generally amorphous. Those that were Cu-In rich always nucleated CIS on deposit. Annealing of all samples produced crystalline CIS. / Adviser: David C. Johnson

Il y a un intérêt croissant concernant la découverte de nouvelles méthodes commercialement viables pour réaliser des analyses spectro-électrochimiques — combinant des techniques électrochimiques et spectrales. Pour ce faire, nous avons préparé un matériau d'électrode transparent et conducteur, l’oxyde d’indium dopé à l’étain. Nous avons utilisé la technique d’électrofilage conduisant à la formation de fibres très fines avec une surface spécifique élevée. Ces électrodes ont ensuite été recouvertes d'une couche supplémentaire de silice poreuse et fonctionnalisée pour maximiser la surface spécifique et introduire des propriétés de détection supplémentaires. Le dispositif a été utilisé dans la détection du bleu de méthylène qui est un colorant industriel mais également un polluant environnemental. il a été mis en évidence qu’avec l'utilisation d'une telle électrode, il était possible de détecter des concentrations inférieures aux niveaux environnementaux nocifs. Enfin, les électrodes fonctionnalisées ont également été utilisées avec succès pour générer une luminescence plus intense et plus stable, ce qui ouvre de nouvelles perspectives pour la conception de capteurs spectroélectrochimiques / There is a growing interest in finding new and commercially viable methods of performing a spectroelectrochemical analysis which combines electrochemical and spectral techniques. For this purpose, an electrode material that is transparent and conductive needs to be prepared. In this work, such electrode was prepared by electrospinning which is a technique capable of forming very thin fibers with high surface area. Those electrodes were also covered with additional layer of porous and functionalized silica to maximize the surface area and introduced additional sensing properties. This material was used in the detection of methylene blue which is an industrial dye and an environmental pollutant. It was found that using such electrode it was possible to detect concentrations that are smaller than the harmful environmental levels. Finally, the layers were also used with success to generate luminescence which is opening new prospects for the design of spectroelectrochemical sensors

Made available in DSpace on 2016-06-02T20:36:45Z (GMT). No. of bitstreams: 1 5302.pdf: 3050627 bytes, checksum: d14aad95482698e7d39d217f3b9d0922 (MD5) Previous issue date: 2011-11-22 / Universidade Federal de Sao Carlos / In this study, in the first step, Indium tin oxide nanoparticles were synthesized via a non-aqueous route involving the solvothermal treatment of indium (III) acetylacetonate and tin (IV) chloride in polyethylene glycol Mw=1000. The use of microwave heating reduced the reaction time considerably when compared to traditional heating methods. An analysis by transmission electron microscopy (TEM) revealed particles of relatively uniform sizes and shapes. The high crystallinity of the material was observed by high resolution transmission electron microscopy (HRTEM). The nanocristal size founded by count was 5,1nm. A powder X-ray diffraction analysis indicated that all the materials were crystalline. Infrared spectra confirmed the presence of organic material on the nanoparticle surface. By thermogravimetric analysis (TGA) determined that 11.3% of the total mass corresponds to the polymer. Resistivity values below 10-1 Ω.cm were obtained in thin films and pellets, and semiconductor behavior. In the second step, a model to control the covered area of graphene oxide (GO) sheets by ITO nanoparticles was proposed. The method used was add graphene oxide at the synthetic route to obtain pure ITO. The composites were characterized by XRD, FT-IR, TGA and TEM. XRD results for the synthesized materials confirmed the diffraction patterns of ITO in the different composites synthesized. Through the analysis of FT-IR was possible confirm the presence of the polymer formed on the surface of the oxide nanoparticle and functional groups of graphene oxide sheets. The polymer attached on the oxide surface is responsible for the strong interaction between the ITO and graphen oxide sheets. TEM images for the samples with different cover percentage showed the controller achieved with the synthesis proposed. The composite with 100 or 10% of metal oxides covering the sheets surface did not show the presence of nanocrystals out sheets. The percent value of the covered area obtained of 15% founded by image J analisys is near to the calculated value. From this value we can say that the model works well to control the covered area of GO by nanocristals. The electrical resistivity values found are comparable to the pure ITO, however, with a smaller amount of ITO. / Neste estudo, na primeira etapa, nanopartículas de óxido de índio dopado com estanho foram sintetizadas por uma rota não aquosa envolvendo o tratamento solvotermal de acetilacetonato de índio (III) e cloreto de estanho (IV) em polietilenoglicol de massa molecular 1000. O uso de aquecimento auxiliado por microondas reduziu o tempo de reação quando comparado aos métodos tradicionais de aquecimento. A análise por microscopia eletrônica de transmissão (TEM) mostrou partículas com tamanho e forma relativamente uniformes. A alta cristalinidade do material foi observada por microscopia eletrônica de alta resolução (HRTEM). O tamanho dos nanocristais obtidos por contagem foi de 5,1 nm. A análise de difração de Raios-X (DRX) indicou a cristalinidade do material. O espectro de infravermelho (FT-IR) confirmou a presença do material orgânico na superfície das nanopartículas. Pela análise termogravimétrica (TGA) determinou que 11,3% da massa total corresponde ao polímero. Resistividade abaixo de 10-1 Ω.cm foi obtido no filme e na pastilha, com comportamento semicondutor do óxido. Na segunda etapa, um modelo de controlar a área das folhas de óxido de grafeno (OG) coberta por nanocristais foi proposto. O método usado foi adicionar óxido de grafeno à rota de síntese do ITO puro. Os compósitos foram caracterizados por DRX, FT-IR, TGA e TEM. Os resultados de difração de Raios-X confirmaram o padrão de difração do ITO nos diferentes compósitos. Pela análise de FT-IR foi possível confirmar a presença do polímero na superfície das nanoparticulas e os grupos funcionais das folhas de óxido de grafeno. O polímero ligado na superfície do óxido e responsável pela forte interação entre o ITO e as folhas de óxido de grafeno. As imagens de TEM para as amostras com porcentagens de cobertura diferente mostraram o controle alcançado com o método de síntese proposto. Os compósitos com 100% e 10% de óxido metálico cobrindo a superfície das folhas mostraram que não ocorreu a formação de nanopartículas fora das folhas. O valor de 15 % de porcentagem de área coberta obtido é próximo ao valor calculado. A partir deste valor, pode-se dizer que o modelo funciona bem para controlar a área de OG coberta por nanocristais. Os valores de resistividade elétrica encontrados são comparáveis ao ITO puro, no entanto, com uma quantidade menor de ITO.

Made available in DSpace on 2014-10-09T12:33:45Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:00Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP