Photoluminescence spectroscopy of bulk zinc oxide under different annealing conditions was examined. The effect of the annealing atmosphere, temperature and time on the optical properties of zinc oxide were studied to investigate the influence on the intrinsic defects present. The wafers used were bulk +c ZnO grown by Tokyo Denpa using the hydrothermal technique. The annealing effect on both zinc and oxygen faces was investigated. The dominant donor bound exciton related to aluminum, labelled in the literature as I₆ demonstrated a splitting of 0.3 meV. The origin of this splitting has been linked to an interaction between aluminum and hydrogen, through its reaction to atmospheric dependent annealing. The removal of the hydrothermal hydrogen peak at 3.3624 eV has uncovered some fine structure. After Arrhenius analysis of this fine structure it was shown it is excited states of bound excitons. This fine structure has been loosely associated with vibrational and rotational excited states. The behaviour of all the optical features present in the photoluminescent spectra under annealing has a relation with the carrier concentration of the samples.

abstract: Zinc oxide nanowires ( NWs) have broad applications in various fields such as nanoelectronics, optoelectronics, piezoelectric nanogenerators, chemical/biological sensors, and heterogeneous catalysis. To meet the requirements for broader applications, the growth of high-quality ZnO NWs and functionalization of ZnO NWs are critical. In this work, specific types of functionalized ZnO NWs have been synthesized and correlations between specific structures and properties have been investigated. Deposition of δ-Bi2O3 (narrow band gap) epilayers onto ZnO (wide band gap) NWs improves the absorption efficiency of the visible light spectrum by 70%. Furthermore, the deposited δ-Bi2O3 grows selectively and epitaxially on the {11-20} but not on the {10-10} facets of the ZnO NWs. The selective epitaxial deposition and the interfacial structure were thoroughly investigated. The morphology and structure of the Bi2O3/ZnO nanocomposites can be tuned by controlling the deposition conditions. Various deposition methods, both physical and chemical, were used to functionalize the ZnO NWs with metal or alloy nanoparticles (NPs) for catalytic transformations of important molecules which are relevant to energy and environment. Cu and PdZn NPs were epitaxially grown on ZnO NWs to make them resistant to sintering at elevated temperatures and thus improved the stability of such catalytic systems for methanol steam reforming (MSR) to produce hydrogen. A series of Pd/ZnO catalysts with different Pd loadings were synthesized and tested for MSR reaction. The CO selectivity was found to be strongly dependent on the size of the Pd: Both PdZn alloy and single Pd atoms yield low CO selectivity while Pd clusters give the highest CO selectivity. By dispersing single Pd atoms onto ZnO NWs, Pd1/ZnO single-atom catalysts (SACs) was synthesized and their catalytic performance was evaluated for selected catalytic reactions. The experimental results show that the Pd1/ZnO SAC is active for CO oxidation and MSR but is not desirable other reactions. We further synthesized ZnO NWs supported noble metal (M1/ZnO; M=Rh, Pd, Pt, Ir) SACs and studied their catalytic performances for CO oxidation. The catalytic test data shows that all the fabricated noble metal SACs are active for CO oxidation but their activity are significantly different. Structure-performance relationships were investigated. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2017

Made available in DSpace on 2018-08-01T22:57:12Z (GMT). No. of bitstreams: 1 tese_10883_DISSERTAÇÃO FRANCIELLI GENIER 2017 PÓS DEFESA PDF.pdf: 2142232 bytes, checksum: 955dfa826de57674f0045dc8adc7d71b (MD5) Previous issue date: 2017-07-05 / Grande parte dos insucessos das cirurgias de transplante metálico ocorre devido à rejeição corporal à superfície do material empregado e às infecções pós-operatórias na região implantada. Dessa forma, prevenir o crescimento bacteriano sobre esses materiais e simultaneamente contribuir para a sua adaptação ao organismo são as principais metas de pesquisas recentes em nanomedicina. Como uma forma de alcançar esses objetivos, o revestimento de próteses metálicas com nanopartículas representa uma alternativa viável aos métodos tradicionais de tratamento, como por exemplo, o uso de antibióticos cuja eficácia decresce com o surgimento de cepas resistentes. Nesse trabalho, foi realizada a aplicação de nanopartículas de óxido de zinco dopado com cobre (Cu-ZnO) para o revestimento de superfícies de titânio metal comumente utilizado em implantes artificiais, a partir da técnica de deposição eletroforética. A escolha das nanopartículas de Cu-ZnO foi pautada em suas características antibacterianas, como demonstrado na literatura. Utilizando as técnicas de caracterização por microscopia (MEV e MET), espectroscopia (EDS) e difração de raios-X (DRX), pôde-se confirmar seu formato e os elementos presentes nas nanopartículas bem como o tamanho médio do cristalito (228,24 nm) e os parâmetros de rede. As nanopartículas foram suspensas e depositadas por eletroforese em placas de titânio por 1 minuto sob tensões entre 100 e 180 V a fim de se obter a melhor condição de deposição, sendo esta a de 160 V. O pH e a condutividade elétrica da suspensão também foram avaliados antes e após a EPD. Os resultados de EDS confirmaram a presença do nanomaterial no depósito e as imagens obtidas por MEV confirmaram o aumento da rugosidade superficial após a deposição eletroforética. Assim sendo, almejou-se nesse trabalho explorar o potencial de dessa técnica para o revestimento em implantes artificiais e, por conseguinte, contribuir para a pesquisa em nanotecnologia e suas aplicações em medicina.

The theoretical part of thesis deals with microalgae, primary and secondary metabolism of plants, formation of the reactive oxygen species and origin of oxidative stress. Also it describes secondary metabolites, the characteristic of nanoparticles and impact on microalgae. The practical part deals with the impact of ZnO nanoparticles on secondary metabolism in Scenedesmus quadricauda. At first was observed the impact of nanoparticles on growth of microalgae. Then the content of photosynthetic pigments, total polyphenols, flavonoids and total antioxidant capacity was determined using spectrophotometric method. Also the content of chosen secondary metabolites was detected using HPLC. The growth of microalgae was stimulated by ZnO nanopartlicles during the first 4 days compared to control. Then the inhibition of growth was observed. The content of photosynthetic pigments decreased compared to control in samples with ZnO nanoparticles. Also the change of secondary metabolites, total polyphenols and flavonoids was observed.

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Recently, efforts have been made for self-powering the batteries and portable electronic devices by piezoelectric nanogenerators. The piezoelectric nanogenerators can work as a power source for nano-systems and also as an active sensor. The piezoelectric nanogenerator is a device that converts random mechanical energy into electrical energy by utilizing the semiconducting and piezoelectric properties. Also, the mechanical energy is always available in and around us for powering these nano devices. The aim of the present thesis work is to explore 1D and 2D ZnO nanostructures (nanorods and nanosheets) on metal alloy substrates for the development of piezoelectric nanogenerators in energy harvesting and sensors applications. Hydrothermal synthesis method was adopted for the growth of ZnO nanostructures. The nanogenerators were fabricated by using the optimized synthesis parameters and subsequently studied their performance for power generation and as an active speed sensor. These 1D and 2D nanostructures based nanogenerators have opened up a new window for the energy harvesting applications and sensors development. The thesis is divided into following six chapters. Chapter 1: This chapter gives a general introduction about energy harvesting devices such as nanogenerators, available energy sources, mechanical energy harvesting, ZnO material and the details on hydrothermal synthesis process. A brief literature survey on different applications of piezoelectric nanogenerators is also included. Chapter 2: A novel flexible metal alloy (Phynox) and its properties along with its applications are discussed in this chapter. Details on the synthesis of 1D ZnO nanorods on Phynox alloy substrate by hydrothermal method are presented. Further, the optimization of parameters such as growth temperature, seed layer annealing and substrate temperature effects on the synthesis of ZnO nanorods are discussed in detail. As-synthesized ZnO nanorods have been characterized using XRD, FE-SEM, TEM and XPS. Chapter 3: It reports on the fabrication of piezoelectric nanogenerator on Phynox alloy substrate as power generating device by harvesting the mechanical energy. Initially, the performance of the nanogenerator for power generation due to finger tip impacts was studied and subsequently its switching polarity test was also carried out. Output voltage measurements were carried out using the in-house developed experimental setup. Stability test was also carried out to see the robustness of the nanogenerator. Finally, the output voltage response of the nanogenerator was studied for its use as an active speed sensor. Chapter 4: Synthesis of Al doped 2D ZnO nanorsheets on Aluminum alloy (AA-6061) substrate by hydrothermal method is reported in this chapter. The optimized parameters such as growth temperature and growth time effects on the synthesis of ZnO nanosheets are discussed. As-synthesized ZnO nanosheets were characterized using XRD, FE-SEM, TEM and XPS. The Al doping in ZnO is confirmed by EDXS and XPS analysis. Chapter 5: Cost effective fabrication of Al doped 2D ZnO nanosheets based nanogenerator for direct current (DC) power generation is reported in this chapter. The performance of the nanogenerator for DC power generation due to finger tip impacts was studied and subsequently its switching polarity test was also carried out. Output voltage measurements were carried out using the in-house developed experimental setup. Stability test was also carried out to see the robustness of the nanogenerator. Finally, the DC output voltage response of the nanogenerator was studied for its use as an active speed sensor. Chapter 6: The first section summarizes the significant features of the work presented in this thesis. In the second section the scope for carrying out the further work is given.

Zinc oxide is a semiconducting material that has received lot of attention due to its numerous proeprties such as wide direct band gap, piezoelectricity, and numerous low cost and robust methods of synthesizing nanomaterials. Its piezoelectric properties have been harnessed for use in energy production through nanogenerators, and to tune carrier transport, birthing a field known as piezotronics. However, one weakness of ZnO is that it is notoriously difficult to dope p-type. Antimony was investigated as a p-type dopant for ZnO, and found to have a stability of up to 3 years, which is completely unprecedented in the literature. Furthermore, a variety of zinc oxide structures ranging from ultra-long nanowires to thin films were produced and their piezotronic properties were demonstrated. By making p-n homojunctions using doped and undoped ZnO, enhanced nanogenerators were produced which could see application in gesture recognition. As a proof of concept, a simple photodetector was also derived from a core-shell nanowire structure. Finally, the ability to integrate this material with other semiconductors was demonstrated by growing a heterojunction with silicon nanowires, and investigating its electrical properties. All this work together lays the foundation for a fundamentally new material that could see application in future electronics, optoelectronics, and human-machine interfacing.

Described in this thesis are the growth and characterization of high quality ZnO epitaxy layers.Zinc oxide (ZnO) epitaxy layers were grown on sapphire and epi-GaN substrates respectively, using plasma assisted molecular beam epitaxy (MBE) . Various growth conditions, such as growth temperature, II/VI ratio, and buffer layers, were employed to optimize the quality of the ZnO film. The subsequent characterization of the films was carried out to evaluate the surface, optical and crystalline properties of the film, using AFM, SEM, PL and XRD techniques. It was found out that the high quality of the ZnO film was grown on epi-GaN substrates under the Low temperature of ~ 300 degrees C, flash annealing up to ~680 degrees C, followed by high temperature growth at ~600 degrees C.

As a wide band semiconductor with a large binding energy (about 60meV), ZnO is a promising candidate semiconductor material for the next generation of optoelectronic , light emission or high power and high frequency devices. In order to make electrical device from ZnO, it is necessary to investigate optical properties of ZnO.In this thesis, PL setup and the properties of ZnO are introduced briefly and the optical properties of ZnO are investigated in detail. Temperature dependence of PL spectra of ZnO are measured and analyzed. Sharp emission line of PL spectra of rare earth (RE) doped ZnO are also investigated.

The development of nanostructured materials for environmental applications has received considerable attention in recent years. The properties of nanoparticles or nanostructured materials, such as large surface areas or high aspect ratios, translate into large improvements in the performance of existing devices and in the discovery of novel applications. On the other hand, photocatalysis is an attractive technology for the elimination of organic pollutants in water due to its simplicity, ease of implementation and reasonable cost compared to other advanced oxidation processes. A key disadvantage of many photocatalysts is their use in powder form which makes their recovery from treated water costly. In addition, incomplete removal can lead to accumulation over time with adverse effects to the environment. As a result significant effort has been placed in immobilizing photocatalytic materials on different substrates. The immobilization of photocatalyst results in a decrease in photocatalytic performance mainly due to reduction of surface area; therefore, research is now focusing on developing nanostructured materials which combine the attributes of nanotechnology and photocatalysis. In the present thesis, a systematic study of the relationship between properties of supported ZnO nanostructures and their photocatalytic activity was performed. Analysis was carried out by producing ZnO nanostructured films via anodization. The effects of voltage, temperature, reaction time and type of electrolyte on the morphology of ZnO nanostructures was studied. Results show that the type of electrolyte and its concentration determine the morphology and size of the nanostructures. Voltage, time and temperature affect the distribution and density of the nanostructures along the surface and affect the crystal size of the ZnO. The band gaps of the films were in the range of 3.27 and 3.50 eV. Although ZnO is a hydrophilic material, some of the films displayed hydrophobic and super-hydrophobic behaviour. The results obtained in this study and some data already published in the literature were correlated to the synthesis parameters, and were used to devise design guidelines to obtain ZnO films with specific nanostructures and macroscopic properties by controlling the anodization parameters. The photocatalytic activity of the ZnO nanostructured films (ZnO-NFs) were studied using three different photocatalytic reactors, (i) a thermo-stated batch reactor, (ii) a recirculating flat plate reactor, and (iii) a recirculating tubular annular reactor. Phenol and methyl orange (MO) were used as a model compounds. It was found that crystal size does not affect the photocatalytic performance of the films while morphology has an important impact on the degradation of phenol. The stability of the ZnO nanostructures was tested under different levels of oxygen, degradation of phenol occurred even at anoxic conditions following the Mars-van Krevelen mechanism. The formation of new nanostructures produced during the photocatalytic reaction was studied and a mechanism of formation was proposed. The study of the photocatalytic performance in the flat plate reactor showed that there was a mass transfer limitation in the process. ZnO nanostructures showed higher photocatalytic activity and morphology stability in the tubular annular reactor. Degradation of MO and phenol was produced in darkness by the nanostructures supported in Zn foil. It was also demonstrated that oxygen plasma post-treatment enhances the photocatalytic activity of the ZnO-NF by 36% while making the photocatalyst more stable for the photocatalytic degradation of phenol compared to those treated with heat. An electrical current was applied to the photocatalyst in the tubular annular reactor, which improved the degradation of phenol and participated in the formation of nanostructures in the Zn wire surface.