京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19722号 / 工博第4177号 / 新制||工||1644(附属図書館) / 32758 / 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 髙岡 義寛, 教授 山田 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

This dissertation presents an innovative solid-state current amplifier based on impact-ionization. Unlike avalanche photodetectors which use the same amplification principle, this device can be integrated with any external current source. A discrete amplifier was built on a silicon surface using standard CMOS fabrication processes including lithography, oxidation, ion implantation, diffusion, chemical wet etching, metal deposition, annealing, and rapid thermal processing. Testing was performed by connecting the device to a silicon photodiode, indium-gallium-arsenide photodiodes, and a function generator to demonstrate its compatibility with arbitrary current sources. Current gains above 100 along with pre-amplified leakage currents of less than 10 nA were measured. This amplifier can also be cascaded to achieve very high gains similar to the photomultiplier tube but with much smaller size and no vacuum environment required. Testing was done by amplifying the output signal from an external silicon photodiode. Current gains over 600 were measured when two amplifying devices were cascaded. Additionally, the gain saturation phenomenon of the amplifier due to the space-charge effect is investigated. The measured gain saturation is observed to match very well with the theoretical based predictions. We also present a design rule for obtaining high current gain from the cascaded structure without experiencing gain saturation. Initial bandwidth of the SIM when connected to a silicon photodiode was measured to be about 300 kHz. As we replace the photodiode by a function generator, the bandwidth improved to 450 kHz which is the frequency limit of the system. These results were made on the first generation of SIM devices. We discovered that the space-charge resistance Rsc plays a significant role in determining frequency response. In future generations of the device, we can begin with optimizing the device geometry to reduce this resistance. Also, we can reduce the size of the metal pad and increase the oxide layer thickness to further minimize the device capacitance for faster response. Because of the low-noise gain mechanism employed, this device is of potential interest to a variety of fields requiring high-sensitivity optical or electronic detection.

The soft x-rays (wavelengths less than 30 nm) emitted by the sun are responsible for the production of high energy photoelectrons in the D and E regions of the ionosphere, where they deposit most of their energy. The photoelectrons created by this process are the main drivers for dissociation of nitrogen ($N_2$) molecules in the altitude range below 200 km. The dissociation of $N_2$ is one of main mechanisms responsible for the production of nitric oxide (NO) at these altitudes. These processes are important to understand because NO plays a critical role in controlling the temperatures of various regions of Earth's atmosphere. In order to estimate the dissociation rate of $N_2$ we need its dissociation cross-sections. The dissociation cross-sections of $N_2$ due to inelastic collisions with electrons is primarily es- timated from the cross-sections of its excitation states (using predissociation factors) and dissociative ionization channels. Predissociation is the transition without emission of radi- ation from a stable excited state to an unstable excited state of a molecule that leads to dissociation. Unfortunately, the lack of cross-section data, particularly at high electron en- ergies and of higher excited states of N 2 and N 2 + , introduces uncertainty in the dissociation cross-section and subsequently the dissociation rate calculation, which leads to uncertainties in the NO production rate. We have updated a photoelectron model with thoroughly-revised electron impact cross- section data of all major species and experimentally determined predissociation factors. The dissociation rates of $N_2$ using this model are compared to the dissociation rates obtained using another existing (Solomon and Qian [2005]) model. A parameterized version of the updated dissociation rates are used in a one-dimensional global average thermospheric/ ionospheric model, ACE1D (Atmospheric Chemistry and Energetics), to obtain the updated production rates of NO. In the final chapter, we use the ACE1D model to show that the energies deposited by the solar soft x-rays in the lower thermosphere at altitudes between 100 -150 km affect the temperature of the Earth's thermosphere at altitudes well above 300 km. By turning off the input solar flux in the different wavelength bins of the model iteratively, we are able to demonstrate that the maximum change in exospheric temperature is due to changes in the soft solar x-ray bins. We also show, using the thermodynamic heat equation, that the molecular diffusion via non-thermal photoelectrons is the main source of heat transfer to the upper ionosphere/thermosphere. Moreover, these temperature changes and heating effects of the solar soft x-rays are comparable to that of the much stronger He II 30.4nm emission. Finally, we show that the uncertainties in the solar flux irradiance at these soft x-rays wavelengths result in corresponding uncertainties in the modeled exospheric temperature, and these uncertainties increase substantially with increased solar activity. / Doctor of Philosophy / The radiation from the sun covers a wide range of the electromagnetic spectrum. The soft x-rays with wavelengths less than 30 nm are the most energetic and variable part of the spectrum, and would have detrimental effects on humans were they not absorbed by the atmosphere. The absorption of soft x-rays by the Earth's atmosphere at altitudes near 100- 150 km creates ionized and energized particles. These energetic changes can affect and even damage the satellites in low Earth orbit, and can cause radio communication blackouts and radiation storms (large quantities of energetic particles, protons and electrons accelerated by processes at and near the Sun). Therefore, we need to have good models that can quantify these changes in order to correctly predict their effects on our atmosphere, and help to mitigate any harmful effects. The soft x-rays and the extreme ultraviolet (EUV) are responsible for ionization of the major neutral species, $N_2$ , $O_2$ and O, in the Earth's atmosphere, which leads to the production of ions and energetic photoelectrons. These high energy photoelectrons can cause further ion- ization, excitation and dissociation. We study the dissociation of $N_2$ by these photoelectrons to create neutral N atoms. The N atoms created via this process combine with the $O_2$ in the atmosphere to produce nitric oxide (NO), which is one of the most important minor constituents because of its role in regulating atmospheric heating/cooling. The production of NO peaks near 106 km altitude, where most of the energy of the soft x-rays are deposited. However, they also affect the temperature of the upper atmosphere well above this altitude. This is because the energy of the photoelectrons is conducted to the upper atmosphere by collisions of electrons and ions with ambient neutral atoms and molecules, thus increasing their temperature. In this study, we use modeling of soft x-ray irradiance, photoelectron ionization, excitation and dissociation rates and atmospheric neutral temperature to quantify the effects of soft x-rays on the Earth's atmosphere.

Les mémoires non-volatiles à grille flottante sont utilisées pour le stockage d'information sous la forme d'une charge électrique contenue dans la grille flottante d'un transistor. Le comportement de ces dispositifs mémoire est fortement lié aux propriétés de leur oxyde tunnel, qui permet à la fois le passage de cette charge lors d'opérations de programmation ainsi que sa rétention en l'absence d'alimentation électrique. Au cours de ce travail, des mesures de courant tunnel ont été réalisées sur des capacités semiconducteur-oxyde-semiconducteur de grande surface représentatives de la zone d'injection des cellules mémoire. L'application de pulses courts sur la grille de ces structures de test, au cours desquels le courant peut être mesuré en temps réel, a permis de mettre en évidence les principales propriétés transitoires et stationnaires pouvant affecter le fonctionnement des dispositifs mémoire. L'effet de la dégradation des oxydes tunnel, qui impacte le comportement des cellules mémoire lors des opérations de programmation et de la rétention, a été observé et interprété dans le cas d'un stress à tension constante. Les résultats obtenus sur les capacités de grande surface ont pu être utilisés dans le cadre d'une modélisation de cellules EEPROM. / Floating gate non-volatile memory devices are used to store data under the form of an electric charge contained in the floating gate of a transistor. The behavior of these memory devices is strongly linked to the properties of their tunnel oxide, which allows the transit of this charge during write/erase operations as well as its retention while the transistor is not polarized. During this work, tunneling current measurements have been performed on large area semiconductor-oxide-semiconductor capacitors that are representative of the injection zone of memory cells. The application of short pulses to the gates of these test structures, during which the current can be measured as a function of time, allowed the observation of the main transient and steady-state properties that can affect the functioning of memory devices, The effect of tunnel oxide degradation, which impacts the behavior of memory cells during write/erase operations as well as data retention, has been observed and interpreted in the case of a constant voltage stress. The results obtained on large area capacitors have been used to model EEPROM cells.

97% des articles publiés sur les études climatiques racontent que le réchauffement climatique est entièrement causé par les activités humaines. Les gaz émis lors de la production d'énergie électrique ainsi que d'autres gaz rejetés par les voitures ont un réel impact sur l'atmosphère. Une solution consiste à mettre au point des composants présentant des pertes de conduction plus faibles et des caractéristiques de claquage plus élevées qui pourraient être utilisés dans des centrales nucléaires, des cellules de commutation à haute puissance, des voitures hybrides (électriques), etc.De nos jours, les composants à base de silicium contrôlent environ 95% des dispositifs électroniques. Le carbure de silicium SiC et le nitrure de gallium GaN sont actuellement à l’étape de R&D, et commencent à être intégrés dans certains circuits électroniques. D'autres matériaux tels que Ga2O3, AlN ou le diamant sont encore à l’étape de recherche. Les derniers sont connus sous le nom de matériaux à bande ultra large et semblent être la solution requise pour les faibles pertes de puissance. Le diamant est reconnu comme le matériau ultime pour la prochaine génération de composants de puissance en raison de ses propriétés physiques exceptionnelles telles qu'un champ de claquage élevé (>10 MV/cm) permettant d'utiliser le dispositif pour une commande de puissance élevée, une mobilité de porteurs élevée (2 000 cm^2/V.s pour les trous), une vitesse de saturation élevée, une conductivité thermique élevée (22 W/cm.K) pour une parfaite dissipation de chaleur et une faible constante diélectrique. Théoriquement, le diamant est le semi-conducteur offrant le meilleur compromis entre résistance à l'état passant et tension de claquage. En particulier, en raison de l'ionisation incomplète des dopants, il est encore plus efficace à haute température. Diverses diodes Schottky en diamant (SBD) avec de bonnes performances à l’état passant et bloqué (7,7 MV/cm) ont été rapportées. En plus des SBDs, des transistors à effet de champ (FET) ont également été étudiés à travers des oxyde-métal semi-conducteur FETs (MOSFETs) utilisant une surface hydrogénée avec des densités de courant élevées à l'état passant ou des surface oxygéné avec de bonnes caractéristiques de blocage. Pour les composants de haute-tension, il est nécessaire de changer l’architecture de l’électrode afin d’éviter un claquage prématuré due à l’encombrement du champ électrique aux bords. Dans ce but, les techniques de terminaison de bord sont utilisées pour atteindre les caractéristiques idéales. La tâche évidente avant toute fabrication de composant est la partie simulation qui prédit l’optimisation de l’architecture et les caractéristiques attendues. Une bonne prédiction nécessite la connaissance des paramètres du matériau. Les paramètres importants pour le claquage sont les coefficients d'ionisation par impact. Plusieurs coefficients ont été publiés pour le diamant. Toutefois, ils ont été extraits en « fittant » des structures non optimisées, d'où un manque de précision.Dans cette étude, deux structures de terminaisons de bord pour des diodes Schottky, appelées plaque de champ et anneaux à champ flottant, ont été étudiées. Leur efficacité de distribution du champ de surface par analyse de courant induit par faisceau d'électrons (EBIC) a été observée. De plus, des FETs ont été fabriqués et caractérisés, un MESFET et un RB-MESFET. Les FETs présentent un claquage élevé, jusqu’à 3 kV et une faible résistance. Le développement des transistors est indissociable de la diode Schottky, car ils sont tous deux nécessaires à la fabrication de cellules de commutation. Et enfin, les coefficients d'ionisation par impact pour les électrons ont été mesurés à l'aide d’EBIC pour un champ >0,5 MV/cm dans une région sans défaut. Les valeurs mesurées sont (sous l’equation de Chynoweth) an = 971 /cm et bn=2,39x10^6 V/cm. Ces valeurs sont proches des coefficients mesurés expérimentalement et rapportés dans la littérature. / 97% of the published climate studies articles agree with the fact that recent global warming is entirely caused by human activities. The gases emitted to produce electrical energy plus other gases rejected by cars impact considerably on the atmosphere by greenhouse effect (without referring other factors). A solution to this problem is the development of components with lower power conduction losses and higher breakdown characteristics that could be used in nuclear power plants, high power commutation cells, hybrid (electric) cars and so on.The choice of the material to reach low power conduction losses and higher breakdown is of great importance. Nowadays, silicon-based devices control about 95% of all electronic components. Silicon carbide SiC and gallium nitride GaN are at present under research and development and start to be integrated into some electronic circuits. Other materials like Ga2O3, AlN or diamond are under research for power electronic application. The last ones are known as ultra wide bandgap materials and they seem to be the required solution to low power losses. Diamond is recognized as the ultimate material for the next next-generation of power devices owing to its exceptional physical properties such as high breakdown field (>10 MV/cm) to use the device for high power control, high carrier mobility (2000 cm^2/V.s for holes) for fast switching and high frequency devices, high saturation velocity, high thermal conductivity (22 W/cm.K) for a perfect heat dissipation and low dielectric constant. Theoretically, diamond is the best semiconducting material showing the best trade-off between on-resistance and breakdown voltage. Especially, due to the incomplete ionization of the dopant, it is even more efficient at high temperature. Various diamond Schottky barrier diodes (SBDs) with good forward and reverse performances (7.7 MV/cm) were reported. In addition to SBDs, switches diamond field effect transistors (FETs) were also investigated through metal-oxide-semiconductor FETs (MOSFETs) using either an H-terminated diamond surface with high current densities in on-state or an O-terminated one with high blocking characteristics. For the high blocking voltage devices, one needs to properly terminate the edge of the electrode at the surface in order to avoid premature breakdown of the devices due to electric field crowding at the borders. In that aim, edge termination (ET) techniques are used to push the limit of the devices and reach ideal features. The obvious task before any device fabrication if the simulation part that predicts the device optimization and expected characteristics. A good device prediction requires knowledge of the material parameters. Important parameters for device breakdown in the off-state are the impact ionization coefficients. At present, several ionization coefficients were reported for diamond, however, they were extracted by fitting non-optimized structures and hence there is a lack of accuracy.In this study, two edge terminations structures for Schottky barrier diodes called field plate (FP) oxide and floating field rings were investigated. Their effectiveness in surface field distribution via electron beam induced current (EBIC) analysis was observed. In addition, normally-on FETs were fabricated and characterized, a MESFET and a reverse blocking (RB)-MESFET. The FETs exhibited a high BV, up to 3 kV and a low on-resistance. The development of transistors is inseparable from the Schottky diode since both are required to fabricate commutation cells. And finally, impact ionization coefficients for electrons were measured using EBIC for a field >0.5 MV/cm in a defect-free region. The measured values are (in a Chynoweth form) an = 971 /cm and bn = 2.39x10^6 V/cm. These values are close to the experimentally measured coefficients reported in the literature.

Transport Properties of Wide Band Gap Semiconductors Louis Tirino III 155 pages Directed by Dr. Kevin F. Brennan The objective of this research has been the study of the transport properties and breakdown characteristics of wide band gap semiconductor materials and their implications on device performance. Though the wide band gap semiconductors have great potential for a host of device applications, many gaps remain in the collective understanding about their properties, frustrating the evaluation of devices made from these materials. The model chosen for this study is based on semiclassical transport theory as described by the Boltzmann Transport Equation. The calculations are performed using an ensemble Monte Carlo simulation method. The simulator includes realistic, numerical energy band structures derived from an empirical pseudo-potential method. The carrier-phonon scattering rates and impact ionization transition rates are numerically evaluated from the electronic band structure. Several materials systems are discussed and compared. The temperature-dependent, high-field transport properties of electrons in gallium arsenide, zincblende gallium nitride, and cubic-phase silicon carbide are compared. Since hole transport is important in certain devices, the simulator is designed to simulate electrons and holes simultaneously. The bipolar simulator is demonstrated in the study of the multiplication region of gallium nitride avalanche photodiodes.

In this dissertation, different approaches have been employed to address the quest of understanding the formation and growth mechanisms of carbon-containing molecular ions with relevance to astrochemistry. Ion mobility mass spectrometry and DFT computations were used to investigate how a second nitrogen in the pyrimidine ring will affect the formation of a covalent bond between the benzene radical cation and the neutral pyrimidine molecule, after it was shown that a stable covalent adduct can be formed between benzene radical cation and the neutral pyridine. Evidence for the formation of a more stable covalent adduct between the benzene radical cation and the pyrimidine is reported here. The effect of substituents on substituted-benzene cations on their solvation by an HCN solvent was also investigated using ion mobility mass spectrometry and DFT computations were also investigated. We looked at the effect of the presence of electron-withdrawing substituents in fluorobenzene, 1,4 di- fluorobenzene, and benzonitrile on their solvation by up to four HCN ligands, and compared it to previous work done to determine the solvation chemistry of benzene and phenylacetylene by HCN. We report here the observed increase in the binding of the HCN molecule to the aromatic ring as the electronegativity of the substituent increased. We also show in this dissertation, DFT calculations that reveal the formation of both hydrogen-bonded and electrostatic isomers, of similar energies for each addition to the ions respectively. The catalytic activity of the 1st and 2nd row TM ions towards the polymerization of acetylene done using the reflectron time of flight mass spectrometry and DFT calculations is also reported in this dissertation. We explain the variation in the observed trend in C-H/C-C activity of these ions. We also report the formation of carbide complexes by Zr+, Nb+, and Mo+, with the acetylene ligands, and show the thermodynamic considerations that influence the formation of these dehydrogenated ion-ligand complexes. Finally, we show in this dissertation, a novel ionization technique that we employed to generate ions that could be relevant to the interstellar and circumstellar media using the reflectron time of flight mass spectrometry.

Cette thèse est consacrée à l’étude de la dynamique des porteurs de charges sous forte concentration. La méthode Monte Carlo « Full-Band » a été utilisée pour la modélisation du transport et la relaxtion des porteurs de charge dans les semi-conducteurs III-V (GaAs, InAs, GaSb, In0.53Ga0.47As et GaAs0.50Sb0.50). Les structures électroniques ont été calculées par la Méthode des Pseudo-potentiels Non-Locaux Empiriques, ce qui a notamment permis de traiter le cas de l’alliage ternaire GaAs0.50Sb0.50 dans une approche de type Cristal Virtuel, matériau qui souffre d’un manque de caractérisations expérimentales. Dans ces semi-conducteurs polaires fortement dopés, le couplage entre phonons optiques polaires et plasmons a été pris en compte via le calcul de la fonction diélectrique totale incluant les termes associés à l’amortissement dans le système phonon-plasmon auto-cohérents. Ce phénomène de couplage phonon-plasmon, est apparu primordial pour l’analyse de la mobilité des électrons dans GaAs, In0.53Ga0.47As et GaAs0.50Sb0.50 en fonction de la concentration en accepteurs. Dans des semi-conducteurs fortement photo-excités, la relaxation des électrons et des trous a été étudiée en tenant compte du chauffage de la population de phonon (qui ralentit la relaxation des porteurs) avec un modèle Monte Carlo dédié à la dynamique des phonons (Thèse de H. Hamzeh). L’étude a montré que le ralentissement de la relaxation dépend fortement des concentrations de porteurs photo-excités à cause du couplage phonon-plasmon dans ces matériaux. Les processus de génération et recombinaison de porteurs tels que l’absorption optique, la recombinaison radiative, l’ionisation par choc et les recombinaisons Auger, ont été implémentés. Les taux de génération et recombinaison associés sont calculés directement sur les distributions de porteurs modélisées, sans supposer des distributions à l’équilibre. Ces processus sont cruciaux pour l’optimisation de Cellules Solaires à Porteurs Chauds. Le photo-courant de ce type de cellule théorique à haut rendement de 3ème génération avec un absorbeur en In0.53Ga0.47As a été étudié. / The aim of this work is the study of charge carriers dynamic under high carrier concentration regimes. The « Full-Band » Monte Carlo method is used for charge carrier transport/relaxation modeling in III-V semiconductors (GaAs, InAs, GaSb, In0.53Ga0.47As and GaAs0.50Sb0.50). Electronic band structures are calculated with the Non-Local Empirical Pseudopotential Method which enables the study of ternary alloys within a Virtual Crystal approach. This method has been applied to In0.53Ga0.47As and GaAs0.50Sb0.50, the latter being a promising material for Heterojunction Bipolar Transistor applications though it lacks experimental characterizations. In highly doped polar semiconductors, the polar optical phonon – plasmon coupling is accounted for via the calculation of the total dielectric function including self-consistent damping parameters. This coupling appeared crucial for the calculation of minority electron mobilities in highly p-doped GaAs, In0.53Ga0.47As and GaAs0.50Sb0.50. In strongly photo-excited semiconductors, phonon population heating has been included in the study of electrons and holes relaxation. Hot phonon populations, that slow the charge carrier relaxation through the phonon bottleneck effect, have been dealt with a phonon dedicated Monte Carlo model (PhD H. Hamzeh). The study showed that carrier relaxation slowing depends strongly on the photo-excited carrier concentration because of phonon-plasmon coupling in those semiconductors. Charge carrier generation and recombination processes such as photon absorption, radiative recombination, impact ionization and Auger recombinations, have been implemented. The associated generation and recombination rates are directly calculated with the sampled carrier distribution. Thus, the use of coefficients and lifetimes is avoided, and non equilibrium regimes were modeled. Those processes are of prime importance for Hot Carrier Solar Cells optimization. The theoretical photo-current of this kind of 3rd generation solar cell with an In0.53Ga0.47As absorber have been studied.

V této práci je prezentována studie fragmentačního procesu zvolené molekuly a jeho vztah ke složení fragmentačních produktů. Práce je zaměřená na výpočet fragmentační energie molekuly pomocí ab initio kvantově chemických metod, metodou „density functional theory (DFT)“ a také srovnáním s experimentem. Je prezentován vliv výpočetní metody, bázového setu, a geometrie molekuly na simulaci. Byla porovnána fragmentace methylfenylsilanu (MPS), dimethylfenylsilanu (DMPS), a trimetylfenylsilanu (TMPS). Fragmentace byla iniciována monochromatickým elektronovým svazkem (EII). Hmotnostní spektrometrie byla využita ke studiu složení fragmentačních produktů MPS a TMPS. Fragmentační produkty MPS a TMPS měřené v rámci této práce byly doplněny o experimentální studii DMPS, která byla prezentována v literatuře. Takto byla získána řada molekul, které jsou strukturně podobné, ale mají výrazně rozdílné chování během fragmentace. Pomocí měření účinného průřezu byly měřeny disociační energie vazeb a tyto disociační energie byly vypočteny pomocí metody DFT. Kombinací teoretického výpočtu metodou DFT a experimentálního měření jsme poukázali na společné rysy a na rozdíly ve fragmentačním schématu všech tří molekul. Navrhli jsme odštěpení dvou vodíkových atomů během plazmově indukovaného fragmentačního procesu. Vodíky mohou být odštěpeny pomocí dvou mechanismů: i. odštěpení dvou vodíků jeden po druhém a ii. odštěpení molekuly H2 v jednom kroku. Z profilů energie dokážeme určit, který mechanismus bude v tom konkrétním případě pravděpodobnější. Předpokládaný mechanismus je v korelaci s experimentálními výsledky fragmentace zjištěnými z hmotnostních spekter.

Thesis deals with environmental scanning electron microscopy and with detection of signal electrons by using ionization detector. First part talks about the principle of environmental scanning electron microscope. Second part describes signals generated by interaction of primary electron beam with sample. Third section explains the principle of impact ionization and ionization detector. Experimental part deals with usage of segmental ionization detector and with measuring of signal amplification from copper and platinum. Thesis also examines arrangement of electrodes of ionisation detector on material contrast and examines also on influence of voltage contrast on base - emitter junction of an NPN bipolar transistor. All experiments were carried out in dependency on saturated water vapour pressure in sample chamber.