Semiconductor nanowires (NWs) are anticipated to play a crucial role in future electronic and optoelectronic devices. Their practical applications remain hindered by an urging need for feasible strategies to tailor their optical and electronic properties. Strategies based on strain and alloying are limited by issues such as defects, interface broadening and alloy scattering. In this thesis, a novel method to engineer the optoelectronic properties based on strain-free periodic structural modulations in chemically homogeneous Nanowire Twinning Superlattices (NTSLs) is experimentally demonstrated. NTSLs are an emerging new class of nanoscale material, composed of periodically arranged rotation twin-planes along the length of NWs. The main objective of this thesis is to establish the relationship between the electronic energy band gap (Eg) and the twin-plane spacing (d) in NTSLs, quantified using a periodicity parameter, based on ZnSe. ZnSe was chosen because of its excellent luminescence properties, and potential in fabrication of optoelectronic devices in the near-UV and blue region of the spectrum. A prerequisite to establishing this correspondence is a prior knowledge of the photoluminescence (PL) response and the nature of fundamental optical transitions in defect-free single crystal ZnSe NWs with zinc-blende (ZB) and wurtzite (WZ) crystal structures. There has been no systematic work done yet on understanding these fundamental optical processes, particularly on single NWs and in relation to their crystalline microstructure. Therefore, the secondary objective of this thesis is to study the influence of native point defects on the optical response of single ZnSe NWs in direct relation to their crystalline microstructure. The PL response from single ZB and WZ NWs was determined unambiguously, and excitonic emission linewidths close to 1 meV were observed, which are the narrowest reported linewidths thus far on ZnSe NWs. Based on this and extensive optical and structural characterization on individual NTSLs, a linear variation in Eg is shown through a monotonic shift in PL peak position from ZnSe NTSLs as a function of d, with Eg's that lie between those of ZB and WZ crystal structures. This linear variation in Eg was also validated by ab Initio electronic structure calculations. This establishes NTSLs as new nanoscale polytypes advantageous for applications requiring tunable band gaps.

Semiconductor nanowires (NWs) are anticipated to play a crucial role in future electronic and optoelectronic devices. Their practical applications remain hindered by an urging need for feasible strategies to tailor their optical and electronic properties. Strategies based on strain and alloying are limited by issues such as defects, interface broadening and alloy scattering. In this thesis, a novel method to engineer the optoelectronic properties based on strain-free periodic structural modulations in chemically homogeneous Nanowire Twinning Superlattices (NTSLs) is experimentally demonstrated. NTSLs are an emerging new class of nanoscale material, composed of periodically arranged rotation twin-planes along the length of NWs. The main objective of this thesis is to establish the relationship between the electronic energy band gap (Eg) and the twin-plane spacing (d) in NTSLs, quantified using a periodicity parameter, based on ZnSe. ZnSe was chosen because of its excellent luminescence properties, and potential in fabrication of optoelectronic devices in the near-UV and blue region of the spectrum. A prerequisite to establishing this correspondence is a prior knowledge of the photoluminescence (PL) response and the nature of fundamental optical transitions in defect-free single crystal ZnSe NWs with zinc-blende (ZB) and wurtzite (WZ) crystal structures. There has been no systematic work done yet on understanding these fundamental optical processes, particularly on single NWs and in relation to their crystalline microstructure. Therefore, the secondary objective of this thesis is to study the influence of native point defects on the optical response of single ZnSe NWs in direct relation to their crystalline microstructure. The PL response from single ZB and WZ NWs was determined unambiguously, and excitonic emission linewidths close to 1 meV were observed, which are the narrowest reported linewidths thus far on ZnSe NWs. Based on this and extensive optical and structural characterization on individual NTSLs, a linear variation in Eg is shown through a monotonic shift in PL peak position from ZnSe NTSLs as a function of d, with Eg's that lie between those of ZB and WZ crystal structures. This linear variation in Eg was also validated by ab Initio electronic structure calculations. This establishes NTSLs as new nanoscale polytypes advantageous for applications requiring tunable band gaps.

abstract: The larger tolerance to lattice mismatch in growth of semiconductor nanowires (NWs) offers much more flexibility for achieving a wide range of compositions and bandgaps via alloying within a single substrate. The bandgap of III-V InGaAsP alloy NWs can be tuned to cover a wide range of (0.4, 2.25) eV, appealing for various optoelectronic applications such as photodetectors, solar cells, Light Emitting Diodes (LEDs), lasers, etc., given the existing rich knowledge in device fabrication based on these materials. This dissertation explores the growth of InGaAsP alloys using a low-cost method that could be potentially important especially for III-V NW-based solar cells. The NWs were grown by Vapor-Liquid-Solid (VLS) and Vapor-Solid (VS) mechanisms using a Low-Pressure Chemical Vapor Deposition (LPCVD) technique. The concept of supersaturation was employed to control the morphology of NWs through the interplay between VLS and VS growth mechanisms. Comprehensive optical and material characterizations were carried out to evaluate the quality of the grown materials. The growth of exceptionally high quality III-V phosphide NWs of InP and GaP was studied with an emphasis on the effects of vastly different sublimation rates of the associated III and V elements. The incorporation of defects exerted by deviation from stoichiometry was examined for GaP NWs, with an aim towards maximization of bandedge-to-defect emission ratio. In addition, a VLS-VS assisted growth of highly stoichiometric InP thin films and nano-networks with a wide temperature window from 560◦C to 720◦C was demonstrated. Such growth is shown to be insensitive to the type of substrates such as silicon, InP, and fused quartz. The dual gradient method was exploited to grow composition-graded ternary alloy NWs of InGaP, InGaAs, and GaAsP with different bandgaps ranging from 0.6 eV to 2.2 eV, to be used for making laterally-arrayed multiple bandgap (LAMB) solar cells. Furthermore, a template-based growth of the NWs was attempted based on the Si/SiO2 substrate. Such platform can be used to grow a wide range of alloy nanopillar materials, without being limited by typical lattice mismatch, providing a low cost universal platform for future PV solar cells. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2018

As CMOS manufacturing technology approaches fundamental limits, researchers are looking for revolutionary technologies beyond the end of the CMOS roadmap. Recent progress on devices, nano-manufacturing, and assembling of nanoscale structures is driving researchers to explore possible new fabrics, circuits and architectures based on nanoscale devices. Several fabric architectures based on various nanoscale devices have been proposed for nanoscale computation. These show great advantages over conventional CMOS technology but focus on FPGA-style applications. There has been no work shown for nanoscale architectures tuned for a processor application. This dissertation proposes a novel nanowire-based 2-D fabric referred to as Nanoscale Application-Specific IC (NASIC). Compared with other nanoscale fabric architectures, NASIC designs can be optimized for higher density and performance in an application-specific way (similar to ASIC in this aspect) and used as a fabric for processors. We present the design of a wire-streaming processor (WISP-0), which exercises many NASIC circuit styles and optimizations. A major goal of NASIC, and for other nanoscale architectures, is to preserve the density advantage of underlying nanodevices. Topological, doping and interconnect constraints can severely impact the effective density that can be achieved at the system level. To handle these constraints, we propose a comprehensive set of optimizations at both circuit and logic levels. Evaluations show that with combined optimizations, WISP-0 is still 39X denser than the equivalent design in 18nm CMOS technology (expected in 2018 by ITRS). Another key challenge for nanoscale computing systems is dealing with the unreliable nanodevices. The defect rate of nanodevices is expected to be orders of magnitude higher than what we are accustomed to with conventional CMOS processing based on lithography. In this dissertation, we first investigate various sources of defects/faults in NASIC circuits and analyze their impacts. Then, a hierarchical, multi-layer solution is proposed to tolerate defects/faults. Simulation shows that the yield of WISP-0 is as high as 50% even if as many as 15% transistors are defective. Estimations of the speed, power consumption of NASIC designs are also presented.

Orientador: Mônica Alonso Cotta / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-19T18:21:16Z (GMT). No. of bitstreams: 1 Oliveira_DouglasSoaresde_M.pdf: 3151118 bytes, checksum: 954bfe85e80e3ae53e5e5c87d10aa961 (MD5) Previous issue date: 2012 / Resumo: O estudo em nanofios semicondutores é crescente, seja pelo grande potencial de aplicações previsto para eles, seja para entender a dinâmica de formação dessas nanoestruturas. Entretanto, estes dois elementos estão ligados, pois é necessário entender o processo de síntese dos nanofios semicondutores para utilizar todo o seu potencial para aplicações. Neste trabalho, crescemos e estudamos nanofios de fosfeto de índio. Os nanofios foram crescidos pela técnica vapor-líquido-sólido em uma câmara de crescimento epitaxial por feixe químico (CBE). Através de microscopia eletrônica de varredura e microscopia eletrônica de transmissão, obtivemos dados para análise dos nossos resultados. Os parâmetros de crescimento utilizados foram escolhidos de forma que nossos nanofios apresentassem um número bastante significativo de falhas de empilhamento. Utilizamos também nanopartículas catalisadoras muito pequenas (~5nm). Nosso resultado principal foi uma nova morfologia para nanofios. Obtivemos nanofios com variações periódicas de diâmetro sem modificar os parâmetros durante o crescimento. Sendo a distância entre essas variações de diâmetro crescente com o inverso do fluxo do precursor de índio (Trimetil-índio) fornecido durante o crescimento. Análise por microscopia eletrônica de transmissão nos mostrou que essas oscilações periódicas de diâmetro estão associadas com um aumento muito grande no número de falhas de empilhamento e mudanças na fase cristalográfica, de wurtzita para blenda de zinco. Esta morfologia foi modelada por nós como a nanopartícula englobando parcialmente a lateral do nanofio periodicamente durante o crescimento. Nosso modelo é baseado em considerações sobre a competição entre as rotas de incorporação de índio durante o crescimento, as condições termodinâmicas para a nucleação na linha de três fases e estabilidade mecânica da nanopartícula sobre o nanofio durante o crescimento / Abstract: The study of semiconductor nanowires is growing, either due to the great potential for applications or to understand the dynamics of formation of these nanostructures. However, these two elements are linked since it is necessary to understand the synthesis of semiconductor nanowires in order to use all its potential for applications. In this work, we studied and grew nanowires of indium phosphide. These nanowires were grown by the vapor-liquid-solid method on a chemical beam epitaxy (CBE) chamber. They were studied by scanning and transmission electron microscopy. The growth parameters used were chosen so that our NWs presented a significant number of stacking faults and very small (~5nm) catalyst nanoparticles (NPs). Our main result was the observation of a new NW morphology. We have obtained NWs with periodical variations in diameter without any changes in growth parameters during the run. The distance between these oscillations depends almost linearly on the inverse of the Indium precursor flow (TMI) provided during growth. Analysis by transmission electron microscopy has shown that the periodic oscillations in diameter are associated with a very large increase of SF densities and crystallographic phase changes, from Wurtzite to Zinc Blende phase. We have modeled the formation of this morphology as the NP partly wetting the NW sidewalls periodically during growth. Our model is based in considerations of competition between the routes of incorporation of indium during growth, the thermodynamic conditions for nucleation at the three-phase line and mechanical stability of the NP on the NW during growth / Mestrado / Física / Mestre em Física

Orientador: Fernando Iikawa / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-14T10:28:22Z (GMT). No. of bitstreams: 1 Gadret_EvertonGeiger_M.pdf: 38585296 bytes, checksum: 3da598e65313d603b738c440498d2858 (MD5) Previous issue date: 2009 / Resumo: Neste trabalho foram estudadas as propriedades ópticas de nanofios de InP crescidos pelo método Vapor-Liquid-Solid (VLS) no sistema Chemical Beam Epitaxy (CBE) através da técnica de micro-fotoluminescência variando parâmetros de medida, tais como potência de excitação, polarização do sinal emitido e temperatura da amostra. Devido à formação de politipismo (InP nas fases cúbica, do tipo blenda de zinco (ZB), e hexagonal, do tipo wurtzita (WZ)) esta estrutura se torna interessante sob o ponto de vista das propriedades ópticas, devido às interfaces InP¿ZB/InP¿WZ do tipo II. Notamos que há poucas informações na literatura a respeito da estrutura eletrônica do InP na fase wurtzita porque esta fase só foi relatada em nanofios. Concentramos, assim, nossa investigação sobre a estrutura eletrônica de nanofios que contenham ambas as fases. Identificamos emissões ópticas dos poços quânticos tipo II em nanofios de InP assim como emissões envolvendo impurezas aceitadoras rasas e recombinação no gap do InP¿WZ. A emissão óptica dos poços quânticos tipo II é dominante a baixas temperaturas, abaixo de 100K, e está entre 1,44 e 1,46eV a 10K. O comportamento desta emissão como função da temperatura, potência de excitação e polarização da luz está de acordo com a estrutura proposta e é confirmada por imagem de microscopia eletrônica de transmissão (TEM). A emissão óptica da impureza rasa está ~ 43meV abaixo da emissão do poço quântico, valor bem próximo do carbono aceitador no InP na fase cúbica. A emissão óptica associada ao InP¿WZ em 1,49eV (10K) foi observada a temperaturas de 10K a 300K, em concordância com resultados relatados na literatura. Observamos também transição óptica relacionada a portadores localizados nas barreiras dos poços quânticos a temperaturas mais altas, acima de 150K. / Abstract: Optical properties of InP nanowires grown by Vapor-Liquid-Solid (VLS) method in a Chemical Beam Epitaxy system were investigated by using micro-photoluminescence spectroscopy varying experimental parameters such as excitation power, emitted signal polarization and sample temperature. Due to polytypism (InP in cubic, zincblende (ZB), and hexagonal, wurtzite (WZ) phases), this structure becomes interesting by the point of view of optical properties, due to type¿II InP¿ZB/InP¿WZ interfaces. We have noticed that there are few informations in the literature about electronic structures of InP in wurtzite phase, because this phase has been only reported in nanowires. We focused, thus, our investigation about electronic structure of nanowires having both structural phases. We identified optical emissions from type II quantum wells in InP nanowires as well as emissions involving shallow acceptor impurities and InP¿WZ gap recombination. The type II quantum well optical emission is dominant at low temperatures, below 100K, which is in 1,44 ¿ 1,46eV range at 10K. This emission behavior as function of temperature, excitation power and light polarization is in agreement with the proposed structure and is supported by transmission electronic microscopy (TEM) imagem. The shallow impurity emission is ~ 43meV below the quantum well emission, a value close to the carbon acceptor in InP in cubic phase. The optical emission associated to the InP¿WZ at 1,49eV (10K) was observed from temperatures of 10K to 300K, in agreement with results reported in literature. We also observed an additional optical transition related to the carrier localized at the barriers of the quantum wells at at high temperatures, above 150K. / Mestrado / Física da Matéria Condensada / Mestre em Física

This dissertation addresses the fundamental problem of how to build computing systems for the nanoscale. With CMOS reaching fundamental limits, emerging nanomaterials such as semiconductor nanowires, carbon nanotubes, graphene etc. have been proposed as promising alternatives. However, nanoelectronics research has largely focused on a `device-first' mindset without adequately addressing system-level capabilities, challenges for integration and scalable assembly. In this dissertation, we propose to develop an integrated nano-fabric, (broadly defined as nanostructures/devices in conjunction with paradigms for assembly, inter-connection and circuit styles), as opposed to approaches that focus on MOSFET replacement devices as the ultimate goal. In the `fabric-centric' mindset, design choices at individual levels are made compatible with the fabric as a whole and minimize challenges for nanomanufacturing while achieving system-level benefits vs. scaled CMOS. We present semiconductor nanowire based nano-fabrics incorporating these fabric-centric principles called NASICs and N3ASICs and discuss how we have taken them from initial design to experimental prototype. Manufacturing challenges are mitigated through careful design choices at multiple levels of abstraction. Regular fabrics with limited customization mitigate overlay alignment requirements. Cross-nanowire FET devices and interconnect are assembled together as part of the uniform regular fabric without the need for arbitrary fine-grain interconnection at the nanoscale, routing or device sizing. Unconventional circuit styles are devised that are compatible with regular fabric layouts and eliminate the requirement for using complementary devices. Core fabric concepts are introduced and validated. Detailed analyses on device-circuit co-design and optimization, cascading, noise and parameter variation are presented. Benchmarking of nanowire processor designs vs. equivalent scaled 16nm CMOS shows up to 22X area, 30X power benefits at comparable performance, and with overlay precision that is achievable with present-day technology. Building on the extensive manufacturing-friendly fabric framework, we present recent experimental efforts and key milestones that have been attained towards realizing a proof-of-concept prototype at dimensions of 30nm and below.

Ternary InGaN and AlGaN alloys have been sought after for the application of various optoelectronic devices spanning a large spectral range between the deep ultraviolet and infrared, including light-emitting diodes, and laser diodes. Their non-ideal alloy mixing, and differences in bond energy and in adatom diffusion are established as the cause for various types of nanoscale compositional inhomogeneity commonly observed in nitride thin films. Growth in a nanowire geometry can overcome the phase separation, surface segregation, and chemical ordering by providing enhanced strain relaxation of the large lattice mismatch at the free surfaces. In this dissertation, the spectral and spatial luminescence distributions of ternary III-N alloy nanowire heterostructures are investigated and correlated to structural and chemical properties with scanning transmission electron microscopy. Quantitative elemental mapping of InGaN/GaN dot-in-a-wire structures using electron energy-loss spectroscopy revealed compositional non-uniformity between successive quantum dots. Local strain mapping of the heterostructure showed a dependence of the incorporation of indium on the magnitude of the out-of-plane compressive strain within the underlying GaN barrier layer. Cathodoluminescence spectroscopy on individual nanowires presented diverse emission properties, nevertheless, the In-content variability could be directly correlated to the broad range of peak emission energies. Atomic-level chemical ordering within the InGaN was then reported, and attributed to the faceted growth surface in nanowires that promotes preferential site incorporation by In-atoms that allows for better strain relaxation. Distinct atomic-scale alloy inhomogeneities were also investigated in AlGaN nanowires, which evidenced spatial localization of carriers taking place at the resulting energy band fluctuations. A high spectral density of narrow emission lines arose from such compositional modulations, whose luminescence behaviours exhibit a dependence on the nature of the compositional fluctuations from which they originate. / Thesis / Doctor of Philosophy (PhD)

Les nanofils (NFs) de semi-conducteur (SC) sont des objets possédant des propriétés très intéressantes pour la fabrication de futurs composants électroniques à l'échelle nanométrique. Ils sont élaborés grâce à l'utilisation d'un catalyseur métallique (Au) formant un point eutectique profond en s'alliant à la phase SC (Si) permettant la germination et la croissance du NF à basses températures. Ce travail a pour but l'étude de la formation, de la structure et du comportement de ces gouttes d'alliage eutectique en interaction avec le substrat dont les propriétés futures du NF vont dépendre. L'étude a été menée in-situ, par utilisation du rayonnement synchrotron qui est un outil parfaitement dédié à la caractérisation de structures à l'échelle atomistique. Les gouttes d'eutectique ont été obtenues par le démouillage d'un film d'or. L'étude de ce procédé a révélé des changements dans les relations d'épitaxies entre l'or et le silicium. Les gouttes ainsi formées sont accompagnées d'une couche de mouillage, se révélant être une reconstruction de surface, dont les conditions de formation ainsi que la structure atomique ont été déterminées. Lors du refroidissement, une augmentation des effets de surfusion a été observée en présence de cette reconstruction et sont expliqués par la structure même de cette dernière qui semble stabiliser l'état liquide. Des expériences similaires ont été faites sur d'autres systèmes (Au-Ge, Al-Si) et une synthèse a été réalisée pour comparer les connaissances actuelles sur le ce sujet avec les résultats de ce travail. / Semiconductor (SC) nanowires (NMs) have been identified as important components for future electronic and sensor nanodevices. They are produced using a metal catalyst (Au) that forms a low eutectic point with the SC phase (Si) and enables their nucleation and their growth at low temperatures. The aim of this study is to investigate the formation, the structure as well as the behaviour of such liquid eutectic droplets in interaction with the substrates on which the futur NMs properties will later depend. This work has been performed in-situ, using synchrotron radiation which is the perfect tool to characterize this mechanism at the atomistic scale. The eutectic droplets have been obtained through the dewetting of thin gold films. This process has been found to modify the epitaxial relationships between the gold and the silicon substrate. The obtained droplets are accompanied by a wetting layer (WL) whose conditions of formation as well as atomic structure, which turned to be a surface reconstruction, have been determined. During the cooling process, the supercooling effects in such AuSi eutectic droplets have been found to be enhanced in the presence of this reconstruction. They are explained by the specific structure of the reconstruction which is likely to stabilize the liquid phase. Similar experiments on other systems (Au-Ge or Al-Si) were performed and a synthesis has been made in order to present the current knowledge on this topic in comparison with the results of this work.

Cette thèse porte sur la conversion thermoélectrique de nanofils semi-conducteurs désordonnés en configuration de transistor à effet de champ.On considère d’abord le régime de transport élastique à basse température. En utilisant un modèle d'Anderson 1D, on dérive des expressions analytiques pour le coefficient Seebeck typique d’un nanofil en fonction de la tension de grille, et on montre que celui-ci augmente fortement en bord de bande. Ces résultats sont confirmés par un calcul numérique du Seebeck, basé sur un algorithme de fonctions de Green récursif.On considère ensuite le régime inélastique où les électrons, assistés par les phonons, sautent entre états localisés. En résolvant numériquement le réseau de résistances aléatoires de Miller-Abrahams, on montre que le coefficient Seebeck peut atteindre des valeurs très élevées au voisinage des bords de bande du nanofil. La théorie de percolation de Zvyagin étendue au cas unidimensionnel nous permet de décrire qualitativement nos résultats. Par ailleurs, les échanges de chaleur entre électrons et phonons en bord de bande entraînent la formation de points chauds et froids à la surface du substrat, qui pourraient être utilisés pour le refroidissement de circuits électroniques. Cet effet est étudié pour un ensemble de fils en parallèle. Le facteur de puissance et la figure de mérite de ces systèmes sont aussi estimés.Enfin, on étudie un système général à trois terminaux en réponse linéaire. On calcule les coefficients de transport locaux et non-locaux, et les figures de mérite généralisées, puis l'on discute à l'aide de deux exemples la possibilité d’améliorer la performance d’une machine thermique quantique générique. / This thesis is focused on thermoelectric conversion in disordered semiconductor nanowires in the field effect transistor configuration. We first consider a low temperature regime, when electronic transport is elastic. For a 1D Anderson model, we derive analytical expressions describing the typical thermopower of a single nanowire as a function of the applied gate voltage, and we show that it is largely enhanced at the nanowire band edges. Our results are confirmed by numerical simulations based on a Recursive Green Function calculation of the thermopower. We then consider the case of inelastic transport, achieved by phonon-assisted hopping among localized states (Variable Range Hopping). By solving numerically the Miller Abrahams random resistor network, we show that the thermopower can attain huge values when the nanowire band edges are probed. A percolation theory by Zvyagin extended to nanowires allows to qualitatively describe our results. Also, the mechanism of heat exchange between electrons and phonons at the band edges lead to the generation of hot and cold spots near the boundaries of a substrate. This effect, of interest for cooling issues in microelectronics, is showed for a set of parallel nanowires, a scalable and hence promising system for practical applications. The power factor and figure of merit of the device are also estimated.Finally, we characterize a general three-terminal system within the linear response (Onsager) formalism: we derive local and non-local transport coefficients, as well as generalized figures of merit. The possibility of improving the performance of a generic quantum machine is discussed with the help of two simple examples.