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[pt] Os dispositivos orgânicos de conversão ascendente são dispositivos eletrônicos que convertem luz infravermelha em luz visível. Para isso, utilizam fotodetectores orgânicos com bandas de absorção na faixa do infravermelho próximo (NIR) que absorvem fótons de baixa energia e, utilizando uma determinada arquitetura de filmes finos orgânicos capazes de transportar, bloquear e recombinar portadores de carga, emitem fótons de mais alta energia na faixa visível. Nos últimos anos, os OUDs tornaram-se candidatos-chave para uma ampla gama de aplicações em medicina, comunicação óptica, segurança, sensores químicos e biológicos, entre outras. O caminho percorrido até hoje na construção desses dispositivos é consideravelmente curto, devido à sua complexidade de fabricação e aos desafios técnicos necessários para alcançar boas eficiências e estabilidade operacional, motivo pelo qual tem poucos trabalhos na literatura. Pelo anterior, esse trabalho visou contribuir na pesquisa dos OUDs, explorando seu funcionamento desde novas arquiteturas não reportadas. Assim, foram fabricados OUDs por deposição térmica resistiva com diferentes ftalocianinas e naftalocianinas como camadas fotodetectoras: a ftalocianina de estanho SnPc, a naftalocianina de estanho SnNc e a ftalocianina de cloroalumínio ClAlPc, todas apresentando bandas de absorção no NIR. Uma vez fabricados os dispositivos foram caracterizados do ponto de vista elétrico (curvas de corrente em função da voltagem) e óptico (luminância) no Laboratório de Optoeletrônica Molecular (LOEM). Como resultado, a naftalocianina SnNc apresentou os melhores parâmetros de desempenho: densidade de corrente da ordem de 10-2 𝑚𝐴 𝑐 𝑚 22, razão de brilho 𝐿 𝑁𝐼𝑅 𝐿 𝐷𝐴𝑅𝐾 por volta de 2350 em 12 V e eficiência de conversão fóton–fóton de 4,8%. Os demais compostos, SnPc e ClAlPc, também apresentaram resultados favoráveis para seus parâmetros, atingindo eficiências de conversão fóton–fóton de 3,7% e 3,4% respectivamente. / [en] Organic Up-Conversion Devices (OUDs) are electronic devices that convert infrared light into visible light. To achieve this, they utilize organic photodetectors with absorption bands in the near-infrared (NIR) range that absorb low-energy photons. By using a specific architecture of organic thin films capable of transporting, blocking, and recombining charge carriers, they emit higher-energy photons in the visible range. In recent years, OUDs have become key candidates for a wide range of applications in medicine, optical communication, security, chemical and biological sensors, among others. The path taken so far in the construction of these devices is considerably short due to their manufacturing complexity and the technical challenges required to achieve good efficiencies and operational stability. This is why there are few works in the literature on this subject. Given this context, this work aimed to contribute to the research on OUDs by exploring some characteristics and investigating their operation using previously unreported architectures. Thus, OUDs were fabricated by resistive thermal deposition using different phthalocyanines and naphthalocyanines as photodetector layers: tin phthalocyanine SnPc, tin naphthalocyanine SnNc, and chloroaluminum phthalocyanine ClAlPc, all presenting absorption bands in the NIR. Once the devices were fabricated, they were characterized from an electrical perspective (current-voltage curves) and an optical perspective (luminance) at the Molecular Optoelectronics Laboratory (LOEM). As a result, naphthalocyanine SnNc exhibited the best performance parameters: current density of the order of 10-2 𝑚𝐴 𝑐 𝑚 22, brightness ratio 𝐿 𝑁𝐼𝑅 𝐿 𝐷𝐴𝑅𝐾 of around 2350 at 12 V, and photon–photon conversion efficiency of 4.8%. The other compounds, SnPc and ClAlPc, also showed favorable results for their parameters, achieving photon–photon conversion efficiencies of 3.7% and 3.4%, respectively.

<div>Global warming poses an existential threat to humanity and is inevitable unless significant efforts are made to eliminate its root causes. The need to replace fossil fuels with renewable sources has been obvious for many years, yet the world still receives the vast majority of its energy from non-renewable reservoirs. Harnessing solar radiation is the most promising route to ensure a carbon-free energy future, as the sun is the sole source of energy that can meet humankind’s energy demands for generations to come.<br></div><div><br></div><div>The most widely recognized technology associated with the sun is a photovoltaic (PV) cell, which converts electromagnetic radiation directly into electricity that can either be used immediately or stored for later use. Silicon-based solar cells currently dominate (>90% market share) the global PV market, driven in part due to parallel research in the microelectronics industry. However, silicon is an indirect bandgap material, resulting in inflexible solar modules, and it requires high capital expenditures and high energy inputs for terawatt scale manufacturing.</div><div><br></div><div>The remainder of the commercial PV market consists of thin-film technologies based on Cu(In,Ga)Se₂ (CIGSe) and CdTe. These materials have a direct bandgap, so they can be used in flexible applications, and they are readily scalable due to their amenability to low-cost, roll-to-roll manufacturing. The power conversion efficiencies of CIGSe and CdTe cells have exceeded 20% and are nearing those of silicon cells, but concerns over the long-term supply of indium and tellurium cast doubt on whether these materials can be deployed at large scales. Alternative materials, such as Cu₂ZnSnS_4-xSe_x (CZTSSe), have been researched for many years; the allure of a material with earth abundant elements and properties similar to CIGSe and CdTe was quite enticing. However, recent work suggests that CZTSSe is fundamentally limited by the formation of defects and band tails in the bulk material, and the efficiencies of CZTSSe-based devices have been saturated since 2013.</div><div><br></div><div>New materials for the PV market must meet several criteria, including constituent earth abundant elements, outstanding optoelectronic properties, and low propensity for defect formation. In this regard, the copper-arsenic-sulfur family of materials is an attractive candidate for PV applications. Cu, As, and S are all earth abundant elements with sufficiently different ionic radii, suggesting high defect formation energies. In addition, previous computational work has suggested that several ternary phases, most notably enargite Cu₃AsS₄, have appropriate bandgaps, high absorption coefficients, and high predicted efficiencies in a thin-film PV device. The system must be investigated experimentally, with attention not only paid to synthesis and device performance, but also to characteristics that give clues as to whether high efficiencies are achievable.</div><div><br></div><div>This dissertation studies the Cu-As-S system in the context of thin-film photovoltaics, with an emphasis on Cu₃AsS₄ and detours to related materials discussed when appropriate. The first synthesis of Cu₃AsS₄ thin-films is reported using solution-processed nanoparticles as precursors. Initial device efficiencies reach 0.18%, which are further boosted to 0.35% through optimization of the annealing procedure. Several limitations to the initial approach are identified (most notably the presence of a carbonaceous secondary phase) and addressed through post-processing treatments and ligand exchange. Cu₃AsS₄ is also rigorously characterized using a suite of optoelectronic techniques which demonstrate favorable defect characteristics that motivate continued research. The current limitations to Cu₃AsS₄ performance stem from improper device architecture rather than material properties. Further development of Cu-As-S thin films must focus on identifying and fabricating ideal device architectures in parallel with continued improvements to film fabrication.</div><div><br></div><div>This dissertation ultimately demonstrates high promise for Cu₃AsS₄ as a thin-film PV material. It also may serve as an example for other researchers studying new materials, as the examination of fundamental optoelectronic properties early in the material’s development phase is key to ensure that limited scientific resources are invested into the compounds with the highest potential impact on society.<br></div>

Photodetectors are a kind of semiconductor devices that convert incoming light to an electrical signal. Photodetectors are classified based on their different structure, fabrication technology, applications and different sensitivity. Infrared photodetectors are widely used in many applications such as night vision, thermal cameras, remote temperature sensing, and medical diagnosis etc.   All detectors have material inside that is sensitive to incoming light. It will absorb the photons and, if the incoming photons have enough energy, electrons will be excited to higher energy levels and if these electrons are free to move, under the effect of an external electric field, a photocurrent is generated.   In this project Fourier Transform Infrared (FT-IR) Spectroscopy is used to investigate a new kind of photodiodes that are based on self-assembled semiconductor nanowires (NWs) which are grown directly on the substrate without any epi-layer. The spectrally resolved photocurrent (at different applied biases) and IV curves (in darkness and illumination) for different temperatures have been studied respectively. Polarization effects (at low and high Temperatures) have been investigated.  The experiments are conducted for different samples with high concentration of NWs as well as with lower concentration of NWs in the temperature range from 78 K (-195ºC) to 300 (27ºC). These photodiodes are designed to work in near infrared (NIR) spectral range.   The results show that the NW photodetectors indeed are promising devices with fairly high break down voltage, change of photocurrent spectra with polarized light, low and constant reverse saturation current (Is). The impact of different polarized light on photocurrent spectra has been investigated and an attempt has been made to clarify the observed double peak of InP photocurrent spectrum. Our investigations also include a comparison to a conventional planar InP p-i-n photodetector.

Quantum dots exhibit strongly size-dependent optical and electrical properties. The ability to join the dots into complex assemblies creates many opportunities for scientific discovery. This motivated our present research work on QDIPs, DWELLs, and graphene like QDs. The intention of this research was to study the size dependent achievements of QDIPs, DWELLs, and graphene like QDs with those of competitive technologies, with the emphasis on the material properties, device structure, and their impact on the device performance. In this dissertation four research studies pertaining to optical properties of quantum dot and dot-in-a-well infrared photodetectors, I-V characteristics of graphene quantum dots, and energy and spin texture of germanene quantum dots are presented. Improving self-assembled QD is a key issue in the increasing the absorption and improving the performance. In the present research work, an ideal self-assembled QD structure is analyzed theoretically with twenty-hole levels (Intraband optical transitions within the valence band) and twenty-electron energy levels (DWELL). Continuing the efforts to study self-assembled QDs we extended our work to graphene like quantum dots (graphene and germanene) to study the electronic transport properties. We study numerically the intraband optical transitions within the valence band of InxGa1-xAs/GaAs pyramidal quantum dots. We analyze the possibility of tuning of corresponding absorption spectra by varying the size and composition of the dots. Both ‘x ’ and the size of the quantum dot base are varied. We have found that the absorption spectra of such quantum dots are more sensitive to the in-plane incident light. We present numerically obtained absorption optical spectra of n-doped InAs/In0.15Ga0.85As/GaAs quantum dot-in-a-well systems. The absorption spectra are mainly determined by the size of the quantum dot and have weak dependence on the thickness of the quantum well and position of the dot in a well. The dot-in-a-well system is sensitive to both in-plane and out-of-plane polarizations of the incident light with much stronger absorption intensities for the in-plane-polarized light. We also present theoretically obtained I-V characteristics of graphene quantum dots, which are realized as a small piece of monolayer graphene. We describe graphene within the nearest-neighbor tight-binding model. The current versus the bias voltage has typical step-like shape, which is due to discrete energy spectrum of the quantum dot. The current through the dot system also depends on the position of the electrodes relative to the quantum dot. In relation to graphene quantum dots, we present our study of buckled graphene-like materials, like germanene and silicene. We consider theoretically germanene quantum dot, consisting of 13, 27, and 35 germanium atoms. Due to strong spin-orbit interaction and buckled structure of the germanene layer, the direction of the spin of an electron in the quantum dot depends on both the electron energy and external perpendicular electric field. With variation of energy, the direction of spin changes by approximately 4.50. Application of external electric field results in rotation of electron spin by approximately 0.50, where the direction of rotation depends on the electron energy.

Made available in DSpace on 2014-10-09T12:51:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:28Z (GMT). No. of bitstreams: 1 11295.pdf: 3731608 bytes, checksum: 642672d3ddbbe81953275dd174a58822 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:01/09049-5

Made available in DSpace on 2014-10-09T12:51:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:28Z (GMT). No. of bitstreams: 1 11295.pdf: 3731608 bytes, checksum: 642672d3ddbbe81953275dd174a58822 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho, os cristais de TlBr foram crescidos pelo método de Bridgman, a partir de materiais purificados pela técnica de fusão zonal. A eficiência da purificação e avaliação da superfície cristalina em relação ao desempenho como detectores de radiação foi observada. Bons resultados foram obtidos com os aprimoramentos realizados nos processos de purificação, crescimento de cristais e na fabricação dos detectores. A resposta à radiação foi verificada excitando os detectores com fontes de raios gama: 241Am (59 keV), 133Ba (80 e 355 keV), 57Co (122 keV), 22Na (511 keV) e 137Cs (662 keV) à temperatura ambiente. Os valores de resolução em energia mais satisfatórios encontrados nesse trabalho foram a partir de detectores mais puros. Os melhores valores de resolução em energia obtidos foram de 10keV (16%), 12keV (15%), 12keV (10%), 28 keV (8%), 31keV (6%) e 36keV (5%) para as energias de 59, 80, 122, 355, 511 e 662 keV, respectivamente. Também foi realizado um estudo da resposta à detecção a uma temperatura de -20ºC e da estabilidade desses detectores. Nos detectores desenvolvidos não houve diferença significativa na resolução tanto em temperatura ambiente quanto na reduzida. Em relação à estabilidade foi observada uma degradação das características espectrométricas sob operação contínua do detector a temperatura ambiente e esta instabilidade variou para cada detector. Ambas características também foram observadas por outros autores. A viabilidade de utilização do cristal de TlBr como fotodetector para acoplamento em cintiladores também foi estudada neste trabalho. TlBr é um material promissor para ser utilizado como fotodetector devido a sua adequada eficiência quântica na região de 350 a aproximadamente 500 nm. Como uma aplicação para este trabalho foram iniciados estudos para fabricação de sondas cirúrgicas utilizando cristais de TlBr como o meio detector. / Neste trabalho, os cristais de TlBr foram crescidos pelo método de Bridgman, a partir de materiais purificados pela técnica de fusão zonal. A eficiência da purificação e avaliação da superfície cristalina em relação ao desempenho como detectores de radiação foi observada. Bons resultados foram obtidos com os aprimoramentos realizados nos processos de purificação, crescimento de cristais e na fabricação dos detectores. A resposta à radiação foi verificada excitando os detectores com fontes de raios gama: 241Am (59 keV), 133Ba (80 e 355 keV), 57Co (122 keV), 22Na (511 keV) e 137Cs (662 keV) à temperatura ambiente. Os valores de resolução em energia mais satisfatórios encontrados nesse trabalho foram a partir de detectores mais puros. Os melhores valores de resolução em energia obtidos foram de 10keV (16%), 12keV (15%), 12keV (10%), 28 keV (8%), 31keV (6%) e 36keV (5%) para as energias de 59, 80, 122, 355, 511 e 662 keV, respectivamente. Também foi realizado um estudo da resposta à detecção a uma temperatura de -20ºC e da estabilidade desses detectores. Nos detectores desenvolvidos não houve diferença significativa na resolução tanto em temperatura ambiente quanto na reduzida. Em relação à estabilidade foi observada uma degradação das características espectrométricas sob operação contínua do detector a temperatura ambiente e esta instabilidade variou para cada detector. Ambas características também foram observadas por outros autores. A viabilidade de utilização do cristal de TlBr como fotodetector para acoplamento em cintiladores também foi estudada neste trabalho. TlBr é um material promissor para ser utilizado como fotodetector devido a sua adequada eficiência quântica na região de 350 a aproximadamente 500 nm. Como uma aplicação para este trabalho foram iniciados estudos para fabricação de sondas cirúrgicas utilizando cristais de TlBr como o meio detector. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:01/09049-5

La tomographie d'émission par positrons (TEP) se distingue des autres modalités d'imagerie par sa capacité à localiser et quantifier la présence de molécules marquées, appelées radiotraceurs, au sein d'un organisme. Cette capacité à mesurer l'activité biologique des différents tissus d'un sujet apporte des informations uniques et essentielles à l'étude de tumeurs cancéreuses, au fonctionnement du cerveau et de ses maladies neurodégénératives et de la pharmacodynamique de nouveaux médicaments. Depuis les tout débuts de la TEP, les scientifiques rêvent de pouvoir utiliser l'information de temps de vol des photons pour améliorer la qualité de l'image TEP. L'arrivée des photodiodes avalanche monophotoniques (PAMP), rend maintenant ce rêve possible. Ces dispositifs détectent la faible émission de lumière des scintillateurs et présentent une réponse grandement amplifiée avec une faible incertitude temporelle. Mais le potentiel des PAMP n'est pas encore entièrement exploré. Plutôt que de faire la somme des courants d'une matrice de PAMP, il est possible d'utiliser leur nature intrinsèquement binaire afin de réaliser un photodétecteur numérique capable de déterminer avec précision le temps d'arrivée de chaque photon de scintillation. Toutefois, la conception de matrices de PAMP numériques en est encore à ses débuts, et les outils de conception se font rares. Ce projet de doctorat propose un simulateur facilitant la conception de matrices de PAMP, que celles-ci soient analogiques ou numériques. Avec cet outil, l'optimisation d'une matrice de PAMP numérique basée dans une technologie Teledyne DALSA HV CMOS \SI{0,8}{\micro\metre} est proposée. En plus de guider les choix de conception de l'équipe, cette optimisation permet de mieux comprendre quels paramètres influencent les performances du détecteur. De plus, puisque le photodétecteur n'est pas l'unique acteur des performances d'un détecteur TEP, une étude sur l'impact des scintillateurs est aussi présentée. Cette étude vérifie l'amélioration apportée par l'intégration de photons prompts dans des scintillateurs LYSO. Enfin, une approche novatrice pour discriminer l'énergie des évènements TEP basée sur l'information temporelle des photons de scintillation a été développée et vérifiée à l'aide du simulateur. Bien que ce simulateur et les études réalisées dans le cadre de cette thèse soient concentrés sur des détecteurs TEP, l'utilité des PAMP et du simulateur ne se limite pas à cette application. Les matrices de PAMP sont prisées pour le développement de détecteur en physique des particules, physique nucléaire, informatique quantique, LIDAR et bien d'autres. / Abstract : Positron emission tomography (PET) stands out among other imaging modalities by its ability to locate and quantify the presence of marked molecules, called radiotracers, within an organism. The capacity to measure biological activity of various organic tissues provides unique information, essential to the study of cancerous tumors, brain functions and the pharmacodynamics of new medications. Since the very beginings of PET, scientists dreamed of using the photon's time-of-flight information to improve PET images. With the recent progress of Single Photon Avalanche Diodes (SPAD), this dream is now possible. These photodetectors detect the scintillators' low light emission and offers a greatly amplified response with only a small time uncertainty. However the potential of SPAD has not yet been entirely explored. Instead of summing the currents of a SPAD array, it is possible to use their intrinsically binary operation to build a digital photodetector, able to establish with precision the time of arrival of each scintillation photon. With this information, the time-of-flight measurements will be much more precise. Yet the design of digital SPAD arrays is in its infancy and design tools for this purpose are rare. This project proposes a simulator to aid the design of SPAD arrays, both analog and digital. With this tool, we propose an optimised design for a digital SPAD array fabricated in Teledyne Dalsa HV CMOS \SI{0.8}{\micro\metre} technology. In addition to guiding the design choices of our team, this optimisation led to a better understanding which parameters influence the performance of a PET detector. In addition, since the photodetector is not the sole actor in the performance of a PET detector, a study on the effect of scintillators is also presented. This study evaluates the improvement brought by incorporating a prompt photon emission mechanism in LYSO crystals. Finally, we describe a novel approach to energy discrimination based on the timing information of scintillation photons was developped and tested using the simulator. While this simulator and the studies presented in this thesis focus on PET detectors, SPAD are not limited to this sole application. SPAD arrays are promising for a wide variety of fields, including particle physics, high energy physics, quantum computing, LIDAR and many more.

In this thesis, the strength of the LBIC system is enhanced in different aspects that includes its feasibility as a non-destructive characterization tool, the signal analysis and development of analytical solution to have better understanding on the defects and inhomogeneities in the quantum dot based hetero-structures for device applications, finally understanding its limits due to the size of the laser beam and interpretation of artefacts in the signal appearance due to the presence of co-devices. Chapter#1 provides the introduction and literature survey of the LBIC system. It covers the importance and area of application of the LBIC. Chapter#2 various tools and instrumentation are discussed briefly for the systems that are developed in the lab as well as standard tools utilised for the material characterization. A LBIC instrumentation a novel colloidal quantum dots (CQD) thin film deposition system is discussed. In the last part along with the standard characterization systems a software tool (semiconductor device simulator) is discussed, which is used to visualize and understand the LBIC profile that is obtained experimentally. Chapter#3 provides the information of colloidal synthesis of PbS and HgxCd1-xTe quantum dots. Device fabrication process is explained step by step for the following devices. p-n junction silicon diodes, PbS-CQD/Si hetero-structures, ITO/PbS-CQD/Al crossbar structures and HgCdTe-CQD/Si hetero-structures. Chapter#4 deals with the major constraints imposed on the LBIC due to the need of Ohmic contacts. To overcome this major limitation, in this work, the origin of the signal is studied with the remote contact geometry for silicon p-n junction devices. It was observed that the signals can be collected with the capacitively coupled remote contacts, where LBIC was ultimately demonstrated as contactless measurement tool without any compromise on the measurements and thus obtained physical parameters. The effect of finite laser beam size is also described, which was found to have effect on the actual dimensions measured with the LBIC images. LBIC utility is further enhanced with the Si/CQD based hetero-structure devices, which are the potential candidates in the evolving device technology to be utilized in various modular systems such as PDs and LED applications. Chapter#5 discusses the origin and possible mechanisms for lateral photo-voltage which is closely monitored in the PbS-CQD/Si hetero-junction device systems. Interestingly, it is observed that there are two different line profiles for n and p type Si substrates. Different mechanisms that give rise to this kind of profiles were found to be distinct and are related to the band alignment of the CQD/Si hetero-structure. It lead to the revelation of an interesting phenomenon and believed to be universally observed irrespective of the materials involved in the formation of hetero-junction. Simulations and experimental results are quite consistent and in agreement with each other, which confirm the underlying physical mechanism that connects the LBIC anomalies with the band alignment. Chapter#6 deals with the spatial variations in the transverse photocurrent in the PbS-CQD film which is studied as a function of applied bias. Analytical equation is setup for the photocurrent in the CQD film under applied bias with the help of available transport mechanism and equations from the literature. The spatial non-uniformity that exists in the photocurrent proved to be the result of spatial inhomoginities in the physical parameters. By correlating the spatial data to the analytical equation, it is shown that the inhomoginities can be predicted. This approach is important for the devices, where monolithic detectors are fabricated by depositing CQD film on Read-Out-Integrated-Circuit (ROIC), where the manifestation of non-uniformity can be understood and probably fixed. Chapter#7 HgCdTe CQD based devices are studied for the purpose of photo-detector applications in MWIR (3  5 μm) region. HgxCd1-xTe Colloidal quantum dots are technologically important due to their wide absorption range that covers different regions of the atmospheric window. HgxCd1-xTe are successfully synthesised, which covers the absorption edge up to ~6.25 m in the IR region. Absorption and photo-response studies are carried out on HgxCd1-xTe/Si hetero-junctions under incident IR radiation. It is observed that the band gap of the quantum dots can be tuned easily by controlling the growth time as a parameter, thus moulded HgxCd1-xTe CQD/Si hetero-structures were found to have good photo-response. Chapter#8 the summary and the future direction and scope of the work is discussed. This includes the interesting observations during this thesis work which are not reported here in details.

Materials for studies related to nanoscience and nanotechnology have gained tremendous attention owing to their unique physical, chemical and electronic properties. Among various anisotropic nanostructures, one dimensional (1D) materials have received immense interest in numerous fields ranging from catalysis to electronics. Imparting multi-functionality to nanostructures is one of the major areas of research in materials science. In this direction, use of nanosized materials in energy systems such as fuel cells has been the subject of focus to achieve improved performance. Tuning the morphology of nanostructures, alloying of catalysts, dispersing catalytic particles onto various supports (carbon nanotubes, carbon nanofibers, graphene, etc.) are some of the ways to address issues related to electrochemical energy systems. It is worth mentioning that highly stable and corrosion resistant electrodes are mandatory as electrochemical cells operate under aggressive environments. Additionally, carbon, which is often used as a support for catalysts, is prone to corrosion and is subsequently implicated in reduced performance due to poor adherence of catalyst particles and loss in electrochemically active area. Hence, there is a quest for the development of stable and durable electrocatalysts / supports for various studies including fuel cells. The present thesis is structured in exploring the multi-functional aspects of titanium carbide (TiC), an early transition metal carbide. TiC, a fascinating material, possesses many favorable properties such as extreme hardness, high melting point, good thermal and electrical conductivity. Its metal-like conductivity and extreme corrosion resistance prompted us to use this material for various electrical and electrochemical studies. The current study explores the versatility of TiC in bulk as well as nanostructured forms, in electrical and electrochemical studies towards sensing, electrocatalytic reactions and active supports. 1D TiC nanowires (TiC-NW) are prepared by simple solvothermal method without use of any template and are characterized using various physico-chemical techniques. The TiC-NW comprise of 1D nanostructures with several µm length and 40 ± 15 nm diameter (figure 1). Electrical properties of individual TiC-NW are probed by fabricating devices using focused ion beam deposition (FIB) technique. The results depict the metallic nature of TiC-NW (figure 2). Figure 1. (a) SEM, (b) TEM and (c) HRTEM images of TiC-NW prepared by solvothermal method. Figure 2. (a) SEM image and (b) I-V characteristics of TiC-NW - based device as a function of temperature. The contact pads are made of Pt. Subsequently, oxidized TiC nanowires are prepared by thermal annealing of TiC-NW, leading to carbon - doped TiO2 nanowires (C-TiO2-NW) (figure 3). Photodetectors are fabricated with isolated C-TiO2-NW and the device is found to respond to visible light (figure 3) radiation with very good responsivity (20.5 A/W) and external quantum efficiency (2.7 X 104). The characteristics are quite comparable with several reported visible light photodetectors based on chalcogenide semiconductors. Figure 3. (a) HRTEM, (b) EDAX, (c) Scanning TEM-DF images of C-TiO2-NW along with (d) Ti (e) O and (f) C mapping. (g) Current – voltage curves of single C-TiO2-NW recorded in dark (black) and in presence of visible light radiation (red) of intensity 57.7 mW/cm2 at 25oC. Inset of (g) shows the SEM image of the device (top) and schematic illustration of fabricated photodetector (bottom). The next chapter deals with the electrochemical performance of TiC demonstrated for studies involving oxygen reduction and borohydride oxidation reactions. Electrochemical oxygen reduction reaction (ORR) reveal that TiC-NW possess high activity for ORR and involves four electron process while it is a two electron reduction for bulk TiC particles (figure 4). The data has been substantiated by density functional theory (DFT) calculations that reveal different modes of adsorption of oxygen on bulk and nanowire morphologies. Stable performance is observed for several hundreds of cycles that confirm the robustness of TiC. The study also demonstrates excellent selectivity of TiC for ORR in presence of methanol and thus cross-over issue can be effectively addressed in direct methanol fuel cells. In the chapter on borohydride oxidation, bare TiC electrode is explored as a catalyst for the oxidation of borohydride. One of the major issues in direct borohydride fuel cells (DBFC) is the hydrolysis of borohydride that happens on almost all electrode materials leading to low efficiency. The present study reveals that TiC is a very good catalyst for borohydride oxidation with little or no hydrolysis of borohydride [figure 5 (a)] under the experimental conditions studied. Further, shape dependant activity of TiC has been studied and fuel cell performance is followed [figure 5 (b)]. Polarization data suggests that the performance of TiC is quite stable under fuel cell experimental conditions. Figure 4. (a) Linear sweep voltammograms for ORR recorded using (i) bulk TiC particles and (ii) TiC-NW in O2-saturated 0.5 M KOH at 1000 rpm. Scan rate used is 0.005 Vs-1. (b) Variation of number of electrons with DC bias. Black dots correspond to TiC bulk particles while red ones represent nanowires. Figure 5. (a) Cyclic voltammograms of borohydride oxidation on TiC coated GC electrode in 1 M NaOH containing 0.1 M NaBH4. Scan rate used is 0.05 Vs-1. (b) Fuel cell polarization data at 70oC for DBFC assembled with (i) bulk TiC particles and (ii) TiC-NW as anode catalysts and 40 wt% Pt/C as cathode. Anolyte is 2.1 M NaBH4 in 2.5 M NaOH, and catholyte is 2.2 M H2O2 in 1.5 M H2SO4. Anode loading is 1.5 mg cm-2 and cathode loading is 2 mg cm-2. The corrosion resistance nature of TiC lends itself amenable to be used as an active support for catalytic particles (Pt and Pd) for small molecules oxidation reactions. In the present study, electro-oxidation of methanol, ethanol and formic acid have been studied. As shown in figure 6 (a), the performance of Pd loaded TiC (Pd-TiC) is found to be higher than that of Pd loaded carbon (Pd-C) suggesting the active role of TiC. The catalytic activities of TiC-based supports are further improved by tuning their morphologies. Figure 6 (c) reveals that the activities are higher in case of Pd-TiC-NW than that of Pd-TiC. Figure 6. (a) Cyclic voltammograms of Pd-TiC and Pd-C for ethanol oxidation, (b) T EM image of Pd-TiC-NW and (c) voltammograms of Pd-TiC-NW in N2-saturated 1 M ethanol in 1 M KOH medium, scan rate used is 0.05 Vs-1. The next aspect explored, is based on the preparation of C-TiO2 and its use as a substrate for surface enhanced Raman spectroscopy (SERS). Carbon doped titanium dioxide is prepared by thermal annealing of TiC. It is observed that the amount of dopant (carbon content) is dependent on the experimental conditions used. SERS studies using 4¬mercaptobenzoic acid (4-MBA) as the analyte, indicates that C-TiO2 [figure 7 (a)] enhances Raman signals based on chemical interactions between the analyte and the substrate. Raman signal intensities can be tuned with the amount of carbon content in C¬TiO2. Enhancement factors are calculated to be (7.7 ± 1.2) x 103 (for 4-MBA) and (1.7 ± 1.2) x 103 (for 4-nitrothiophenol). The SERS substrates are found to be surface renewable using visible light, a simple strategy to re-use the substrate [figure 7 (b)]. The regeneration of SERS substrates is based on self cleaning action of TiO2 that produces highly reactive oxygen containing radicals known to degrade the molecules adsorbed on TiO2. Thus, the versatility of TiC has been demonstrated with various studies. In addition to using TiC-based materials, nanoparticles of Rh, Ir and Rh-Ir alloy structures have also been used for borohydride oxidation reaction. This is explained in the last section. In Appendix-I, preliminary studies on the preparation of TiC-polyaniline (PANI) composites using liquid-liquid interfacial polymerization is explained. Raman spectroscopy results suggest that the presence of TiC-NW makes PANI to assume preferential orientation in the polaronic (conducting) form. Appendix-II discusses the role of TiC-NW as a fluorescence quencher for CdS semiconductor nanoparticles.