In this thesis, we study the physical properties of doped organic semiconductors. We first demonstrate the impact of doping on C60 films. In contrast to previous reports for organic thin films, the n-doped C60 films show a decrease of mobility with increasing doping levels; i.e., they follow the well-known Matthiessen rule which is generally observed in inorganic semiconductors. Using further strong organic donors and acceptors, we realize p-i-n homojunctions of several organic matrices: zinc-phthalocyanine, pentacene, and an iridium-complex TER004. We observe stable and reproducible diode characteristics, which can be described by the standard Shockley theory with an exception concerning the temperature dependence of the diode parameters. The current-voltage characteristics of the pentacene homojunctions under illuminated conditions indicate that the thermodynamic limitation of the open-circuit voltage is determined by the built-in voltage of 1.65 V, and that the recombination process is influenced by the distinct charge transport properties of electrons and holes. The very high built-in voltage of 2.2 V in the TER004 homojunction allows a red phosphorescent homo-OLED, which shows visible emission around 650 nm with low operation voltage. We examine the charge balance status in the homojunction structure, revealing that TER004 has superior electron transport properties.

In this work, we have explored 2D semiconducting transition metal dichalcogenides (TMDs), black phosphorus (BP), and graphene for various applications using liquid and mechanical exfoliation routes. The topical areas of interest that motivate our work include considering factors such as device integration, stability, doping, and the effect of gasses to modulate the electronic transport characteristics of the underlying 2D materials. In the first area, we have integrated solution-processed transparent conducting oxides (TCOs), specifically indium-doped tin oxide (ITO) with BP, which is a commonly used TCO for solar cell devices. Here we have found surface treatment of glass substrates with a plasma before spin-coating the solution-processed ITO, to be effective in improving coverage and uniformity of the ITO film by promoting wettability and film adhesion. The maximum transmittance obtained was measured to be ~75% in the visible region, while electrical measurements made on BP/ITO heterostructures showed improved transport characteristics compared to the bare ITO film. Within the integration realm, inkjet-printing of BP and MoS2 p-n hetero-junctions on standard ITO glass substrates in a vertical architecture was also demonstrated. To address the issue of stability which some 2D materials such as BP face, we experimented with ionic liquids (ILs) to passivation the hydrophilic surface of BP to minimize its oxidative degradation. The enhanced stability of BP was inferred through Raman spectroscopy and scanning probe microscopy techniques, where no observable changes in the A1g and A2g Raman vibrational modes were observed for the BP films passivated with ILs over time under ambient conditions. On the other hand, a blue-shift in these Raman modes was evident for unpassivated samples. Atomic force microscopy measurements on the unpassivated samples clearly revealed the difference in surface characteristics through localized regions of degradation that intensified with time which was absent in IL passivated BP samples. The electronic device measurements for IL coated BP devices showed a more stabilized Ids−Vds characteristic in the 5.4 K to 335 K temperature range. Prototypical demonstrations of stabilized ILs/BP devices at ambient printed on flexible polyimide substrates were also successfully made. At the same time, doping is one of the essential steps required for the modulation of carrier density and electronic transport in electronic and optoelectronic devices, which is the third topical area we have addressed in this work with semiconducting TMDs. Of the conventional approaches used to dope 3D semiconductors, ion-implantation is commonly adopted but given the ultra-thin nature of 2D materials, this approach is not feasible as it causes severe damage to the delicate crystalline lattice of ultra-thin 2D membranes. Instead, we have used plasma-based doping routes with UV-ozone treatement and solution processing using 1,2 dichloroethane, to characterize the temperature-dependent two-terminal and three-terminal electronic and optoelectronic transport of mechanically exfoliated 2D MoS2 and WSe2. A significant difference was seen in the optoelectronic properties between the two dopants, owing to differences in their respective doping mechanisms and the intrinsic structural attributes of the exfoliated flakes. A significant reduction in barrier height was evident after doping using both techniques in MoS2, while an increase in barrier height after soaking in 1,2 dichloroethane was seen in WSe2. Lastly, in the fourth topical area for sensing devices, we have studied the effect of gas-flow in inkjet-printed and spin-coated graphene and MoS2 to modulate the electronic transport for the 2D materials since their increased surface area is an ideal platform to observe interactions with external stimuli, in this case, in-coming gas species. Here, the chamber pressure and change in current with flow of gas was measured in the steady-state, as well as time-dependent dynamic transport toward nitrogen and carbon dioxide. We observed significant differences in the electrical response of mono-elemental graphene and binary MoS2, owing to differences in microstructure and joule heating response to the ambient gas. In conclusion, the findings obtained from our work will provide an important framework to help guide strategies in further improving integration schemes, stability, doping and sensing behavior driven by the unique structural attributes inherent to 2D materials for high-performance devices in the future.

The doping of quasi-freestanding graphene (QFG) on H-terminated, Si-face 6H-, 4H-, and 3C-SiC is studied by angle-resolved photoelectron spectroscopy (ARPES) close to the Dirac point. Using semi-insulating as well as n-type doped substrates we shed light on the contributions to the charge carrier density in QFG caused by i) the spontaneous polarization of the substrate, and ii) the band alignment between the substrate and the graphene layer. In this way we provide quantitative support for the previously suggested model of polarization doping of graphene on SiC [Phys. Rev. Lett. 108, 246104 (2012)].

京都大学 / 新制・課程博士 / 博士(人間・環境学) / 甲第23265号 / 人博第980号 / 新制||人||232(附属図書館) / 2020||人博||980(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 吉田 寿雄, 教授 田部 勢津久, 教授 中村 敏浩 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

Manganese (Mn) doped III-V dilute ferromagnetic semiconductors (DFSs) are a candidate materials for semiconductor spintronics due to their intrinsic ferromagnetism mediated by holes. In this thesis, Mn doped III-V dilute ferromagnetic semiconductors (DFSs), including (Ga,Mn)As, (In,Mn)As, (Ga,Mn)P, and (In,Ga,Mn)As have been successfully prepared by ion implantation and pulsed laser melting. All (In,Ga,Mn)As films are confirmed to be well recrystallized and ferromagnetic while their Curie temperatures depend on the Ga concentration. (Ga,Mn)As and (Ga,Mn)P have an inplane easy axis, while an out-of-plane easy axis for (In,Mn)As is observed. However, all of them do not present strong in-plane uniaxial anisotropy between [110] and [110] directions, which always occurs in low temperature molecular beam epitaxy (LT-MBE) grown (Ga,Mn)As samples. The reason is ascribed to the fact that the ultra-fastrecrystallization induced by pulsed laser melting weakens the formation of Mn-Mn dimers along the [100] direction which occurs in LT-MBE grown (Ga,Mn)As. Then selected samples were co-doped with Zn or irradiated with He ions. The Zn co-doping leads to the increase of conductivity of (Ga,Mn)P, however both the Curie temperature and magnetization decrease, which is probably due to the suppression of active Mn substitution by Zn co-doping. By using Rutherford Backscattering Spectroscopy and Particle-Induced X-ray Emission, the substitutional Mn atoms in (Ga,Mn)As are observed to shift to interstitial sites, while more Zn atoms occupy Ga sites. This is consistent with first-principles calculations, showing that the formation energy of substitutional Zn and interstitial Mn is 0.7 eV lower than that of interstitial Zn and substitutional Mn. For ion irradiated (Ga,Mn)As, (In,Mn)As and (Ga,Mn)P, both Curie temperature and magnetization decrease due to the hole compensation. However, the compensation effect is the strongest in (In,Mn)As and the least in (Ga,Mn)P. This is due to the different energy level of the produced defect relative to the band edges in different semiconductors. The results in the thesis point to an important issue: the difference in the band alignment and the hole binding energy of Mn dopants in different III-Mn-V dilute ferromagnetic semiconductors have strong influence on their magnetic properties and should be taken into account in the material design.

Loeffler, Bernd Matthias Nikolaus Untersuchungen zur Pharmakokinetik von Coffein, Theophyllin und Theobromin beim Hund nach Aufnahme von Kaffee, Tee und Schokolade aus dem Institut für Pharmakologie, Pharmazie und Toxikologie der Veterinärmedizinischen Fakultät der Universität Leipzig Leipzig im April 2000 (83 S., 24 Abb., 12 Tab., 187 Lit.) Methylxanthine stimulieren das zentrale Nervensystem, das Herz-Kreislauf-System und führen zur Bronchodilatation. Die Ergebnisse der Dopinguntersuchungen im Windhundrennsport zeigen, daß die Methylxanthine wie Coffein, Theophyllin und Theobromin nicht nur therapeutisch, sondern auch mißbräuchlich zur Leistungssteigerung eingesetzt werden. In der vorliegenden Studie wurde die Pharmakokinetik von Coffein, Theophyllin und Theobromin bei Hunden untersucht. Speziell in Hinblick auf die Dopingproblematik im Windhundsport wurden bei den Hunden zusätzlich Plasma- und Harnproben nach Applikation von Kaffee, Tee und Schokolade analysiert. Nach oraler Applikation von Coffein und Theophyllin (10 mg/kg KM) wurden im Plasma mittlere Konzentrationsmaxima an Coffein von 61,8 µmol/l und an Theophyllin von 42,5 µmol/l nach 1,6 bzw. 4,8 Stunden erreicht. Die Elimination erfolgte jeweils mit einer Halbwertszeit von etwa 3 Stunden. Im Urin konnten die applizierten Methylxanthine ebenfalls nachgewiesen werden, nach Applikation von Coffein war Theobromin als Metabolit in hohen Konzentrationen nachweisbar. Nach Aufnahme von Kaffee und Tee durch Hunde konnte in Plasma und Urin Coffein, Theophyllin und Theobromin nachgewiesen werden. Nach Verfütterung von Schokolade wurde im Wesentlichen nur Theobromin gefunden, so daß aus dem Metabolitenmuster der Methylxanthine zum Teil auf das aufgenommene Nahrungsmittel geschlossen werden kann. Um nicht in Konflikt mit geltenden Dopingbestimmungen zu kommen, sollten Hundehalter darauf achten, daß ihre Tiere in den Tagen vor einem Rennen keinen Zugang zu methylxanthinhaltigen Produkten wie Kaffee, Tee und Schokolade haben. / Loeffler, Bernd Matthias Nikolaus Investigations of the pharmacokinetics of caffeine, theophylline and theobromine in the dog. Institute of Pharmacology, Pharmacy and Toxicology of the Veterinary Faculty of the University of Leipzig Leipzig, April 2000 (83 p., 24 fig., 12 tab., 187 ref.) Methylxanthines are often used as stimulants of the central nervous system, of the cardiovascular system and as bronchodilators. Doping samples of racing greyhounds demonstrate that methylxanthines like caffeine, theophylline, and theobromine besides their therapeutic use, are illegally used to strengthen the animals. In this study the pharmacokinetics of caffeine, theophylline and theobromine in dogs were examined. Additionally samples of plasma and urine were taken after application of coffee, tea, and chocolate. After oral application of caffeine and theophylline (10 mg/kg) highest plasma concentrations of caffeine were about 61.8 µmol/l and of theophylline about 42.5 µmol/l after 1.6 and 4.8 hours, respectively. The elimination half-lives for both methylxanthines were 3 hours. The methylxanthines administered could also be detected in the urine, after application of caffeine its metabolite theobromine reached high concentrations. After the administration of coffee and tea to dogs caffeine, theophylline and theobromine can be found in plasma and urine. After the feeding of cocoa products (chocolate) theobromine was the predominant methylxanthine to be analysed. Therefore the quantitative relationship of the various methylxanthine metabolites detected can indicate the origin of the ingested methylxanthines. In order to avoid violation of doping regulations, dog owners should assure that their animals have no access to methylxanthine-containing diets in the days before racing competitions.

Chemical bath deposition (CBD) is the analog in liquid phase of the well-known chemical vapor deposition technique in the vapor phase. In CBD, deposition of thin films takes place from aqueous solutions at low temperatures by a chemical reaction between dissolved precursors, with the help of a complexing agent. Among all techniques used to grow Group II-VI semiconductors, CBD has the advantage of being a simple, low temperature, and inexpensive large-area deposition technique. So far, its contribution in thin film solar cells industry has been mainly limited to growing n-type CdS and/or ZnS window layers for CdTe-based and CIGS-based solar cells. In this work we first optimize the CBD process of CdS using nitrilotriacetic acid and hydrazine as complexing agents as an alternative to ammonia. We then study the effect of the cadmium precursor on the optical/electrical properties, as well as crystal structure, morphology, and composition of CBD-CdS films. A better understanding of the CBD process of CdS as a whole has been achieved and high quality CBD-CdS films have been obtained. Next, we investigate in-situ doping of CBD-CdS with group III elements, such as B, Al, In, and Ga. The objective is to show that CBD is capable of not only growing CdS but also of doping it to reduce its resistivity and, as a result, facilitate its use in solar cells as well as other optoelectronic device fabrication. A four orders of magnitude drop of film resistivity has been achieved without a significant change in film bandgap, structure, or morphology. Finally, we test the possibility of using CBD to grow transparent conducting oxide (TCO) films, such as Al-doped ZnO films and cadmium stannate films. First, we study CBD of ZnO and later in-situ doping of ZnO using Al. High quality ZnO thin films have been grown using CBD with the help of four different complexing agents. Post heat treatment in argon ambient helped reduce resistivity of CBD-ZnO undoped films to ~ 10-1 Ω-cm. In-situ doping of such films using Al shows promising results. Such films could be an alternative to indium tin oxide (ITO) layers that are commonly used as TCO layers for solar cells. Another approach is to use CBD to grow CdO and SnO2 thin films, with the goal of obtaining Cd2SnO4 by later annealing of these two layers. Cadmium stannate is another TCO candidate that could replace ITO in the near future. We have succeeded in growing CBD-CdO thin films using three different complexing agents. Undoped CBD-CdO films with a resistivity as low as 1.01 x10-2 Ω-cm and a carrier density as high as 2.59 x 1020 cm-3 have been obtained. SnO2 films have been successfully grown using CBD. Fabrication of Cadmium stannate thin films using CBD is investigated. In summary, our objective to expand the use of CBD beyond just growing CdS and ZnS, and to test the possibility of using it for in-situ doping of group II-VI semiconductors as well as TCO layers fabrication proved to be successful. We believe that this may have a significant impact on solar cells as well as other optoelectronic devices fabrication industry, due to the simplicity and the cost-effectiveness of CBD.

Das Gesetz gegen Doping im Sport ist das Ergebnis eines jahrelangen rechtspolitischen Ringens. Umstritten waren vor allem die Einführung eines strafbewehrten Verbots des Selbstdopings sowie das Verhältnis von staatlichem Straf- und dem Recht der Sportverbände. Fünf Jahre nach Inkrafttreten haben die Verfasser das Gesetz im Auftrag der Bundesregierung evaluiert. Das Werk zeigt anhand von Fallstudien und Interviews die Stärken und Schwächen des international vorbildgebenden Gesetzes gegen Doping im Sport. Damit dient es sowohl dem Verständnis der nationalen Rechtspraxis als auch der Orientierung nationaler und internationaler Gesetzgeber und Sportverbände. / The act against doping in sport stands at the end of an intensive legal discussion. The main points of contention were the introduction of a punishable ban on self-doping and the relationship between national criminal law and the law governing sports associations. Five years after the act came into force, the authors undertook an evaluation of its provisions and its practical application on behalf of the German Federal Government. The book uses case studies and interviews to illustrate the strengths and weaknesses of the act against doping in sport. In this way, the book serves both to understand national legal practice and to provide guidance for legislators and sports associations.

Doping violates the Spirit of Sport and is thought to contradict the values which underpin this spirit. Values-based education (VBE) has been cited as a key element for creating a clean sport culture across age groups. Culturally relevant VBE requires understanding of the values that motivate athletes from different countries to practice their sport and uphold clean sport values. WADA's new International Standards for Education makes this study both needed and timely. Overall, 1,225 athletes from Germany, Greece, Italy, Russia, and the UK responded to measures assessing their general values, Spirit of Sport values, and their perceived importance of “clean sport”. MaxDiff analysis identified the most important values to participants based on their respective country of residence. Correlation analysis was conducted to assess the relationship between importance of clean sport and Spirit of Sport values. There were significant differences between participant nationality and their perceived importance of clean sport [F(4, 1,204) = 797.060, p < 0.000], the most important general values (p < 0.05), and Spirit of Sport values (p < 0.05). Moderate positive correlations were observed between the perceived importance of clean sport and honesty and ethics (r = 0.538, p < 0.005) and respecting the rules of sport (r = 0.507, p < 0.005). When designing the values-based component of anti-doping education programs, athletes' different value-priorities across countries should be considered.

Structurally precision graphene nanoribbons (GNRs) have attracted great interest considering their prospective applications as organic carbon materials for nanoelectronics. The electronic properties of GNRs not only critically depend on the edge structure and width but also on the heteroatom type, doping position, and concentration. Motivated by the recent undisputable progress in the synthesis of stable boron-doped polycyclic aromatic hydrocarbons (B-PAHs), considerable efforts have been devoted to the precision synthesis of the corresponding boron-doped GNRs (B-GNRs) via bottom-up synthesis approach in recent years in view of the extraordinary ability of boron doping on modulating their physiochemical properties. In this review, an overview of the bottom-up organic synthesis of B-GNRs, including the precursor design and synthesis, structure characterization of the resulting B-GNRs, and investigation of their electronic properties is provided. Moreover, the future challenges and perspectives regarding the bottom-up synthesis of B-GNRs are also discussed. The authors hope that this review will further stimulate the synthesis and device integrations of B-GNRs with a combined effort from different disciplines.