Rozprawy doktorskie na temat „Nanostructured Semiconductors Crystals”

This work reports the study of semiconductor nanocrystals, also known as quantum dots, focusing specifically on zinc sulfide (ZnS). Two different capping agents were used (glutathione and N-acetyl-L-cysteine) for the preparation of ZnS nanocrystals via aqueous route. The study aimed specifically at evaluating the efficacy of the capping agents in the stabilization of semiconductor nanocrystal suspensions towards coalescence as well as in controlling nanocrystal size and optical properties. In addition the effect of doping the ZnS nanocrystals with transition metal ions (Cu2+ and Co2+) on the photoluminescence properties has also been studied. Finally the possibility of energy transfer between the semiconductor nanocrystals and the safranine dye was also evaluated. Spherical-shaped glutathione and N-acetyl-L-cysteine-capped ZnS nanocrystal were obtained with diameters below 5 nm free from coalescence, showing that both iv capping agents were efficient as stabilizers. Both capping agents lead to the formation of ZnS nancrystals with blue fluorescence, typical of the involvement of surface defect states of ZnS. However, samples prepared with glutathione exhibited higher fluorescence intensities than those obtained with N-acetyl-L-cysteine. Upon doping glutathione-capped ZnS nanocrystals with both copper and cobalt the fluorescence intensities decreased gradually following the increase in nominal concentration of dopants, suggesting that cobalt ions played a similar role as copper. Considering both the effect on the intensities and the absence of d-d metal transitions this study suggests that doping reduced the concentration of cation vacancies as well as the involvement of at least one cobalt state in the transition processes. Changes in emission wavelength with different dopant concentrations were not observed probably owing to lack of influence on the nanocrystal size. Finally the preliminary study of fluorescence quenching of semiconductor nanocrystals by safranine dye indicated that significantly low concentrations were able to quench the emissions. Different components of the emission band were distinctly affected. Data analysis by Stern-Volmer plots suggested the occurrence of more than one transfer processes (energy and/or electron transfer). This study will be refined in future works.
No presente trabalho foram estudados nanocristais semicondutores, tambem conhecidos como pontos quanticos ou quantum dots, selecionando-se especificamente o sulfeto de zinco (ZnS). Foram utilizados ois diferentes agentes estabilizantes (glutationa e N-acetil-L-cisteina) na obtencao de nanocristais de ZnS por via aquosa. Buscou-se avaliar, especificamente, a eficiencia dos agentes tiois na estabilizacao das suspensoes de nanocristais frente a agregacao, no controle e distribuicao de tamanhos das particulas, bem como nas propriedades opticas. Estudou-se, alem disto, o efeito da dopagem com ions de metais de transicao (Cu2+ e Co2+) nas propriedades de fluorescencia. Por fim, foi avaliada a possibilidade de transferencia de energia entre os nanocristais semicondutores dopados e o corante safranina. Os nanocristais semicondutores de ZnS estabilizados por glutationa e por N-acetil-L-cisteina foram obtidos com tamanhos abaixo de 5 nm, formas aproximadamente esfericas e livres de agregacao, evidenciando que ambos agentes ii estabilizantes foram eficientes. Ambos agentes estabilizantes levaram a formacao de nanocristais com emissoes na regiao do azul, caracteristicas do envolvimento de estados de defeito de superficie do ZnS. No entanto, as amostras preparadas com glutationa apresentaram maiores intensidades de fluorescencia, quando comparadas com aquelas preparadas com N-acetil-L-cisteina. A dopagem dos nanocristais semicondutores ZnS/Glu com ions cobre e cobalto teve um efeito de diminuir as intensidades de fluorescencia dependente da concentracao nominal dos dopantes em ambos os casos, sugerindo que o cobalto atua de modo analogo ao cobre. Considerando-se tanto o efeito sobre as intensidades de emissao do ZnS quanto a ausencia de transicoes d-d do metal, o estudo sugeriu que a dopagem reduz a concentracao de vacancias de cations, bem como o envolvimento de pelo menos um dos estados eletronicos do cobalto nos processos de transicao. Nao se observou variacoes nos comprimentos de onda para diferentes concentracoes dos dopantes, provavelmente pela ausencia de interferencia no tamanho dos nanocristais semicondutores formados. Por fim, o estudo preliminar da supressao de fluorescencia dos nanocristais semicondutores pelo efeito de diferentes concentracoes do corante safranina mostrou que concentracoes significativamente baixas do corante foram suficientes para diminuir a intensidade de fluorescencia. Diferentes componentes das bandas de emissao dos nanocristais semicondutores foram influenciados de modo distinto. A analise dos dados pelos graficos de Stern-Volmer sugeriu a ocorrencia de mais de um processo de transferencia (energia e/ou eletrons). Este estudo sera aprofundado nos trabalhos futuros.

The dissertation starts from the understanding of dislocation dissipation mechanism due to the image force acting on the dislocation. This work implements a screw dislocation in solids with free surfaces by a novel finite element model, and then image forces of dislocations embedded in various shaped GaN nanorods are calculated. As surface stress could dramatically influence the behavior of nanostructures, this work has developed a novel analytical framework to solve the stress field of solids with dislocations and surface stress. It is successfully implemented in this framework for the case of isotropic circular nanowires (2D) and the analytical result of the image force has been derived afterwards. Based on the finite element analysis and the analytical framework, this work has a semi-analytical solution to the image force of isotropic nanorods (3D) with surface stress. The influences of the geometrical parameter and surface stress are illustrated and compared with the original finite element result. In continuation, this work has extended the semi-analytical approach to the case of anisotropic GaN nanorods. It is used to analyze image forces on different dislocations in GaN nanorods oriented along polar (c-axis) and non-polar (a, m-axis) directions. This work could contribute to a wide range of nanostructure design and fabrication for dislocation-free devices.

Semiconductor nanostructures have attracted great interest owing to their unique physical properties and potential applications in nanoscale functional devices. The enhancement of the physical properties of semiconductor nanostructures and their performance in devices requires a deeper understanding of their fundamental microstructural properties. Thus this thesis is focused on the experimental and theoretical studies of the microstructural properties of two important semiconductor nanostructures: axial heterostructured silicon nanowires with varying doping and indium nitride colloidal nanoparticles. In this thesis, axial heterostructured silicon nanowires with varying doping were synthesized on an oxide-removed Si{111} substrate using a vapour-liquid-solid approach. Their fundamental microstructural properties, including the crystalline structure, wire growth direction and morphologies, were studied using various characterization techniques. It is found that a very small fraction of the silicon nanowires crystallize in a hexagonal (wurtzite) phase, which is thermodynamically unstable in bulk silicon under ambient conditions, while a large majority of the synthesized silicon nanowires exhibit the expected diamond cubic crystalline structure. About 75% of the diamond cubic silicon nanowires synthesized grow in a single <111> direction, while the rest contain growth-related kinks, where the nanowire switches to another direction during the growth. The ~109° silicon nanowire kinks are the most commonly observed, and the growth direction before and after such ~109° kink are both <111>. The sidewalls of silicon nanowires do not change abruptly at the ~109° kink, but exhibit an elbow-shaped structure. It is also found that the nanowire sidewalls exhibit periodic nanofaceting, which is strongly doping-dependent. The nanofaceting is found to occur during the enhanced sidewall growth that arises when the diborane dopant gas is introduced. A thermodynamic model predicting the dependence of nanofacet period on the wire diameter is developed. Another semiconductor nanostructure studied in this thesis is indium nitride colloidal nanoparticles, which were grown using a solution-phase chemical method. The formation of such indium nitride colloidal nanoparticles is confirmed by studying their compositions, crystalline structures and shape using various electron microscopy techniques. The size of the indium nitride colloidal nanoparticles was controlled by varying the time of solution-phase reactions. The most probable size of the colloidal nanoparticles increases and the size distribution broadens with the increase of reaction time. The crystalline structures of the indium nitride colloidal nanoparticles are found to be particle size dependent. The observed dependence of the band gap blueshift of the indium nitride colloidal nanoparticles on the reaction time (hence the particle size) is explained by the quantum-size effect.

La consommation d’énergie liée aux technologies de l’information augmente trèsrapidement et dans la mesure où la société a besoin d’être toujours plus connectée tout ens’appuyant sur des solutions durables, les technologies actuelles ne suffisent plus. La photoniqueintégrée s’impose dès lors comme une alternative à l’électronique pour réaliser du traitementdu signal économe en énergie. Au cours de cette thèse, j’ai étudié des structures sub-longueurd’onde en semiconducteur, les cristaux photoniques, qui présentent des propriétés non linéairesimpressionnantes. Plus précisément, le confinement fort et la propagation en lumière lente permettentun traitement sur puce de signal ultra-rapide tout optique, soit à partir de mélange àquatre ondes ou d’auto-modulation de phase. L’originalité est l’utilisation de nouveaux matériauxsemi-conducteurs ayant moins d’absorption non linéaires et par porteurs libres, effets qui limitentla pleine exploitation des effets non linéaires dans les structures photoniques en Silicium. Dansma thèse, des semiconducteurs III-V ont été utilisés pour développer des guides et des cavitéscristal photonique de grande qualité qui sont en mesure de supporter des densités de puissanceoptiques extrêmement élevées ainsi que de grands niveaux de puissance moyenne. J’ai amélioré laconductivité thermique des guides d’ondes grâce à l’intégration hétérogène de membranes GaInPavec du dioxyde de silicium. Cette plateforme permettra à terme de démontrer de l’amplificationsensible à la phase dans le régime continu que j’ai déjà démontré dans le régime pulsé en utilisant des membranes suspendues en GaInP. En parallèle, j’ai démontré des cristaux photoniques de grande qualité dans du Gallium phosphure, qui est un matériau très prometteur en raison de lagrande bande interdite et de la très bonne conductivité thermique. Les résultats préliminaires ontpermis la réalisation d’un régime non linéaire intense (mini-peigne de fréquence, compression etfission de soliton ...)
The energy consumption of the whole ICT ecosystem is growing at a fast paceand in a global context of the search for an ever more connected yet sustainable society, a technologicalbreakthrough is desired. Here, integrated nonlinear photonics will help by providingnovel possibilities for energy efficient signal processing. In this PhD thesis, I have been investigatingsub-wavelength semiconductor structures, particularly photonic crystals, which have shownremarkable nonlinear properties. More specifically the strong confinement and slow light propagationenables on-chip ultra-fast all-optical signal processing, either based on four-wave-mixingor self-phase modulation. The main point here is the use of novel semiconductor materials withimproved nonlinear properties with respect to Silicon. In fact, it has now been acknowledgedthat the nonlinear and free-carriers absorption in Silicon integrated photonic structures is anissue hindering the full exploitation of nonlinear effects. In my thesis, wide-gap III-V semiconductorshave been used to develop high quality photonic crystal waveguides and cavities whichare able to sustain extremely high optical power densities as well as large average power levels.I have demonstrated PhC waveguides with much improved thermal conductivity through heterogeneousintegration of GaInP membranes with silicon dioxide. This will allow continuous wave phase-sensitive amplification, which I already demonstrated in the pulsed regime using GaInPself-suspended membranes. In parallel, I have demonstrated high quality PhC in Gallium Phosphide,which is a very promising material because of the large bandgap and the very good thermalconductivity. Preliminar results demonstrate the achievement of extremely large nonlinear regime(mini-comb, soliton compression and fission ...)

This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within the inorganic semiconductors. Inorganic semiconductor nanowires and their blends with semiconducting polymers have been investigated using state-of-the-art ultrafast optical techniques to provide information on the sub-picosecond to nanosecond photoexcitation dynamics in these systems. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising nanowires in hybrid organic photovoltaic devices, revealing the performances to date. The experimental methods used during the thesis are detailed in Chapter 3. Chapter 4 describes the crucial roles of surface passivation on the ultrafast dynamics of exciton formation in gallium arsenide (GaAs) nanowires. By passivating the surface states of nanowires, exciton formation via the bimolecular conversion of electron-hole plasma can observed over few hundred picoseconds, in-contrast to the fast carrier trapping in 10 ps observed in the uncoated nanowires. Chapter 5 presents a novel method to passivate the surface-states of GaAs nanowires using semiconducting polymer. The carrier lifetime in the nanowires can be strongly enhanced when the ionization potential of the overcoated semiconducting polymer is smaller than the work function of the nanowires and the surface native oxide layers of nanowires are removed. Finally, Chapter 6 shows that the carrier cooling in the type-II wurtzite-zincblend InP nanowires is reduced by order-of magnitude during the spatial charge-transfer across the type-II heterojunction. The works decribed in this thesis reveals the crucial role of surface-states and bulk defects on the carrier dynamics of semiconductor nanowires. In-addition, a novel approach to passivate the surface defect states of nanowires using semiconducting polymers was developed.

The objective of this project is to establish a new technology to grow high quality GaN based material by nano selective area growth (NSAG). The motivation is to overcome the limit of the conventional growth method, which yield a high density of dislocation in the epitaxial layer. A low dislocation density in the epitaxial layer is crucial for high performance and high efficiency devices. This project focuses on growth and material characterization of GaN based nanostructures (nanodots and nanostripes) grown using the NSAG method that we developed. NSAG, with a precise control of diameter and position of nanostructures opens the door to new applications such as: 1) single photon source, 2) photonic crystal, 3) coalescence of high quality GaN template, and 4) novel nanodevices.

Dans ce mémoire sont abordées quelques études sur la croissance, l'électromigration et la thermomigration de la surface des semiconducteurs tels que le Ge(111), le Si(100) et le Si(111). Sur le plan expérimental, la Microscopie à Electrons Lents (LEEM) nous a permis d'accéder à la dynamiques des phénomènes in situ et en temps réel. Nous étudions l'électromigration et la thermomigration sur la surface de Si(100) qui présente deux reconstructions de surfaces (2x1) et (1x2) selon l'orientation des dimères. Nous montrons que l'anisotropie de diffusion peut affecter le sens de mouvement des nanostructures (trous et îlots). Nous étudions aussi l'électromigration et la thermomigration sur la surface de Si(111). Nous montrons que les trous (1x1) dans la phase (7x7) bougent dans le sens opposé au courant électrique, et dans le même sens du gradient thermique. Nous avons obtenu la charge effective et le coefficient de Soret des atomes de Si en présence d'un courant électrique et d'un gradient thermique. Enfin est abordée l'étude de la nucléation, la croissance et la coalescence dynamique de gouttelettes d'Au sur la surface d'Au/Ge(111), ainsi que l'électromigration des domaines 2D d'Au/Ge(111)-(√3x√3) dans la phase (1x1)
This thesis is focused on the study of the growth, electromigration and thermomigration of nanostructures on the surface of semiconductors such as Si(100), Si(111) and Ge(111). On an experimental viewpoint, Low Energy Electron Microscopy (LEEM) allows us to access to the dynamics of the phenomena in situ and in real time. We have studied under electromigration and thermomigration the motions of 2D monoatomic holes and islands on the Si (100) surface. We have shown that diffusion anisotropy due to (2x1) and (1x2) surface reconstructions can affect the direction of motion of nanostructures. We have also studied electromigration and thermomigration of Si (111) surface. We show that 2D-(1x1) holes in the (7x7) phase move in the direction opposite to the electric current, while in the direction of the thermal gradient. We have obtained the effective charge and the Soret coefficient of Si atoms in presence of an electric current and a thermal gradient. At last, the nucleation, growth and dynamic coalescence of Au droplets on Au/Ge(111) surface is studied, and the electromigration of 2D Au/Ge(111)-( √3x√3) domains on Au/Ge(111)-(1x1) surface

Nanomaterials have attracted great interest due to the unique physical properties and great potential in the applications of nanoscale devices. Two dimensional atomic crystals, which are atomic thickness, especially graphene, have triggered the gold rush recently due to the fascinating high mobility at room temperature for future electronics. The crystal structure of nanomaterials will have great influence on their physical properties. Thus, this thesis is focused on developing the methods to control the crystal structure of nanomaterials, namely quantum dots as semiconductor, boron nitride (BN) as insulator, graphene as semimetal, with low cost for their applications in photonics, structural support and electronics. In this thesis, firstly, Mn doped ZnSe quantum dots have been synthesized using colloidal synthesis. The shape control of Mn doped ZnSe quantum dots has been achieved from branched to spherical by switching the injection temperature from kinetics to thermodynamics region. Injection rates have been found to have effect on controlling the crystal phase from zinc blende to wurtzite. The structural-property relationship has been investigated. It is found that the spherical wurtzite Mn doped ZnSe quantum dots have the highest quantum yield comparing with other shape or crystal phase of the dots. Then, the Mn doped ZnSe quantum dots were deposited onto the BN sheets, which were micron-sized and fabricated by chemical exfoliation, for high resolution imaging. It is the first demonstration of utilizing ultrathin carbon free 2D atomic crystal as support for high resolution imaging. Phase contrast images reveal moiré interference patterns between nanocrystals and BN substrate that are used to determine the relative orientation of the nanocrystals with respect to the BN sheets and interference lattice planes using a newly developed equation method. Double diffraction is observed and has been analyzed using a vector method. As only a few microns sized 2D atomic crystal, like BN, can be fabricated by the chemical exfoliation. Chemical vapour deposition (CVD) is as used as an alternative to fabricate large area graphene. The mechanism and growth dynamics of graphene domains have been investigated using Cu catalyzed atmospheric pressure CVD. Rectangular few layer graphene domains were synthesized for the first time. It only grows on the Cu grains with (111) orientation due to the interplay between atomic structure of Cu lattice and graphene domains. Hexagonal graphene domains can form on nearly all non-(111) Cu surfaces. The few layer hexagonal single crystal graphene domains were aligned in their crystallographic orientation over millimetre scale. In order to improve the alignment and reduce the layer of graphene domains, a novel method is invented to perform the CVD reaction above the melting point of copper (1090 ºC) and using molybdenum or tungsten to prevent the balling of the copper from dewetting. By controlling the amount of hydrogen during the growth, individual single crystal domains of monolayer over 200 µm are produced determined by electron diffraction mapping. Raman mapping shows the monolayer nature of graphene grown by this method. This graphene exhibits a linear dispersion relationship and no sign of doping. The large scale alignment of monolayer hexagonal graphene domains with epitaxial relationship on Cu is the key to get wafer-sized single crystal monolayer graphene films. This paves the way for industry scale production of 2D single crystal graphene.

Ce travail a porte sur la croissance epitaxiale des nitrures d'elements iii gan, aln, et inn, en utilisant l'epitaxie par jets moleculaires assistee par plasma d'azote. Nous avons optimise les premiers stades de la croissance de gan ou aln sur substrat al#2o#3 (0001). Le processus utilise consiste a nitrurer la surface du substrat a l'aide du plasma d'azote, afin de la transformer en aln, puis a faire croitre une couche tampon d'aln ou de gan a basse temperature, avant de reprendre la croissance de gan ou aln a haute temperature (680 a 750c). Nous avons en particulier etudie les proprietes d'une couche de gan en fonction de la temperature a laquelle est realisee l'etape de nitruration. Lorsque les conditions de demarrage de la croissance sont optimisees, nous avons pu observer des oscillations de rheed pendant la croissance de la couche de gan. Nous avons etudie l'effet du rapport v/iii sur la morphologie de surface et les proprietes optiques et structurales de cette couche. Nous avons propose l'utilisation de l'indium en tant que surfactant pour ameliorer ces proprietes. Nous avons ensuite aborde la realisation de superreseaux gan/aln dont nous avons optimise les interfaces. Les mecanismes de relaxation des contraintes de aln sur gan et gan sur aln ont ete etudies. Nous avons egalement elabore les alliages algan et ingan, comme barrieres quantiques dans les heterostructures. Nous avons montre que la relaxation elastique des contraintes de gan en epitaxie sur aln donne lieu a la formation d'ilots de tailles nanometriques, qui se comportent comme des boites quantiques. Leur densite et leur taille dependent de la temperature de croissance, et des conditions de murissement apres croissance. Les proprietes optiques de ces ilots sont gouvernees a la fois par les effets de confinement quantique et par le fort champ piezo-electrique induit par la contrainte dans les ilots.

博士
國立臺灣大學
物理研究所
99
In this dissertation, we have reported the novel physical properties in the composites consisting of nanostructured semiconductors, photonic crystals (PCs), surface plasmons, and magnetic materials. The results can be divided into four parts which are spin transport in Si0.5Ge0.5/Si multiple quantum wells (MQWs), enhancement of luminescence extraction in Si0.5Ge0.5/Si MQWs by using PCs, manipulation of localized surface plasmon resonance (LSPR) by applying magnetic fields, and magnetoelectric (ME) effect in the composite consisting of piezoelectric semiconductors and ferromagnetic materials. In the first part, we have studied the properties of spin transport in Si0.5Ge0.5/Si MQWs. Circular photogalvanic effect (CPGE) and linear photogalvanic effect for interband transition have been observed simultaneously in Si0.5Ge0.5/Si MQWs. The signature of the CPGE is evidenced by the change of its sign upon reversing the radiation helicity. It is found that the observed CPGE photocurrent is an order of magnitude greater than that obtained for intersubband transition. The dependences of the CPGE on the angle of incidence and the excitation intensities can be well interpreted based on its characteristics. The large signal of spin generation observed here at room temperature should be very useful for the realization of practical application of spintronics. In the second part, we have successfully achieved the selective enhancement and suppression of the photoluminescence (PL) arising from Si0.5Ge0.5/Si MQWs by PCs. The formation of the stop band in PCs is designed to be a filter as well as a reflector. It is found that the self-assembled PCs are able to selectively enhance the luminescence of the type-II transitions at the interface between Si and Si0.5Ge0.5/Si layers and suppress the emission from Si. Our working principle shown here can be extended to many other material systems, and should be very useful for creating high power solid-state emitters. In the third part, magnetically tunable LSPR based on the composite consisting of noble metal nanoparticles and a ferromagnetic thin film have been demonstrated. It is found that both of the frequency and linewidth of the LSPR can be manipulated by applying an external magnetic field. The underlying mechanism is attributed to the variation of the dielectric constant in the ferromagnetic thin film resulted from the change of the magnetization. Our result shown here paves an alternative route to manipulate the characteristics of LSPR, which may be served as a new design concept for the development of magneto-optical devices. In the final part, The ME effect has been demonstrated based on the composite of the InGaN/GaN MQWs and the FeCo thin film. By applying an external magnetic field, the ferromagnetic layer will be deformed due to magnetostriction. This deformation is transmitted to the piezoelectric layers and results in piezoelectric effect, which induces electric polarization in the piezoelectric layers. The induced electric polarization changes the strain and the built-in internal electric field in the InGaN/GaN MQWs and therefore the optical properties of the InGaN/GaN MQWs change. The results shown here open up a possibility for the application of nitride semiconductors in magneto-optical and ME engineering. The novel phenomena discovered in this dissertation provides a more detailed understanding and potential applications of the composites consisting of semiconductor nanostructures, PCs, surface plasmons, and magnetic materials.

Semiconductor nanocrystals, also known as quantum dots (QDs), are a relatively new class of materials with unique size-dependent optical properties that enable the use of these materials in a variety of applications, including fluorescent labels for biomolecules, illumination and display technologies and photovoltaics. When the size of the QD is smaller than the mean separation of an optically excited electron-hole pair, or exciton, size-dependent fluorescence is observed as their emission peak shifts to larger wavelengths with increasing size. Doping of QDs with transition metals enables the tuning of their optoelectronic properties, leading to emission wavelengths longer than their bulk emission. The doping of QDs has recently garnered significant attention because it allows for the ability to tune the QD emission without changing its size. Currently, the most common method for synthesizing QDs involves the injection of organometallic precursors into hot coordinating solvents. To obtain monodisperse nanocrystals with this technique, instantaneous injection of the reactants, uniform nucleation over the entire reactor volume and perfect mixing are required. These conditions are difficult to achieve in practice, and even more difficult in a scaled-up reactor system necessary for commercial applications. The use of microemulsions as templates can enable the synthesis of semiconductor nanocrystals of uniform size and shape, and allow for scalability. The template used in this work consists of para-xylene as the continuous phase, water as the dispersed phase, and a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO37-PPO56-PEO37) block copolymer as the surfactant, with the reactants dissolved in the aqueous dispersed phase. Microemulsions formed by this technique, exhibit very slow droplet to droplet coalescence kinetics and allow for the growth of particles with narrow size distribution. A microemulsion template was used to synthesize Mn-doped ZnSe QDs using zinc-acetate and manganese-acetate as reactants which are dissolved in the aqueous dispersed phase. The microemulsion was placed in a reactor and hydrogen selenide gas was bubbled through the solution. A single ZnSe QD formed in each droplet of the microemulsion via an irreversible reaction between the precursors and coalescence of the resulting nuclei. The size of the nanocrystals was controlled to be between 5 and 8 nm by adjusting the initial concentration of zinc-acetate in water. The quantum confinement threshold for ZnSe is 9 nm and the bulk emission of ZnSe is 460 nm. The as-grown particles initially exhibit a size-dependent emission peak, attributed only to ZnSe, with a wavelength less than 460 nm. An emission peak at 585 nm, attributed to Mn2+ ions, appears after a few days in storage and increases substantially with time, eventually reaching a plateau. This indicates that ZnSe QDs are formed first and Mn2+ ions slowly diffuse into their lattice. The synthesis method employed in this work allows for a detailed study of dopant incorporation into ZnSe nanocrystals as a function of time. The time evolution of the intensity and the ratio of the ZnSe and Mn2+ emission peaks were studied as a function of dopant salt concentration in the precursor solution. A model was developed to describe the Mn2+ incorporation into the ZnSe nanocrystal by assuming that the Mn2+ to ZnSe emission intensity ratio is proportional to the amount of Mn2+ incorporated in the ZnSe lattice. To enable the use of the doped QDs in applications, a procedure was developed for extraction of the QDs from the template, capping with hydrophilic ligands, and stabilization in an aqueous solution. Experiments were also performed to accelerate the Mn2+ incorporation in the ZnSe lattice. A ZnSe layer was grown over the initial QDs and was found to substantially increase the fluorescence emission intensity. Additionally the synthesis technique was expanded to use liquid crystals as templates with the purpose of growing Mn-doped ZnSe nanostructures, such as nanodiscs or nanowires, which have potential applications in nanoelectronics.

Thesis (Ph.D.)--State University of New York at Buffalo, 2005.
Title from PDF title page (viewed on Feb. 24, 2006) Available through UMI ProQuest Digital Dissertations. Thesis adviser: Triantafyllos J. Mountziaris, Paschalis Alexandridis. Includes bibliographical references.

Indiana University-Purdue University Indianapolis (IUPUI)
Fabrication and analysis of Copper Indium Gallium di-Selenide (CIGS) nanoparticles-based thin film solar cells are presented and discussed. This work explores non-traditional fabrication processes, such as spray-coating for the low-cost and highly-scalable production of CIGS-based solar cells. CIGS nanoparticles were synthesized and analyzed, thin CIGS films were spray-deposited using nanoparticle inks, and resulting films were used in low-cost fabrication of a set of CIGS solar cell devices. This synthesis method utilizes a chemical colloidal process resulting in the formation of nanoparticles with tunable band gap and size. Based on theoretical and experimental studies, 100 nm nanoparticles with an associated band gap of 1.33 eV were selected to achieve the desired film characteristics and device performances. Scanning electron microcopy (SEM) and size measurement instruments (Zetasizer) were used to study the size and shape of the nanoparticles. Electron dispersive spectroscopy (EDS) results confirmed the presence of the four elements, Copper (Cu), Indium (In), Gallium (Ga), and Selenium (Se) in the synthesized nanoparticles, while X-ray diffraction (XRD) results confirmed the tetragonal chalcopyrite crystal structure. The ultraviolet-visible-near infra-red (UV-Vis-NIR) spectrophotometry results of the nanoparticles depicted light absorbance characteristics with good overlap against the solar irradiance spectrum. The depositions of the nanoparticles were performed using spray-coating techniques. Nanoparticle ink dispersed in ethanol was sprayed using a simple airbrush tool. The thicknesses of the deposited films were controlled through variations in the deposition steps, substrate to spray-nozzle distance, size of the nozzle, and air pressure. Surface features and topology of the spray-deposited films were analyzed using atomic force microscopy (AFM). The deposited films were observed to be relatively uniform with a minimum thickness of 400 nm. Post-annealing of the films at various temperatures was studied for the photoelectric performance of the deposited films. Current density and voltage (J/V) characteristics were measured under light illumination after annealing at different temperatures. It was observed that the highest photoelectric effect resulted in annealing temperatures of 150-250 degree centigrade under air atmosphere. The developed CIGS films were implemented in solar cell devices that included Cadmium Sulfide (CdS) and Zinc Oxide (ZnO) layers. The CdS film served as the n-type layer to form a pn junction with the p-type CIGS layer. In a typical device, a 300 nm CdS layer was deposited through chemical bath deposition on a 1 $mu$m thick CIGS film. A thin layer of intrinsic ZnO was spray coated on the CdS film to prevent shorting with the top conductor layer, 1.5 μm spray-deposited aluminum doped ZnO layer. A set of fabricated devices were tested using a Keithley semiconductor characterization instrument and micromanipulator probe station. The highest measured device efficiency was 1.49%. The considered solar cell devices were simulated in ADEPT 2.0 solar cell simulator based on the given fabrication and experimental parameters. The simulation module developed was successfully calibrated with the experimental results. This module can be used for future development of the given work.

The present work focuses on the growth and characterizations of GaN and InN layers and nanostructures on p-Si(100) and p-Si(111) substrates by plasma-assisted molecular beam epitaxy and the studies of GaN/p-Si and InN/p-Si heterojunctions properties. The thesis is divided in to seven different chapters. Chapter 1 gives a brief introduction on III-nitride materials, growth systems, substrates, possible device applications and technical background. Chapter 2 deals with experimental techniques including the details of PAMBE system used in the present work and characterization tools for III-nitride epitaxial layers as well as nanostructures. Chapter 3 involves the growth of GaN films on p-Si(100) and p-Si(111) substrates. Phase pure wurtzite GaN films are grown on Si (100) substrates by introducing a silicon nitride layer followed by low temperature GaN growth as buffer layers. GaN films grown directly on Si (100) are found to be phase mixtured, containing both cubic and hexagonal modifications. The x-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy studies reveal that the significant enhancement in the structural and optical properties of GaN films grown with silicon nitride buffer layer grown at 800 oC, when compared to the samples grown in the absence of silicon nitride buffer layer and with silicon nitride buffer layer grown at 600 oC. Core-level photoelectron spectroscopy of SixNy layers reveals the sources for superior qualities of GaN epilayers grown with the high temperature substrate nitridation process. The discussion has been carried out on the typical inverted rectification behavior exhibited by n-GaN/p-Si heterojunctions. Considerable modulation in the transport mechanism is observed with the nitridation conditions. The heterojunction fabricated with the sample of substrate nitridation at high temperature exhibites superior rectifying nature with reduced trap concentrations. Lowest ideality factors (~1.5) are observed in the heterojunctions grown with high temperature substrate nitridation which is attributed to the recombination tunneling at the space charge region transport mechanism at lower voltages and at higher voltages space charge limited current conduction is the dominating transport mechanism. Whereas, thermally generated carrier tunneling and recombination tunneling are the dominating transport mechanisms in the heterojunctions grown without substrate nitridation and low temperature substrate nitridation, respectively. A brief comparison of the structural, optical and heterojunction properties of GaN grown on Si(100) and Si(111) has been carried out. Chapter 4 involves the growth and characterizations of InN nanostructures and thinfilms on p-Si(100) and p-Si(111) substrates. InN QDs are grown on Si(100) at different densities. The PL characteristics of InN QDs are studied. A deterioration process of InN QDs, caused by the oxygen incorporation into the InN lattice and formation of In2O3/InN composite structures was established from the results of TEM, XPS and PL studies. The results confirm the partial oxidation of the outer shell of the InN QDs, while the inner core of the QDs remains unoxidized. InN nanorods are grown on p-Si(100), structural characterizations are carried out by SEM, and TEM. InN nanodots are grown on p-Si(100), structural characterizations are performed. InN films were grown on Si(100) and Si(111) substrates and structural characterizations are carried out. Chapter 5 deals with the the heterojunction properties of InN/p-Si(100) and InN/p-Si(111).The transport behavior of the InN NDs/p-Si(100) diodes is studied at various bias voltages and temperatures. The temperature dependent ZB BH and ideality factors of the forward I-V data are observed, while it is governed through the modified Richardson’s plot. The difference in FB BH and C-V BH and the deviation of ideality factor from unity indicate the presence of inhomogeneities at the interface. The band offsets derived from C-V measurements are found to be Δ EC=1.8 eV and Δ EV =1.3 eV, which are in close agreement with Anderson’s model. The band offsets of InN/p-Si heterojunctions are estimated using XPS data. A type-III band alignment with a valence band offset of Δ EV =1.39 eV and conduction band offset of ΔEC=1.81 eV is identified. The charge neutrality level model provides a reasonable description of the band alignment of the InN/p-Si interface. The interface dipole deduced by comparison with the electron affinity model is 0.06 eV. The transport studies of InN NR/p-Si(100) heterojunctions have been carried out by conductive atomic force microscopy (CAFM) as well as conventional large area contacts. Discussion of the electrical properties has been carried out based on local current-voltage (I-V) curves, as well as on the 2D conductance maps. The comparative studies on transport properties of diodes fabricated with InN NRs and NDs grown on p-Si(100) substrates and InN thin films grown on p-Si(111) substrates have also been carried out. Chapter 6 deals with the growth and characterizations of InN/GaN heterostructures on p-Si(100) and p-Si(111) substarets and also on the InN/GaN/p-Si heterojunction properties. The X-ray diffraction (XRD), scanning electron microscopy (SEM) studies reveal a considerable variation in crystalline quality of InN with grown parameters. Deterioration in the rectifying nature is observed in the case of InN/GaN/p-Si(100) heterojunction substrate when compared to InN/GaN/p-Si (111) due to the defect mediated tunneling effect, caused by the high defect concentration in the GaN and InN films grown on Si(100) and also due to the trap centers exist in the interfaces. Reduction in ideality factor is also observed in the case of n-InN/n-GaN/p–Si(111) when compared to n-InN/n-GaN/p–Si(100) heterojunction. The sum of the ideality factors of individual diodes is consistent with experimentally observed high ideality factors of n-InN/n-GaN/p–Si double heterojunctions due to double rectifying heterojunctions and metal semiconductor junctions. Variation of effective barrier heights and ideality factors with temperature are confirmed, which indicate the inhomogeneity in barrier height, might be due to various types of defects present at the GaN/Si and InN/GaN interfaces. The dependence of forward currents on both the voltage and temperatures are explained by multi step tunneling model and the activation energis were estimated to be 25meV and 100meV for n-InN/n-GaN/p–Si(100) and n-InN/n-GaN/p–Si(111) heterojunctions, respectively. Chapter 7 gives the summary of the present study and also discusses about future research directions in this area.

Group III-nitride semiconductors have received much research attention and witnessed a significant development due to their ample applications in solid-state lighting and high-power/high-frequency electronics. Numerous growth methods were explored to achieve device quality epitaxial III-nitride semiconductors. Among the growth methods for III-nitride semiconductors, molecular beam epitaxy provides advantages such as formation of abrupt interfaces and in-situ monitoring of growth. The present research work focuses on the growth and characterizations of III-nitride based epitaxial films, nanostructures and heterostructures on c-sapphire substrate using plasma-assisted molecular beam epitaxy system. The correlation between structural, optical and electrical properties of III-nitride semiconductors would be extremely useful. The interfaces of the metal/semiconductor and semiconductor heterostructures are very important in the performance of semiconductor devices. In this regard, the electrical transport studies of metal/semiconductor and semiconductor heterostructures have been carried out. Besides, studies involved with the defect induced room temperature ferromagnetism of GaN films and InN nano-structures have also been carried out. The thesis is organized in eight different chapters and a brief overview of each chapter is given below. Chapter 1 provides a brief introduction on physical properties of group III-nitride semiconductors. It also describes the importance of III-nitride heterostructures in the operation of optoelectronic devices. In addition, it also includes the current strategy of the emergence of room temperature ferromagnetism in III-nitride semiconductors. Chapter 2 deals with the basic working principles of molecular beam epitaxy system and different characterization tools employed in the present work. Chapter 3 describes the growth of GaN films on c-sapphire by plasma-assisted molecular beam epitaxy. The effects of N/Ga flux ratio on structural, morphological and optical properties have been studied. The flux ratio plays a major role in controlling crystal quality, morphology and emission properties of GaN films. The dislocation density is found to increase with increase in N/Ga flux ratio. The surface morphologies of the films as seen by scanning electron microscopy show pits on the surface and found that the pit density on the surface increases with flux ratio. The room temperature photoluminescence study reveals the shift in band-edge emission towards the lower energy with increase in N/Ga flux ratio. This is believed to arise from the reduction in compressive stress in the GaN films as it is evidenced by room temperature Raman study. The transport studies on the Pt/GaN Schottky diodes showed a significant increase in leakage current with an increase in N/Ga ratio and is found to be caused by the increase in dislocation density in the GaN films. Chapter 4 deals with the fabrication and characterization of Au/GaN Schottky diodes. The temperature dependent current–voltage measurements have been used to determine the current transport mechanism in Schottky diodes. The barrier height (φb) and the ideality factor (η) are estimated from the thermionic emission model and are found to be temperature dependent in nature, indicating the existence of barrier height inhomogeneities at the Au/GaN interface. The conventional Richardson plot of ln(Is/T2) versus 1/kT gives Richardson constant value of 3.23×10-5 Acm-2 K-2, which is much lower than the known value of 26.4 Acm-2 K-2 for GaN. Such discrepancy of Richardson constant value was attributed to the existence of barrier height inhomogeneities at the Au/GaN interface. The modified Richardson plot of ln(Is/T2)-q2σs2/2k2T2 versus q/kT, by assuming a Gaussian distribution of barrier heights at the Au/GaN interface, provides the Schottky barrier height of 1.47 eV and Richardson constant value of 38.8 Acm-2 K-2 which is very close to the theatrical value of Richardson constant. The temperature dependence of barrier height is interpreted on the basis of existence of the Gaussian distribution of the barrier heights due to the barrier height inhomogeneities at the Au/GaN interface. Chapter 5 addresses on the influence of GaN underlayer thickness on structural, electrical and optical properties of InN thin films grown using plasma-assisted molecular beam epitaxy. The high resolution X-ray diffraction study reveals superior crystalline quality for the InN film grown on thicker GaN film. The electronic and optical properties seem to be greatly influenced by the structural quality of the films, as can be evidenced from Hall measurement and optical absorption spectroscopy. Also, we present the studies involving the dependence of structural, electrical and optical properties of InN films, grown on thicker GaN films, on growth temperature. The optical absorption edge of InN film is found to be strongly dependent on carrier concentration. Kane’s k.p model is used to describe the dependence of optical absorption edge on carrier concentration by considering the non-parabolic dispersion relation for carrier in the conduction band. Chapter 6 deals with the analysis of the temperature dependent current transport mechanisms in InN/GaN heterostructure based Schottky junctions. The barrier height (φb) and the ideality factor (η) of the InN/GaN Schottky junctions are found to be temperature dependent. The temperature dependence of the barrier height indicates that the Schottky barrier height is inhomogeneous in nature at the heterostructure interface. The higher value of the ideality factor and its temperature dependence suggest that the current transport is primarily dominated by thermionic field emission (TFE) other than thermionic emission (TE). The room temperature barrier height and the ideality factor obtained by TFE model are 1.43 eV and 1.21, respectively. Chapter 7 focuses on the defect induced room temperature ferromagnetism in Ga deficient GaN epitaxial films and InN nano-structures grown on c-sapphire substrate by using plasma-assisted molecular beam epitaxy. The observed yellow emission peak in room temperature photoluminescence spectra and the peak positioning at 300 cm-1 in Raman spectra confirms the existence of Ga vacancies in GaN films. The ferromagnetism in Ga deficient GaN films is believed to originate from the polarization of the unpaired 2p electrons of nitrogen surrounding the Ga vacancy. The InN nano-structures of different size are grown on sapphire substrate, the structural and magnetic properties are studied. The room temperature magnetization measurement of InN nano-structures exhibits the ferromagnetic behavior. The saturation magnetization is found to be strongly dependent on the size of the nano-structures. Finally, Chapter 8 gives the summary of the present work and the scope for future work in this area of research.