<p>Single junction silicon photovoltaic cells (SJSPVCs) are unable to transform all the energy in the solar spectrum into electricity, due to the broad nature of the solar spectrum and the limits imposed by a single bandgap. Furthermore, high surface recombination velocity reduces the SJSPVC external quantum efficiency response, particularly to ultraviolet photons. It is the goal of spectral engineering to optimize the light that is incident on the cell, by down-shifting high energy photons to lower energies, for example, to improve the performance of photovoltaic cells.</p> <p>This thesis represents a study into the luminescence of ion implanted films, involving silicon nanocrystals (Si-NCs) and rare-earth ions in fused silica or silicon nitride. Quantum efficiency measurements taken with an integrating sphere were used to characterize some of the samples. Other photoluminescence (PL) characterization work was carried out with a single-wavelength laser and a collection lens normal to the sample. Variable angle spectroscopic ellipsometry (VASE) was used to estimate the optical constants of the implanted films. In secondary work, Rutherford backscattering spectrometry, time-dependent PL, infrared-PL measurements, and electrical conductivity measurements were used to characterize select samples.</p> <p>It was found that the conversion efficiency of Si-NCs in fused silica was about 1% – too low to be useful according to modeled results. However, considerable variation in the peak wavelength of the Si-NC PL was obtained, depending on the peak concentration of implanted silicon. Si-NC-type PL was also produced by low-energy implantation of oxygen into a Czochralski silicon wafer.</p> <p>Oxygen was also implanted into films of cerium-doped high-purity silicon nitride, and it was shown that the photoluminescence from these films is largely dependent on the level of oxygen doping. The internal conversion efficiency of a cerium-doped fused silica sample was found to approach 20%, which indicates that this is a promising avenue for future research.</p> <p>Finally, energy transfer was demonstrated between Si-NCs and erbium ions. The lifetime of the erbium PL appears to increase with increasing implanted silicon fluence.</p> / Master of Applied Science (MASc)

Ag thin film dewetting upon high temperature annealing is a non-trivial problem for its application in the semiconductor industry as an ohmic contact metal. Thus, preventing Ag thin film from dewetting is of great importance. Typically, adhesion-promoting layers of chromium are deposited to prevent dewetting, but this deposition has its own process optimization parameters. In this thesis, we introduce an alternative, novel strategy for dewetting prevention via Si or In ion implantation. Electron microscopy including SEM, AFM and AES are conducted to characterize changes in film morphology after ion implantation. Thermodynamic simulation is established to better understand the mechanism of this anti-dewetting approach as well as to predict the performance of doped Ag thin films. It is found that Ag films implanted by a trace amount of Si dopants remain intact after 24 h annealing at 530℃ rather than break down into isolated particles as pure Ag film did. Furthermore, Ag grains in doped samples are much smaller than that in non-doped samples and higher Si or In doses contribute to smaller grains, indicating that a retarding force against film grain growth is introduced by the implanting species. Fortunately, electrical conductivity and optical reflectivity of doped films change trivially, suggesting an insignificant influence of external species on the film performance. The retarding force suppressing film grain growth is demonstrated to be solute drag, which will introduce a size limit towards Ag grain growth. A grain growth model including the solute drag effect is established here to describe the grain growth process. Combining our thermodynamic simulation with our grain growth model in the presence of the solute drag effect, the critical grain diameter to initiate agglomeration of 100 nm thick Ag thin film is calculated to be 350 nm and the critical Si dose to prevent 100 nm thick Ag thin film from dewetting is predicted to be 2.0×1013 per cm2. Finally, we successfully synthesize ultrathin Si thin films via ion implantation and pattern as-deposited Si films by implanting through a hard mask in order to identify some steps towards synthesizing 2-D silicon, or silicene. The as-achieved pattern has an identical shape as that of mask, suggesting Si atoms only diffuse within the implanting regions during thermal annealing. Even though only amorphous Si films are prepared at present, this novel strategy possesses potential to fabricated CMOS-compatible 2-D silicon films for semiconductor industry. / Thesis / Master of Applied Science (MASc)

Concentration-versus-depth profiles have been calculated for Ti and C in Ti-implanted 52100 steel. A computer formalism was developed to account for diffusion and mixing processes, as well as sputtering and lattice dilation. A Gaussian distribution of Ti was assumed to be incorporated at each time interval. The effects of sputtering and lattice dilation were then included by means of an appropriate coordinate transformation. C was assumed to be gettered from the vacuum system in a one-to-one ratio with the surface Ti concentration up to a saturation point. Both Ti and C were allowed to diffuse. A series of experimental (Auger) concentration-versus-depth profiles of Ti implanted steel were analyzed using the above-mentioned assumptions. A best fit procedure for these curves yielded information on the values of the sputtering yield, range and straggling, as well as the mixing processes that occur during the implantation. The effective diffusivity of Ti was found to be 6x10⁻¹⁵ cm²/sec, a value that is consistent with the cascade mixing mechanism. The effective diffusivity of C was found 6x10⁻¹⁵ cm²/sec, and the sputtering yield by Ti atoms was best fit by a value of about 2. The observed range and straggling values were in very good agreement with the values predicted by existing theories, so long as the lattice was allowed to dilate. / M.S.

Extensive Raman-scattering studies have been performed in order to study the structure of ion-implanted GaAs, prior to any anneal. The spectroscopic evidence is consistent with a fine-scale mixture of amorphous and microcrystalline GaAs. Excessive bombardment with 120-keV SiF₃⁺ ions results in a 500-A thick surface layer which is completely amorphous (a-GaAs). A detailed chemical-etch damage depth profile has been completed for 45-keV Be⁺-implanted GaAs, which is not completely amorphized. The damage is characterized using the microcrystalline longitudinal-optical (LO) phonon frequency, line width, and intensity, and the intensity of the a-GaAs component of the Raman spectrum. The damage layer possesses a 1500-A thick surface layer of constant, high damage. This high-damage plateau is followed by a transition region in which the damage level smoothly decreases until the undisturbed crystal is reached near 4000 A. LO intensities were analyzed, within the amorphous/crystalline mixed-phase model, to obtain the volume fractions of the two components. Consistent estimates of the optical absorption in the high-damage plateau were obtained via two independent means. Resonance-Raman experiments were carried out, using laser lines between 1.5 and 2.71 eV. The intensity of the a-GaAs spectral component was found to depend on scattering volume (optical penetration), thus providing an internal intensity standard allowing the effects of scattering volume and scattering efficiencies to be separated. The LO phonon was found to resonate approaching the E₁ electronic transition at 2.9 eV. The strength of the resonance decreases with smaller crystallite size. A new Raman band was observed near 47 cm⁻¹ for photon energies below 2 eV. It resonates at 1.7 eV, near E₀ and not near E₁. I propose that this new feature arises from GaAs acoustic modes made Raman active by defectassisted scattering involving the crystalline/amorphous interface regions. A quantitative analysis is developed, with some success. Intensities of silicon local are observed to remain constant upon annealing, although conductivity increases by several orders of magnitude. The anneal primarily restores the mobility to that of crystalline GaAs. / Ph. D.

付記する学位プログラム名: 京都大学卓越大学院プログラム「先端光・電子デバイス創成学」 / 京都大学 / 新制・課程博士 / 博士(工学) / 甲第25295号 / 工博第5254号 / 新制||工||2000(附属図書館) / 京都大学大学院工学研究科電子工学専攻 / (主査)教授 木本 恒暢, 教授 白石 誠司, 准教授 船戸 充 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Made available in DSpace on 2017-07-21T19:26:00Z (GMT). No. of bitstreams: 1 Andre Assmann.pdf: 3125745 bytes, checksum: 38854736eae2fcc4e8c2c21a2668f387 (MD5) Previous issue date: 2011-04-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In the present work showing the results on mechanical and tribological properties of duplex stainless steel LDX2101 nitriding by Ion Implantation (II), Plasma Immersion Ion Implantation (PI3) and Glow Discharge (GD). Nitrogen ion implantation was performed at room temperature and 350 C. The nitrogen fluencies were combined to obtain an atomic nitrogen concentration of 27 %. The PI3 was carried out with temperatures of 300 and 350 C working in N2 atmosphere during 3 hours. For GD, the working conditions were gas mixture N2/H2 (in the ratio 80%/20%, 60%/40% and 20%/80%) and N2/CH4 (in the ratio 98%/02%) during 3 hours at temperatures of 300, 350 and 380 C. Structural characterizations of the modified layers were performed by X-Ray Diffraction (XRD) with Bragg-Brentano geometry. Hardness was obtained by instrumented indentation using Oliver and Pharr method’s with Berkovich indenter. Tribological tests were evaluated by reciprocating sliding with a WC(Co) sphere (counter body). XRD patterns for II samples showing only the formation of γN, however, samples treated by GD and PI3 showed the formation of γ’Fe4N and Fe2+XN, over there γN, as a function of the working temperature and nitriding atmosphere. After the nitriding hardness values between 8 and 20 GPa in comparison to 3 GPa of the bulk was obtained. The hardness profile of samples treated by GD at 350 and 380 C exhibit plateaulike for values of hardness between 13 and 20 GPa, indicate the formation of a thicker nitrited layer. The friction coefficient for II samples showed a strong adhesive wear. PI3 samples exhibit long running-in regimes compared to II and untreated samples. GD samples showing a predominant abrasive wear because ploughing of surface for asperities and wear particles formed between the surface and counter body. The significant decrease in the wear was observed in all GD samples, with a reduction of one order of magnitude compared to untreated sample. / No presente trabalho, são apresentados os resultados sobre as propriedades mecânicas e tribológicas do aço inoxidável duplex LDX 2101 nitretado por Implantação Iônica (II), Implantação Iônica por Imersão em Plasma (3IP) e Descarga Luminosa (DL). A Implantação Iônica de nitrogênio foi realizada em temperatura ambiente e em 350 C. As fluências utilizadas foram combinadas para obter uma concentração de átomos de nitrogênio de 27 %. A nitretação 3IP, foi realizada nas temperaturas de 300 e 350 C em atmosfera de N2 durante 3 horas. Para o tratamento por DL as condições de tratamento foram em diferentes atmosferas de N2/H2 (nas proporções de 80%/20%, 60%/40% e 20%/80%) e N2/CH4 (na proporção de 98%/02%) durante 3 horas nas temperaturas de 300, 350 e 380 C. A caracterização estrutural das camadas modificadas foi obtida através de Difração de Raios-X (DRX) com geometria Bragg-Brentano. Os perfis de dureza foram obtidos por indentação instrumentada usando o método de Oliver e Pharr com indentador do tipo Berkovich. Testes tribológicos foram realizados com tribômetro do tipo pino sobre disco em movimento recíproco com uma esfera de WC(Co) de contra corpo. Os padrões de DRX para amostras tratadas por II apresentaram apenas a formação de γN, contudo, as amostras tratadas por DL e 3IP apresentaram a formação de γ’-Fe4N e Fe2+XN, além de γN, como função da temperatura de tratamento e da atmosfera de nitretação. Após as nitretações durezas entre 8 e 20 GPa em comparação a 3 GPa para o substrato foram obtidas. Perfis de dureza para amostras tratadas por DL em 350 e 380 C exibiram valores entre 13 e 20 GPa em forma de platô, indicando a formação de uma espessa camada nitretada. O coeficiente de atrito para as amostras tratadas por II apresentaram um forte desgaste adesivo. Amostras tratadas por 3IP exibiram longos regimes de acomodação comparados as amostras tratadas por II e a amostra referência. Amostras tratadas por DL apresentaram um predominante desgaste abrasivo devido à deformação plástica da superfície causada pelas asperidades e pelas partículas de desgaste formadas entre a superfície e o contra corpo. Uma significante diminuição no desgaste foi observada em todas as amostras tratadas por DL, com uma redução de uma ordem de grandeza quando comparado a amostra sem tratamento.

No description available.

In recent years a great deal of interest has been focused on the synthesis of transitional metal (e.g. Ag, Cu, Fe, Au) nanosystems at the surface to sub-surface regions of Si and SiO2 matrices for fundamental understanding of their structures as well as for development of technological applications with enhanced electronic and optical properties. The applications of the metal nanoparticle or nanocluster (NC) systems range from plasmonics, photovoltaic devices, medical, and biosensors. In all of these applications; the size, shape and distribution of the metallic NCs in the silicon matrix play a key role. Low energy ion implantation followed by thermal annealing (in vacuum or gas environment) is one of the most suitable methods for synthesis of NCs at near surfaces to buried layers below the surfaces of the substrates. This technique can provide control over depth and concentration of the implanted ions in the host matrix. The implanted low energy metal ions initially amorphizes the Si substrates while being distributed at a shallow depth near the substrate surface. When subject to thermal annealing, the implanted ions agglomerate to form clusters of different sizes at different depths depending upon the fluence. However, for the heavier ions implanted with high fluences (~1×1016 - 1×1017 atoms/cm2), there lies challenges for accurately predicting the distribution of the implanted ions due to sputtering of the surface as well as redistribution of the implants within the host matrix. In this dissertation, we report the investigation of the saturation of the concentration of the implanted ion species in the depth profiles with low energies (< 80 keV) metal ions (Ag and Au) in Si (100), while studying the dynamic changes during the ion implantation. Multiple low energies (30-80 keV) Ag ions with different fluences were sequentially implanted into commercially available Si wafers in order to facilitate the formation of Ag NCs with a wide ion distributions range. The light absorption profile according to different sizes of NCs at the near-surface layers in Si were investigated. We have investigated the formation of Ag NCs in the Si matrix as a function of implantation and thermal annealing parameters. The absorbance of light is increased in Ag implanted Si with a significant increase in the current collection in I-V (current-voltage) photo switching measurements. The experimental photovoltaic cells fabricated with the Ag implanted Si samples were optically characterized under AM (air mass) 1.5 solar radiation conditions (~1.0 kW/m2). An enhancement in the charge collection were measured in the annealed samples, where prominent Ag NCs were formed in the Si matrix compared to the as-implanted samples with the amorphous layer. The characterization techniques such as Rutherford Backscattering Spectroscopy, XPS-depth profiling, transmission electron microscopy, optical absorption, and I-V (current-voltage) photo switching measurements were employed to understand the underlying science in the observed properties. The results of these investigations are discussed in this research.

Un matériau semi-conducteur utilisé lors de la fabrication d’antennes térahertz (THz), le quaternaire InGaAsP (E_g = 0,79 eV), subit une implantation ionique de Fe suivi d’un recuit thermique rapide (RTA) dans le but d’améliorer ses propriétés d’émission. Le recuit est nécessaire afin de recristalliser la couche amorphisée lors de l’implantation, donnant lieu à un polycristal rempli de défauts de recristallisation. On constate cependant que les matériaux implantés Fe offrent de meilleures performances que ceux simplement endommagés au Ga. Dans le but de départager l’effet des défauts de recristallisation et des impuretés de Fe, des mesures de spectroscopie transitoire des niveaux profonds (DLTS) et de DLTS en courant (I-DLTS), ainsi que de spectrométrie de masse d’ions secondaires par temps de vol (ToF-SIMS) ont été effectuées sur des échantillons non implantés et d’autres recristallisés. Les mesures DLTS et I-DLTS ont pour but de caractériser les niveaux profonds générés par ces deux procédures postcroissance, tout en identifiant le rôle que jouent les impuretés de Fe sur la formation de ces niveaux profonds. De plus, le voisinage des atomes de Fe dans le matériau recristallisé a été étudié à l’aide des mesures ToF-SIMS. Les mesures DLTS sur matériau recristallisé sont peu concluantes, car la mesure de capacité est faussée par la haute résistivité du matériau. Par contre, les mesures I-DLTS sur matériau recristallisé ont permis de conclure que les impuretés de Fe sont responsables de la formation d’une grande variété de niveaux d’énergie se trouvant entre 0,25 et 0,40 eV, alors que les défauts de structure induisent des niveaux de moins de 0,25 eV. La concentration de Fe est élevée par rapport au seuil de solubilité du Fe dans le matériau recristallisé. Il serait donc plausible que des agrégats de Fe se forment. Toutefois, cette hypothèse est infirmée par l'absence de pic aux masses correspondant à la molécule ^(56)Fe_2^+ sur les spectres ToF-SIMS. De plus, un modèle simple est utilisé afin d’estimer si certaines masses présentes sur les spectres ToF-SIMS correspondent à des liaisons non induites par la mesure dans le matériau recristallisé. Bien qu’aucune liaison avec le Ga et l'As n’est détectable, ce modèle n’exclut pas la possibilité de liens préférentiels avec l’In. / A semiconductor material used in the manufacture of terahertz (THz) antennas, the InGaAsP quaternary (E_g = 0,79 eV), is Fe-ion implanted followed by Rapid Thermal Annealing (RTA) in order to improve its emission properties. The annealing is required to recrystallize the layer that was amorphized during implantation, resulting in a polycrystal filled with recrystallization defects. However, the Fe-implanted materials provide better performance than those simply damaged with Ga. In order to disentangle the effect of recrystallization defects and of Fe impurities, Deep-Level Transient Spectroscopy (DLTS) measurements, current DLTS (I-DLTS) measurements and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) were carried out on non-implanted and on recrystallized samples. The DLTS et I-DLTS measurements aim to characterize deep levels generated by these two post-growth fabrication processes, while identifying the role of Fe impurities on the formation of these deep levels. In addition, a study of the vicinity of Fe atoms in the recrystallized material was performed using ToF-SIMS measurements. The DLTS measurements on recrystallized material were inconclusive because the capacitance measurements were distorted by the high resistivity of the material. On the other hand, the I-DLTS measurements on recrystallized material allowed us to conclude that the Fe impurities are responsible for the formation of a wide variety of energy levels lying between 0.25 and 0.40 eV, while structural defects induce levels lower than 0.25 eV. The Fe concentration is high compared to the solubility threshold of Fe in the material. It is therefore possible that Fe clusters are formed. However, this hypothesis is invalidated by the absence of a peak at the mass channels corresponding to the molecule ^(56)Fe_2^+ on ToF-SIMS mass spectra. Moreover, a simple model is used to estimate whether certain masses present on ToF-SIMS spectra correspond to actual bonds in the recrystallized material, not induced by the measurement. While no bonds with Ga and As were detectable, this model does not exclude the possibility of preferential binding between with In.

Le dopage du silicium par implantation ionique pour le photovoltaïque est une application relativement récente dont l'essor se heurte encore aujourd'hui aux coûts élevés d'intégration au sein des lignes de fabrication des cellules solaires. L'implantation ionique par immersion plasma promet de répondre aux futures exigences du secteur en termes de coûts et de productivité.Ces travaux de thèse ont permis le développement de procédés d'implantation ionique par immersion plasma de l'équipement PULSION®, conçu par IBS, dédiés à la fabrication de cellules solaires en silicium monocristallin. Dans un premier temps, nous montrons qu'il permet la réalisation de profils de dopage d'émetteur de type n variés, répondant aux exigences des cellules solaires à haut rendement. Les émetteurs fabriqués sont caractérisés de manière chimique, physique et électrique afin de démontrer leur excellente qualité. L'intégration de l'implantation ionique des émetteurs au sein d'un processus de fabrication industriel et peu coûteux, développé par l'INES sur silicium monocristallin de type p, permet d'atteindre des rendements de conversion supérieurs à 19,3%, soit un gain de plus de 0,5% par rapport aux rendements obtenus avec des cellules usuelles à émetteurs dopés par diffusion POCl3.La réalisation d'émetteurs de type p est également étudiée dans ce mémoire afin de préparer la transition technologique vers les cellules solaires sur silicium monocristallin de type n. Confirmant les atouts et le potentiel de la technologie d'implantation ionique par immersion plasma, les travaux menés au cours de cette thèse débouchent sur la conception d'un prototype industriel PULSION® dédié au photovoltaïque. / Ion implantation is a major process technology for manufacturing integrated circuits. However, silicon doping by ion implantation for photovoltaics is a relatively recent application, and its growth still faces high costs of integration into solar cell production lines. Plasma-immersion ion implantation (PIII) promises to meet the future industry requirements in terms of costs and productivity.This thesis work has led to the development of processes dedicated to silicon-based solar cell manufacturing using the plasma-immersion ion implanter – PULSION® – designed by IBS. First, we show that PIII enables the realization of various doping profiles for phosphorus-doped emitters which fit the requirements of high-efficiency solar cells. Emitters thus fabricated are chemically, physically and electrically characterized to demonstrate their excellent quality. Those emitters, implanted through plasma immersion and integrated into a low cost solar cell manufacturing line from INES on monocrystalline silicon, enable to raise the conversion efficiency, obtained with conventional POCl3-diffused solar cells, by more than 0.5% absolute to reach efficiencies above 19.3%.Fabrication of p-type boron implanted emitters is also studied in order to improve conversion efficiencies of p-type silicon based solar cells, but also in order to anticipate the technological shift from p-type to n-type silicon material. Thanks to this thesis work, the strength and potential of PIII for photovoltaic applications have been proven and this has convinced IBS to design a PULSION® equipment dedicated to solar cell manufacturing.