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This study indicate that the chemical inter-diffusion between the Cr-doped glass/glass ceramic and quartz (SiO2) influence the fluorescence properties of glass, mainly because of Cr4+ replacing by tetrahedral of Si4+. Cr4+ fluorescence intensity was reduced and its emission band was shifted to longer wavelength (red shift). We selected the SiO2-based glass composition: Mg2SiO4 glass-ceramic and reduced a ratio of SiO2 sintered into the ceramic powder. This paper used diffusion characteristics of quartz (SiO2) to compensate for reduced SiO2 in the ceramic powder. After diffusing with quartz (SiO2), ceramics powder changed into glasses. The intensity of fluorescence and the crystal field had been improved. The center of Cr4+ fluorescence is about 1100nm belonging to Cr4+:Mg2SiO4 crystal. The ratio of Cr4+ in Mg2SiO4 crystal/Cr4+ in MgO-SiO2 glass increases from 0.33 to 1.74. The goal is to develop a novel glass which is resistant to SiO2 inter-diffusion degradation during fiber fabrication, and provide the new fiber technology to avoid the influence of inter-diffusion This study provides new types of treatment: Laser induced crystallization. Laser heat-treatment can more quickly induce crystals in glass during seconds, than traditional heat-treatment which require several hours. This study also indicate that one step laser heat-treatment induce micro-crystals, but one step laser heat-treatment induce nano-crystals. We successfully produced nano-crystallization during seconds.

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Yes / We deposited Os atoms on S- and Se-doped boronic graphenic surfaces by electron bombardment of micelles containing 16e complexes [Os(p-cymene)(1,2-dicarba-closo-dodecarborane-1,2-diselenate/dithiolate)] encapsulated in a triblock copolymer. The surfaces were characterized by energy-dispersive X-ray (EDX) analysis and electron energy loss spectroscopy of energy filtered TEM (EFTEM). Os atoms moved ca. 26× faster on the B/Se surface compared to the B/S surface (233 ± 34 pm·s–1 versus 8.9 ± 1.9 pm·s–1). Os atoms formed dimers with an average Os–Os distance of 0.284 ± 0.077 nm on the B/Se surface and 0.243 ± 0.059 nm on B/S, close to that in metallic Os. The Os2 molecules moved 0.83× and 0.65× more slowly than single Os atoms on B/S and B/Se surfaces, respectively, and again markedly faster (ca. 20×) on the B/Se surface (151 ± 45 pm·s–1 versus 7.4 ± 2.8 pm·s–1). Os atom motion did not follow Brownian motion and appears to involve anchoring sites, probably S and Se atoms. The ability to control the atomic motion of metal atoms and molecules on surfaces has potential for exploitation in nanodevices of the future. / We thank the Leverhulme Trust (Early Career Fellowship No. ECF-2013 414 to NPEB), the University of Warwick (Grant No. RDF 2013-14 to NPEB), the EPSRC (EP/G004897/1 to RKOR), and ERC (Grant No. 247450 to PJS) for support.

In the past decade, rechargeable batteries attracted the attention from the researchers in search for renewable and sustainable energy sources. Up to date, lithium-ion battery is the most commercialized and has been supplying power to electronic devices and hybrid and electric vehicles. Lithium-ion battery, however, does not satisfy the expectations of ever-increasing energy and power density, which of their limits owes to its intercalation chemistry and the safety.1-2 Therefore, metal-air battery drew much attention as an alternative for its high energy density and a simple cell configuration.1 There are several different types of metal-air batteries that convey different viable reaction mechanisms depending on the anode metals; such as Li, Al, Ca, Cd, and Zn. Redox reactions take place in a metal-air cell regardless of the anode metal; oxidation reaction at the anode and reduction reaction at the air electrode. Between the two reaction, the oxygen reduction reaction (ORR) at the air electrode is the relatively the limiting factor within the overall cell reactions. The sluggish ORR kinetics greatly affects the performance of the battery system in terms of power output, efficiency, and durability. Therefore, researchers have put tremendous efforts in developing highly efficient metal air batteries and fuel cells, especially for high capacity applications such as electric vehicles. Currently, the catalyst with platinum nanoparticles supported on carbon material (Pt-C) is considered to exhibit the best ORR activities. Despite of the admirable electrocatalytic performance, Pt-C suffers from its lack of practicality in commercialization due to their prohibitively high cost and scarcity as of being a precious metal. Thus, there is increasing demand for replacing Pt with more abundant metals due economic feasibility and sustainability of this noble metal.3-5 Two different attitudes are taken for solution. The first approach is by optimizing the platinum loading in the formulation, or the alternatively the platinum can be replaced with non-precious materials. The purpose of this work is to discover and synthesize alternative catalysts for metal-air battery applications through optimized method without addition of precious metals. Different non-precious metals are investigated as the replacement of the precious metal including transition metal alloys, transition metal or mixed metal oxides, and chalcogenides. These types of metals, alone, still exhibits unsatisfying, yet worse, kinetics in comparison to the precious metals. Nitrogen-doped carbon material is a recently well studied carbon based material that exhibits great potential towards the cathodic reaction.6 Nitrogen-doped carbon materials are found to exhibit higher catalytic activity compared to the mentioned types of metals for its improved conductivity. Benefits of the carbon based materials are in its abundance and minimal environmental footprints. However, the degradation of these materials has demonstrated loss of catalytic activity through destruction of active sites containing the transition metal centre, ultimately causing infeasible stability. To compensate for these drawbacks and other limits of the nitrogen-doped carbon based catalysts, nitrogen-doped carbon nanotubes (NCNT) are also investigated in the series of study. The first investigation focuses on a development of a simple method to thermally synthesize a non-precious metal based nitrogen-doped graphene (NG) electrocatalyst using exfoliated graphene (Ex-G) and urea with varying amounts of iron (Fe) precursor. The morphology and structural features of the synthesized electrocatalyst (Fe-NG) were characterized by SEM and TEM, revealing the existence of graphitic nanoshells that potentially contribute to the ORR activity by providing a higher degree of edge plane exposure. The surface elemental composition of the catalyst was analyzed through XPS, which showed high content of a total N species (~8 at.%) indicative of the effective N-doping, present mostly in the form of pyridinic nitrogen groups. The oxygen reduction reaction (ORR) performance of the catalyst was evaluated by rotating disk electrode voltammetry in alkaline electrolyte and in a zinc-air battery cell. Fe-NG demonstrated high onset and half-wave potentials of -0.023 V (vs. SCE) and -0.110 V (vs. SCE), respectively. This excellent ORR activity is translated into practical zinc-air battery performance capabilities approaching that of commercial platinum based catalyst. Another approach was made in the carbon materials to further improve the cost of the electrode. Popular carbon allotropes, CNT and graphene, are combined as a composite (GC) and heteroatoms, nitrogen and sulfur, are introduced in order to improve the charge distribution of the graphitic network. Dopants were doped through two step processes; nitrogen dopant was introduced into the graphitic framework followed by the sulfur dopant. The coexistence of the two heteroatoms as dopants demonstrated outstanding ORR performance to those of reported as metal free catalysts. Furthermore, effects of temperature were investigated through comparing ORR performances of the catalysts synthesized in two different temperatures (500 ??? and 900 ???) during the N-doping process (consistent temperature was used for S-doping). Through XPS analysis of the surface chemistry of catalysts produced with high temperature during the N-doping step showed absence of N-species after the subsequent S-doping process (GC-NHS). Thus, the synergetic effects of the two heteroatoms were not revealed during the half-cell testing. Meanwhile, the two heteroatoms were verified in the catalyst synthesized though using low temperature during the N-doping process followed by the S-doping step (GC-NLS). Consequently, ORR activity of the resulting material demonstrated promising onset and half-wave potentials of -0.117 V (vs. SCE) and -0.193 V (vs. SCE). In combination of these investigations, this document introduces thorough study of novel materials and their performance in its application as ORR catalyst in metal air batteries. Moreover, this report provides detailed fundamental insights of carbon allotropes, and their properties as potential elecrocatalysts and essential concepts in electrochemistry that lies behind zinc-air batteries. The outstanding performances of carbon based electrocatalyst are reviewed and used as the guides for further direction in the development of metal-air batteries as a promising sustainable energy resource in the future.

TiO2 nanoparticles are one of the most suitable materials for photocatalysis, specifically for water and air treatment and removal of a wide variety of organic pollutants such as dyes, aromatic compounds, and chlorinated aromatic compounds. Methods of synthesis of TiO2 are generally categorized in two main classes of wet chemical, and dry methods. Wet chemical methods generally provide a better control over size, size distribution, and shape; all of which significantly affect photocatalytic performance of the produced nanoparticles. Despite its advantages over other semiconductor photocatalysts, wide band-gap of titania restrains its photocatalytic activity to only UV light, which only makes up to 5% of the light reaching surface of the earth. To induce visible-light activity, titania has been doped by different dopants, including transition metal-dopants such as Fe, and Co and non-metal dopants such as N, and C. Nitrogen has been shown to be a better dopant, providing a suitably placed energy state within the band-gap of TiO2, and not suffering from issues related to transition-metal dopants such as low thermal and physical stability and high electron-hole recombination rates. To dope titania with nitrogen, one could add the nitrogen source together with other precursors during synthesis, referred to as wet chemical doping methods, or anneal the synthesized titania nanoparticles under a flow of ammonia at high temperatures, referred to as dry doping methods. While different doping methods have been studied individually, the author maintains that there has been an absence of research comparing the effectiveness of these methods, on photocatalytic performance of N-doped TiO2 within a consistent experiment. In this research TiO2 nanoparticles were synthesized by a facile, inexpensive sol-gel method, and doping was done by wet chemical methods, dry methods, and a combination of both these methods. Visible-light photocatalytic activity of these nanoparticles was evaluated by their efficiency in degradation of methyl orange. The results show wet doping methods increase the efficiency of titania nanoparticles more than dry doping, or combination of both. Further investigation showed that the main reason for higher activity of wet chemically doped nanoparticles is due to their higher available surface area of 131.7 m2.g-1. After normalizing the available surface area, measured by the BET method, it was shown that a combination of wet chemical doping, and dry doping at 600 °C result in the most active nanoparticles, but high temperature dry doping severely decreases the surface area, lowering the overall efficiency of the product. Additionally, N-doped TiO2 nanoparticles were synthesized using a simple hydrothermal method, in which the nitrogen source was used not only to dope, but also to control shape, size, size distribution, and morphology of the titania nanoparticles, and to induce aqueous colloidal stability. It was shown that addition of triethylamine during the synthesis, results in ultra-small, colloidally stable, cubic TiO2 nanoparticles, while using triethanolamine results in formation of TiO2 pallets, assembled into spherical, rose-like structures. The synthesized nanoparticles show impressive efficiency in visible-light removal of phenol, 4-chlorophenol, and pentachlorophenol, achieving 100% degradation of a 100-ppm phenol solution in 90 min, more than 98% degradation of a 20-ppm 4-chlorophenol solution in 90 min, and 97% degradation of a 10-ppm pentachlorophenol in 180 min with 500 ppm loading of the catalyst in all cases. Moreover, synthesized nanoparticles showed no sign of deactivation after 5 consecutive runs, removing 4-chlorophenol, showing their reusability. / Graduate

The work presented in this thesis focuses on the investigation and improvement of the window stack of layers for thin film CdTe solar cells fabricated in the Center for Renewable Energy Systems Technology (CREST) laboratories. In particular the aim was to change the standard structure including TCO, high resistive transparent (HRT)layer and CdS which is limited by the low transparency of the CdS layer, to a better performing one. The first result chapter of the thesis describes the study of ZnO HRT layers. ZnO thin films were deposited by radio frequency (RF) magnetron sputtering with different structural, optical and electrical properties which were characterized by X-ray diffraction, electron microscopy, spectrophotometry, Hall Effect method and 4-point probe. ZnO films were then incorporated in CdTe solar cells with the structure: FTO/ZnO/CdS/CdTe/Au back contact and the performance of these devices were compared with the film properties to single out trends and identify optimal film characteristics. By varying the deposition pressure of ZnO films, it was possible to increase their transparency and significantly increase their resistivity. While better transparency positively affected the solar cell current density output and efficiency, the resistivity of ZnO films did not show any clear impact on device efficiency. By increasing the deposition temperature the ZnO film grain size was increased. Increased FF was observed in devices incorporating ZnO layers with bigger grains, although this gain was partially counterbalanced by the Voc degradation, leading to a limited efficiency improvement. Finally the addition of oxygen had the main effect of increasing the resistivity of ZnO films, similarly to what happened with the increase of the sputtering pressure. In this case however, an improvement of FF, Jsc and efficiency was observed, especially at an O2/Ar ratio of 1%. By simulating the solar cells behavior with SCAPS-1D, it was found that these performance change can be explained by the variation of interface properties, precisely the amount of interface defects, rather than by bulk properties. The study presented in the second result chapter focuses on magnesium-doped zinc oxide (MZO) and the variation of its energy band structure. MZO was initially used as the HRT layer within a solar cell structure: FTO/MZO/CdS/CdTe/Au back contact. Sputtering MZO films with a target containing MgO 11 weight% and ZnO 89 weight% allowed for and increased band gap from 3.3 eV of intrinsic ZnO to 3.65 eV for MZO deposited at room temperature. Increasing the superstrate deposition temperature allowed for a further band gap increase up to 3.95 eV at 400 °C due mainly to an conduction band minimum upward shift. It was highlighted the importance to create a positive conduction band offset with the MZO layer conduction band slightly above the CdS conduction band, with an optimum found in this case to be 0.3 eV (efficiency 10.6 %). By creating a positive conduction band offset all the performance parameters (Voc, FF, Jsc, efficiency) significantly increased. One of the reasons for this improvement was found to be a diminished interface recombination due to a more ideal MZO/CdS band alignment. In the second part of this investigation the MZO was used as a replacement for the CdS in a simplified structure: FTO/MZO/CdTe/Au back contact. The concepts used to optimise the performance of these devices also involved tuning the conduction band alignment between MZO/CdTe and efficiencies of 12.5 % were achieved with a at conduction band offset. The efficiency increase was achieved mainly thanks to a better transparency of the MZO layer and a higher Jsc output, compared to devices using a CdS buffer layer. The MZO buffers have been tested in combination with different TCOs. Results are presented in the third result chapter and showed that AZO is a good alternative to FTO working effectively in combination with MZO. AZO/MZO efficiency thin film CdTe solar cells (12.6%, compared to 12.5% with FTO). It was found that increasing the IR transparency of the TCOs leads to a potentially higher Jsc. Achieving a better transparency was obtained by using TCOs with high mobility and lower carrier concentration (AZO and ITiO) and also by using a boro-aluminosilicate glass with low iron content. ITiO yielded the best opto-electrical properties among all the TCO materials. Devices incorporating ITiO however, showed lower performance then those using FTO and AZO. ITO/MZO windows also yielded poor performance. In addition, the ITO films deposited had a high carrier concentration leading to a high NIR absorption by plasma resonance and resulted not ideal for application in thin film CdTe PV.

Physics / D.Phil (Physics)