In this thesis, group IV material oxides for silicon photonics applications were deposited using novel deposition techniques. Erbium and terbium doped silicon oxide thin films were deposited through a novel hybrid radio frequency (RF) magnetron sputtering source in an electron cyclotron resonance (ECR)-plasma enhanced chemical vapour deposition (PECVD) reactor chamber. This approach contrasts with traditional doping methods which use metal-organic precursors to introduce rare-earth dopant species into the host matrix. The effects of sputtering power applied to the rare-earth target and system plasma pressure on the thin film properties were investigated. It was found that the sputtering power strongly influences the rare-earth incorporation, and a wide range of control over the doping level can be achieved. The effect of sputtering power on the refractive index, stoichiometry, and film density were also investigated. Doped thin films deposited with this technique showed low as-deposited hydrogen concentrations. In the case of terbium doped silicon oxide (SiOx), photoluminescence (PL) studies were conducted finding bright emission due to 5D4 → 7F5 transitions visible with the naked eye in films annealed above 1150 °C. Further investigation found that silicon nanostructures formed at the high annealing temperatures and were likely sensitizing the Tb3+ ions. These results demonstrate that hybrid sputtering in ECR-PECVD can be an effective tool for integrating optically active rare-earth dopants into silicon-based thin films. Using alternating current (AC) plasma assisted reactive magnetron sputtering (PARMS), low optical loss germanium oxide (GeO2) thin films were also produced. The films were fabricated at low temperature and high deposition rates of 6–38 nm/min on silicon and thermally oxidized silicon substrates. Prism coupling measurements demonstrated losses of 0.1 dB/cm at wavelengths ranging from 638 to 980 nm attributed to good uniformity and low surface roughness demonstrated through atomic force microscopy (AFM) measurements. The thin films materials developed here are highly promising for their applications in silicon photonics devices, including light sources and amplifiers. / Thesis / Candidate in Philosophy

Submitted by Izabel Franco (izabel-franco@ufscar.br) on 2016-10-06T13:50:45Z No. of bitstreams: 1 TeseMM.pdf: 4347312 bytes, checksum: a5a64729ea719b0ac57b31c2cdeeb425 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-20T16:14:11Z (GMT) No. of bitstreams: 1 TeseMM.pdf: 4347312 bytes, checksum: a5a64729ea719b0ac57b31c2cdeeb425 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-20T16:14:17Z (GMT) No. of bitstreams: 1 TeseMM.pdf: 4347312 bytes, checksum: a5a64729ea719b0ac57b31c2cdeeb425 (MD5) / Made available in DSpace on 2016-10-20T16:14:23Z (GMT). No. of bitstreams: 1 TeseMM.pdf: 4347312 bytes, checksum: a5a64729ea719b0ac57b31c2cdeeb425 (MD5) Previous issue date: 2016-03-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In this study, we present the production and characterization of a novel binary glass system: (100-x)SbPO4-xGeO2 where x = 30, 40, 50, 60, 70, 80 and 90 mol %. The dependence of GeO2 content on thermal, structural and optical properties were investigated by thermal analysis (DSC), Raman spectroscopy, UV-Visible absorption, infrared transmittance and M-lines techniques. Glass transition temperatures (Tg) shows an almost constant value around 400 °C when GeO2 content was increased. Thermal stability (ΔT = Tx-Tg) increases almost linearly with GeO2 content reaching a maximum value (300 °C). Ions Er3+ and Yb3+ were further incorporated into system SG in different proportions. Infrared and up-conversion emission processes were investigated. The emission spectra in the infrared region showed that the incorporation of Yb3+ ions into the glass composition increases the emission intensity at 1538 nm (4I13/2  4I15/2). The up-conversion processes showed a higher intensity emission at 522 nm and 544 nm (green) and 652 nm (red) regions and the emission mechanism has been the same as proposed in several works in literature. Finally, the glass sample showing the highest emission intensity at 1538 nm was chosen for micromachining using femtosecond laser. The waveguides having the lowest propagation losses were used for the optical internal gain proceeds. The best result obtained for internal gain at 1535 nm was around 1.7 dB/cm and this value is in agreement with other glass systems based on germanium and phosphates glasses present in literature. / Neste estudo, foi realizado a preparação e caracterização do sistema vítreo: (100-x) SbPO4-xGeO2 (SG), onde x varia entre 30 e 90% em mol. A dependência da concentração de GeO2 nas propriedades térmicas, ópticas e estruturais foram estudadas. O comportamento térmico foi investigado através da análise térmica (DSC), enquanto as propriedades estruturais foram estudadas por espectroscopia de espalhamento Raman. As propriedades ópticas foram avaliadas usando as espectroscopias na região do UV-Vis, infravermelho e M-Lines. No sistema SG a temperatura de transição vítrea (Tg) apresenta uma pequena variação e se encontra por volta de 400 °C quando a concentração de GeO2 foi alterada. O parâmetro de estabilidade térmica (ΔT = Tx-Tg) aumenta quase linearmente com o aumento da quantidade de GeO2, alcançando um valor máximo de 300 °C. Para o sistema SG foram incorporados ainda íons Er3+ e Yb3+ em diferentes proporções e as emissões na região do infravermelho e os processos de conversão ascendente de energia (upconversion) foram investigados. Os espectros de emissão na região do infravermelho mostram que a incorporação de íons Yb3+ na composição química do vidro, aumenta a intensidade de emissão em 1538 nm (4I13/2  4I15/2). Os processos de up-conversion mostram emissões de alta intensidade na região do verde (522 e 544 nm) e vermelho (652 nm), e os mecanismos das emissões foram estudados e propostos. Por fim, a amostra com a maior intensidade de emissão em 1538 nm foi escolhida para a realização da microfabricação de guias ópticos, usando lasers de femtossegundo. Os guias de onda que apresentaram as menores perdas por propagação, foram utilizados para as medidas de amplificação óptica.

Binary oxides constitute an outstanding class of functional materials with potential applications in many fields such as catalysis, gas sensing, field emission, solar cells, photodetection, etc. Due to the difference in their physical/chemical properties, different oxides have been explored for different applications. For examples, SnO2, Cr2O3 and ZnO are being explored for gas sensing due to their high adsorption capacity for volatile gases, ZnO, Cu2O etc. are being explored in solar cells because of high adsorption coefficient in UV/visible region and so on. Various techniques are available for synthesis of binary oxides and tuning their properties. Most of the physical or chemical synthesis techniques are expensive, need high cost instruments and produces hazardous chemical waste. We need a simple, cost effective and ecofriendly techniques for the synthesis of binary oxides. In present work, a simple and facile thermal oxidation strategy has been employed for the synthesis of various binary oxides (Cu2O, GeO2 and ZnO). For example, CuO nanorods are obtained when Cu is heated around ~ 500 oC, which then heated in Ar atmosphere to obtain a film of porous Cu2O. Similarly, GeO2 with different morphologies and green-luminescent ZnO are obtained by controlling the reaction parameters. These oxides have then been explored for various applications including white light phosphors, catalysis for the degradation of dyes and non-contact thermometry. Overall, we present a thermal oxidation strategy for the synthesis of various binary oxides and explore potential applications in various fields.

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