京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20706号 / 工博第4403号 / 新制||工||1684(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 三浦 清貴, 教授 田中 勝久, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

This research details an investigation into processes employing laser technology to create design-led three-dimensional textiles. An analysis of historical and contemporary methods for making three-dimensional textiles categorises these as processes that construct a three-dimensional textile, processes that apply or remove material from an existing textile to generate three-dimensionality or processes that form an existing textile into a three-dimensional shape. Techniques used in these processes are a combination of joining, cutting, forming or embellishment. Laser processing is embedded in textile manufacturing for cutting and marking. This research develops three novel processes: laser-assisted template pleating which offers full design freedom and may be applied to both textile and non-textile materials. The language of origami is used to describe designs and inspire new design. laser pre-processing of cashmere cloth which facilitates surface patterning through laser interventions in the manufacturing cycle. laser sintering on textile substrates which applies additive manufacturing techniques to textiles for the generation of three-dimensional surface patterning and structures. A method is developed for determining optimum parameters for laser processing materials. It may be used by designers for parameter selection for processing new materials or parameter modification when working across systems.

La texturisation de matériaux par irradiation laser ultracourt est un procédé permettant de modifier les propriétés optiques et électriques de la matière en formant des nano et microstructures en surface, apparaissant au cours des irradiations successives. Le contrôle du procédé et le développement des applications nécessitent une compréhension des mécanismes mis en jeu. Les processus intervenant sont étudiés à l'aide de simulations numériques, et sont comparés à des résultats expérimentaux. L'étude est menée dans le cadre de l'augmentation du rendement des cellules photovoltaïques basées sur du silicium massif. / Ultrashort laser pulsed texturing is a process which allows to modify optical and electrical properties of matter, through formation of nano and micro structures on surface, appearing from pulse to pulse. Control of the process and developments of the potential applications need a good knowledge of the formation mechanisms. Processes occuring during the interaction are studied using numerical simulations and are compared to experimental results. The study aims to increase the efficiency of solar cells based on bulk silicon.

Neste trabalho apresentamos estruturas poliméricas funcionalizadas com nanotubos de carbono, as quais são processadas utilizando técnicas de fabricação a laser. Inicialmente apresentamos uma metodologia para incorporar nanotubos de carbono de parede simples, funcionalizados com ácido carboxílico (NTCPS-COOH) em resinas acrílicas. A funcionalização dessas resinas foi alcançada, sendo possível incorporar nanotubos em uma faixa de 0,01% até 1%, em peso. Adicionalmente, visando aplicações em óptica e optoeletrônica, a inserção de Rodamina B ou MEH-PPV junto às resinas funcionalizadas com nanotubos também foi realizada. Através da técnica de polimerização via absorção multifotônica, microestruturas tridimensionais com boa resolução (aproximadamente 650 nm) e integridade foram fabricadas com essas resinas. A espectroscopia Raman mostrou que os NTCSPS-COOH estão distribuídos por todo o interior das microestruturas, característica necessária para aplicação em dispositivos. A funcionalização das estruturas não se restringiu apenas ao volume. Microestruturas acrílicas foram funcionalizadas com NTCPS-COOH apenas em sua superfície, utilizando a combinação das técnicas de adição de Michael e acoplamento carbodiimida. Análises Raman mostraram também uma boa distribuição dos nanotubos na superfície das amostras funcionalizadas. Mesmo as estruturas que foram funcionalizadas com baixas concentrações de NTCPS-COOH exibiram melhorias nas propriedades mecânicas e elétricas. Estruturas funcionalizadas com 0,01% (em peso) de NTCPS-COOH se mostraram mais resistentes em ensaios de indentação do que as amostras não funcionalizadas. Do ponto de vista elétrico, estruturas com a mesma faixa de funcionalização apresentaram condutividade elétrica superior em duas ordens de grandeza em comparação ao polímero acrílico puro. Por fim, estruturas macroscópicas funcionalizadas com Rodamina B e nanotubos de carbono apresentam potencial aplicabilidade em experimentos de laseres aleatórios. Utilizando microestruturação direta a laser, a fabricação de padrões periódicos dentro dessas estruturas alterou a emissão característica do laser aleatório, fixando os picos de emissão em comprimentos de onda específicos. / In this work we present polymeric structures functionalized with carbon nanotubes, which are processed using laser fabrication techniques. Firstly, we present a methodology to incorporate single-walled carbon nanotubes, functionalized with carboxylic acid (SWCNT-COOH) into acrylate resins. The resins functionalization was obtained, being possible to incorporate nanotubes in a range of 0.01% to 1% by weight. In addition, aiming at optical and optoelectronic applications, such functionalized resins can also be mixed with Rhodamine B or MEH-PPV. Through the multiphoton absorption polymerization technique, threedimensional microstructures presenting good resolution (approximately 650 nm) and integrity were fabricated using these resins. Raman spectroscopy showed that SWCNT-COOH are distributed throughout the volume of the microstructures, a required feature for devices applications. The structures functionalization was not restricted just to the volume. Acrylate microstructures were functionalized with SWCNT-COOH only on their surface, using the combination of Michael addition and carbodiimide coupling techniques. Raman analyzes also showed good distribution of the nanotubes on the polymeric surface. Even structures which were functionalized with low concentrations of SWCNT-COOH exhibited improvements in mechanical and electrical properties. Functionalized structures with 0.01% (by weight) of SWCNT-COOH proved to be more resistant in indentation tests than non-functionalized samples. Regarding the electrical properties, structures with the same functionalization range showed higher conductivity (in two orders) compared to the pure acrylate polymer. Finally, macroscopic structures, functionalized with Rhodamine B and carbon nanotubes present potential applicability in random laser experiments. Using direct laser writing, periodic patterns were fabricated within these functionalized structures, changing the characteristic emission of the random laser, setting the emission peaks at specific wavelengths.

The cost of crystalline silicon solar cells must be reduced in order for photovoltaics to be widely accepted as an economically viable means of electricity generation and be used on a larger scale across the world. There are several ways to achieve cost reduction, such as using thinner silicon substrates, lowering the thermal budget of the processes, and improving the efficiency of solar cells. This thesis examines the use of plasma enhanced chemical vapour deposited silicon nitride to address the criteria of cost reduction for n-type crystalline silicon solar cells. It focuses on the surface passivation quality of silicon nitride on n-type silicon, and injection-level dependent lifetime data is used extensively in this thesis to evaluate the surface passivation quality of the silicon nitride films. The thesis covers several aspects, spanning from characterisation and modelling, to process development, to device integration. The thesis begins with a review on the advantages of using n-type silicon for solar cells applications, with some recent efficiency results on n-type silicon solar cells and a review on various interdigitated backside contact structures, and key results of surface passivation for n-type silicon solar cells. It then presents an analysis of the influence of various parasitic effects on lifetime data, highlighting how these parasitic effects could affect the results of experiments that use lifetime data extensively. A plasma enhanced chemical vapour deposition process for depositing silicon nitride films is developed to passivate both diffused and non-diffused surfaces for n-type silicon solar cells application. Photoluminescence imaging, lifetime measurements, and optical microscopy are used to assess the quality of the silicon nitride films. An open circuit voltage of 719 mV is measured on an n-type, 1 Ω.cm, FZ, voltage test structure that has direct passivation by silicon nitride. Dark saturation current densities of 5 to 15 fA/cm2 are achieved on SiN-passivated boron emitters that have sheet resistances ranging from 60 to 240 Ω/□ after thermal annealing. Using the process developed, a more profound study on surface passivation by silicon nitride is conducted, where the relationship between the surface passivation quality and the film composition is investigated. It is demonstrated that the silicon-nitrogen bond density is an important parameter to achieve good surface pas-sivation and thermal stability. With the developed process and deeper understanding on the surface passivation of silicon nitride, attempts of integrating the process into the fab-rication of all-SiN passivated n-type IBC solar cells and laser doped n-type IBC solar cells are presented. Some of the limitations, inter-relationships, requirements, and challenges of novel integration of SiN into these solar cell devices are identified. Finally, a novel metallisation scheme that takes advantages of the different etching and electroless plating properties of different PECVD SiN films is described, and a preliminary evalua-tion is presented. This metallisation scheme increases the metal finger width without increasing the metal contact area with the underlying silicon, and also enables optimal distance between point contacts for point contact solar cells. It is concluded in this thesis that plasma enhanced chemical vapour deposited silicon nitride is well-suited for n-type silicon solar cells.

The cost of crystalline silicon solar cells must be reduced in order for photovoltaics to be widely accepted as an economically viable means of electricity generation and be used on a larger scale across the world. There are several ways to achieve cost reduction, such as using thinner silicon substrates, lowering the thermal budget of the processes, and improving the efficiency of solar cells. This thesis examines the use of plasma enhanced chemical vapour deposited silicon nitride to address the criteria of cost reduction for n-type crystalline silicon solar cells. It focuses on the surface passivation quality of silicon nitride on n-type silicon, and injection-level dependent lifetime data is used extensively in this thesis to evaluate the surface passivation quality of the silicon nitride films. The thesis covers several aspects, spanning from characterisation and modelling, to process development, to device integration. The thesis begins with a review on the advantages of using n-type silicon for solar cells applications, with some recent efficiency results on n-type silicon solar cells and a review on various interdigitated backside contact structures, and key results of surface passivation for n-type silicon solar cells. It then presents an analysis of the influence of various parasitic effects on lifetime data, highlighting how these parasitic effects could affect the results of experiments that use lifetime data extensively. A plasma enhanced chemical vapour deposition process for depositing silicon nitride films is developed to passivate both diffused and non-diffused surfaces for n-type silicon solar cells application. Photoluminescence imaging, lifetime measurements, and optical microscopy are used to assess the quality of the silicon nitride films. An open circuit voltage of 719 mV is measured on an n-type, 1 Ω.cm, FZ, voltage test structure that has direct passivation by silicon nitride. Dark saturation current densities of 5 to 15 fA/cm2 are achieved on SiN-passivated boron emitters that have sheet resistances ranging from 60 to 240 Ω/□ after thermal annealing. Using the process developed, a more profound study on surface passivation by silicon nitride is conducted, where the relationship between the surface passivation quality and the film composition is investigated. It is demonstrated that the silicon-nitrogen bond density is an important parameter to achieve good surface pas-sivation and thermal stability. With the developed process and deeper understanding on the surface passivation of silicon nitride, attempts of integrating the process into the fab-rication of all-SiN passivated n-type IBC solar cells and laser doped n-type IBC solar cells are presented. Some of the limitations, inter-relationships, requirements, and challenges of novel integration of SiN into these solar cell devices are identified. Finally, a novel metallisation scheme that takes advantages of the different etching and electroless plating properties of different PECVD SiN films is described, and a preliminary evalua-tion is presented. This metallisation scheme increases the metal finger width without increasing the metal contact area with the underlying silicon, and also enables optimal distance between point contacts for point contact solar cells. It is concluded in this thesis that plasma enhanced chemical vapour deposited silicon nitride is well-suited for n-type silicon solar cells.

Neste trabalho apresentamos estruturas poliméricas funcionalizadas com nanotubos de carbono, as quais são processadas utilizando técnicas de fabricação a laser. Inicialmente apresentamos uma metodologia para incorporar nanotubos de carbono de parede simples, funcionalizados com ácido carboxílico (NTCPS-COOH) em resinas acrílicas. A funcionalização dessas resinas foi alcançada, sendo possível incorporar nanotubos em uma faixa de 0,01% até 1%, em peso. Adicionalmente, visando aplicações em óptica e optoeletrônica, a inserção de Rodamina B ou MEH-PPV junto às resinas funcionalizadas com nanotubos também foi realizada. Através da técnica de polimerização via absorção multifotônica, microestruturas tridimensionais com boa resolução (aproximadamente 650 nm) e integridade foram fabricadas com essas resinas. A espectroscopia Raman mostrou que os NTCSPS-COOH estão distribuídos por todo o interior das microestruturas, característica necessária para aplicação em dispositivos. A funcionalização das estruturas não se restringiu apenas ao volume. Microestruturas acrílicas foram funcionalizadas com NTCPS-COOH apenas em sua superfície, utilizando a combinação das técnicas de adição de Michael e acoplamento carbodiimida. Análises Raman mostraram também uma boa distribuição dos nanotubos na superfície das amostras funcionalizadas. Mesmo as estruturas que foram funcionalizadas com baixas concentrações de NTCPS-COOH exibiram melhorias nas propriedades mecânicas e elétricas. Estruturas funcionalizadas com 0,01% (em peso) de NTCPS-COOH se mostraram mais resistentes em ensaios de indentação do que as amostras não funcionalizadas. Do ponto de vista elétrico, estruturas com a mesma faixa de funcionalização apresentaram condutividade elétrica superior em duas ordens de grandeza em comparação ao polímero acrílico puro. Por fim, estruturas macroscópicas funcionalizadas com Rodamina B e nanotubos de carbono apresentam potencial aplicabilidade em experimentos de laseres aleatórios. Utilizando microestruturação direta a laser, a fabricação de padrões periódicos dentro dessas estruturas alterou a emissão característica do laser aleatório, fixando os picos de emissão em comprimentos de onda específicos. / In this work we present polymeric structures functionalized with carbon nanotubes, which are processed using laser fabrication techniques. Firstly, we present a methodology to incorporate single-walled carbon nanotubes, functionalized with carboxylic acid (SWCNT-COOH) into acrylate resins. The resins functionalization was obtained, being possible to incorporate nanotubes in a range of 0.01% to 1% by weight. In addition, aiming at optical and optoelectronic applications, such functionalized resins can also be mixed with Rhodamine B or MEH-PPV. Through the multiphoton absorption polymerization technique, threedimensional microstructures presenting good resolution (approximately 650 nm) and integrity were fabricated using these resins. Raman spectroscopy showed that SWCNT-COOH are distributed throughout the volume of the microstructures, a required feature for devices applications. The structures functionalization was not restricted just to the volume. Acrylate microstructures were functionalized with SWCNT-COOH only on their surface, using the combination of Michael addition and carbodiimide coupling techniques. Raman analyzes also showed good distribution of the nanotubes on the polymeric surface. Even structures which were functionalized with low concentrations of SWCNT-COOH exhibited improvements in mechanical and electrical properties. Functionalized structures with 0.01% (by weight) of SWCNT-COOH proved to be more resistant in indentation tests than non-functionalized samples. Regarding the electrical properties, structures with the same functionalization range showed higher conductivity (in two orders) compared to the pure acrylate polymer. Finally, macroscopic structures, functionalized with Rhodamine B and carbon nanotubes present potential applicability in random laser experiments. Using direct laser writing, periodic patterns were fabricated within these functionalized structures, changing the characteristic emission of the random laser, setting the emission peaks at specific wavelengths.

Processing of Si in the semiconductor and solar cell industry has been dominated by the Diode Pumped Solid State (DPSS) Ultraviolet (UV) laser. Recent advances in laser source technology have produced fibre lasers with Master Oscillator Power Amplifier (MOPA) architectures that offer high repetition rates, high operational efficiencies, and pulse modulation controls exceeding those of typical Q-switched DPSS lasers. The aim of this research is to investigate 1 μm fibre laser machining of Si with a view to identifying the influential laser parameters for optimum processing of high quality, high efficiency micro drilling and surface texturing applications. A secondary aim is to develop a greater understanding of the laser material interactions and material removal mechanism when using fast rise-time nanosecond laser pulse envelopes. The IR fibre laser was able to perform percussion drilling and single pulse machining on the polished Si over a range of intensities up to 1.22 GW/cm2. With the optimum parameters, the micro-sized holes generated by the IR laser have a well defined edge, no heavy recast and no cracks. With a pulse shape of fast rise time (<7.5 ns for a 10-90% rise in signal), a high front peak power zone (approaching 14 kW) and an energetic long tail (40-180 ns), the absorption coefficient of Si at IR wavelength increased dramatically with time and temperature due to the fact that the liquid Si has a metal like absorption behavior. As a result, Si was quickly melted and the rest of pulse energy was able to remove the liquid Si effectively. The machining process left a limited amount of resolidified melt droplets and vapor condensates, which could be washed off ultrasonically. The drilling process was energy efficient when melt expulsion dominated the machining mechanism (0.08-0.2 mJ pulse energy depending on the pulse durations). The low energy pulse (~0.2 mJ) can achieve similar depth as the high energy pulse (~0.7 mJ), so high repetition rates of 100 kHz can be used to instead of 25 kHz, resulted in high processing speed. In addition, by comparing the single pulse machining with the state of the art UV laser, the IR fibre laser machined deeper features and better surface finish in the pulse energy region of >0.07 mJ. With the pulse shaping capability, the material properties can be varied and the wavelength factor can be minimized. The results suggest that applications like microvia drilling can now be carried out with the more flexible and low cost IR fibre laser. The increased repetition rates of fibre laser can increase production speed to satisfy the needs of drilling ~10 thousands holes per second, required by the modern semiconductor and solar cell production. The shortened optical penetration length of 1 μm wavelength laser on Si with increasing temperature and sufficient thermal diffusion length resulted from the asymmetrical fibre laser pulse and the dynamic properties of Si produced a thick liquid layer. A one-dimensional heat conduction model based on the surface heating source predicted that this superheated liquid layer was able to stay above 4706 K (0.905 times the thermal critical temperature 5200 K of Si) for longer than 70 ns to induce explosive boiling. This proposed material removal mechanism was also confirmed by the shadowgraph images, showing particulates ejection lasting up to ten microseconds after the laser pulse. The estimated hole depth based on the explosive boiling alone were different from the measured ones at varying peak power densities (<1.22 GW/cm2) but fixed pulse duration (200 ns), since Si was removed by a mixture of mechanisms. With varying pulse durations (40-200 ns) but fixed peak power density (~0.63 GW/cm2), the estimated depth based on the explosive boiling was in close agreement with the measured ones (6% difference on average). The SEM images at this power density showed a micron- /submicron-sized debris field, which was also observed with the explosive boiling in the past. Although the improved quality of Si machining was demonstrated with the 1 μm MOPA based fibre laser, the setup of this system was only applicable to surface texturing, blind holes and through holes of less than 100 μm in depth. Further research is required to demonstrate the capability of more energetic pulse with higher peak power and large pulse duration range to explore more machining options.

In the present research, a novel method, namely sol-gel/laser-induced technique (SGLIT), has been developed to generate nano-structured TiO2-based films. The TiO2 films based on unloaded (pure) TiO2, Ce-TiO2, W-TiO2 and Ag-TiO2, have been investigated in attempt to stabilise the formation of anatase and consequently of enhancing photo-catalytic and anti-bacterial activities. The TiO2 precursor loaded with Ce2+, W6+ and Ag2+ ions (Ce-TiO2, W-TiO2 and Ag-TiO2) were separately prepared by sol-gel method and spin-coated on microscopic glass slides. A pulsed KrF excimer laser with a wavelength of 248 nm and pulse width of 13-20 ns was employed to irradiate on the sol-gel prepared films at various operating parameters, in terms of laser fluence, number of laser pulses and repetition rate. The work has been focussed on microstructural characterisation of various films prepared by both SGLIT and furnace, in the consideration of crystallographic structure, phase transformation, crystallite sizes, surface morphology, film thickness and optical properties, by means of Raman spectroscopy, XRD, FEG-SEM/EDX, TEM/HR-TEM/EDX, AFM and UV-Vis spectroscopy etc. The results showed that nano-crystallisation of the films after laser irradiation has been achieved, with controllable amount of anatase formation. These coatings presented a unique feature of surface morphology with meso-porosity and much enlarged surface areas, compared with the films prepared by furnace sintering technique. The addition of Ce and Ag, stabilized the anatase structure during the laser irradiations, whereas the addition of W destabilized the anatase structure. The Ce-TiO2 films prepared by SGLIT exhibited anatase structure which was stable up to 500 laser pulses at 35 mJ cm-2 fluence. The anatase was formed after 10 laser pulses only at 65-75 mJ cm-2 fluence in the W-TiO2 films. When a higher number of laser pulses, fluence or higher W6+ loading were chosen, rutile structure started to form. On the other hand, the Ag-TiO2 nano-composite films prepared by SGLIT presented the anatase up to 200 laser pulses at 85 mJ cm-2 fluence. On average, anatase crystallite size of about 38 nm was achieved from both the W-TiO2 and Ag-TiO2 films prepared by SGLIT. In contrast, the furnace-sintered W-TiO2 and Ag-TiO2 films produced anatase crystallite size of 49.4 nm and 29.8 nm respectively. Another achievement of the present research is the development of a single-step laser irradiation technique to generate an Ag-TiO2 nano-composite film on the glass substrate. A pulsed laser beam produced hexagonal Ag nanoparticles along with the crystallization of anatase-based nano-structured TiO2 film which was accomplished in 1 µs only. The films prepared by SGLIT displayed a higher photo-absorption compared to their furnace-sintered counterparts due to the unique surface features with a higher surface roughness. Overall, an enhanced bactericidal activity against E. coli cells was demonstrated under UV light by each of the W-TiO2 films compared to furnace-sintered films except the 1W-TiO2. The E. coli cells did not survive on the W-TiO2 films prepared by SGLIT, after 80 minutes under UV (365 nm) light. In contrast, E. coli cells still survived on the surface of furnace-sintered W-TiO2 films under the same conditions. Ag-TiO2 nano-composite films prepared by SGLIT, demonstrated an enhanced anti-bacterial activity against E. coli compared to the conventionally- made Ag-TiO2 films. No bacteria survived on the Ag-TiO2 films prepared by 50 laser pulses at 85 mJ cm-2 fluence, whereas E. coli colonies always survived on the furnace-sintered Ag-TiO2 films under the UV, natural light and the dark room conditions.

Three-dimensional nanocomposite networks consisting of percolated Si nanowires in a SiOx matrix, Si:SiO2, were studied. The structures were obtained by reactive ion beam sputter deposition of SiOx (x~0.6) thin films at 450 °C and subsequent crystallization using conventional oven as well as millisecond line focus laser annealing. Rutherford backscattering spectrometry, Raman spectroscopy, X-ray diffraction, cross-sectional and energy-filtered transmission electron microscopy were applied for sample characterization. While oven annealing resulted in a mean Si wire diameter of 10 nm and a crystallinity of 72 % within the Si volume, almost single-domain Si structures with 30 nm in diameter and almost free of amorphous Si were obtained by millisecond laser application. The structural differences are attributed to the different crystallization processes: Conventional oven tempering proceeds via solid state, millisecond laser application via liquid phase crystallization of Si. The 5 orders of magnitude larger diffusion constant in the liquid phase is responsible for the three times larger Si nanostructure diameter. In conclusion, laser annealing offers not only significantly shorter process times but moreover a superior structural order of nano-Si compared to conventional heating.