The main subject of this thesis is the study of electronic and magnetic properties of materials containing 3d transition metal atoms. Our motivation stems mainly from the modern fields of spintronic computing and solar energy conversion. The two primary goals of this work are to determine (i) why certain transition metal impurities in certain semiconductors can induce magnetic properties suitable for spintronic computing applications, and (ii) how transition metal impurities can be used to modify the electronic band gaps of semiconductors and insulators in ways useful for harnessing solar energy and for other applications. To accomplish these goals, we have applied both experimental and theoretical tools. We studied high quality materials prepared by advanced synthesis techniques using x-ray spectroscopy methods at synchrotron light sources. The results of these experiments were interpreted using a variety of theoretical techniques, primarily using computational software developed as part of this thesis and discussed herein. Regarding the study of introducing transition metal impurities into semiconductors to induce magnetic properties, we first developed and demonstrated a method to determine the location of impurity atoms within the host semiconductor lattice. This allowed to us explain the presence and absence of ferromagnetism in samples prepared under only slightly different synthesis conditions, which helped to address some long--standing issues in the spintronics field. We then studied an advanced and promising material -- indium (III) oxide with iron impurities -- to determine how magnetic ordering was maintained up to room temperatures. Our techniques unveiled that a portion of the iron atoms were coupled to oxygen vacancies in the material to create conditions which propelled the observed magnetism. This finding confirmed some earlier theoretical predictions by others in the field. For the study of electronic band gap modifications in semiconductors and insulators via the incorporation of transition metal atoms, we investigated a wide range of materials synthesized using different techniques. Again, we used experimental techniques to determine the location of impurity atoms within the materials, and used this to understand how band gaps were modified upon the introduction of the impurities. For Ti implantation into SiO2, Ni substitution into ZnO, and a new material, MnNCN, we have determined the electronic band gaps and used our techniques to explain how the values for the gaps arise. Finally, an additional outcome of this thesis work is a software program capable of simulating x-ray spectra using various advanced quantum models. We rewrote and built upon powerful existing programs and applied the result to the above studies. Our software was further applied in a collaborative effort with other researchers at the Canadian Light Source to study the differences in two experimental techniques for measuring x-ray absorption: partial and inverse partial fluorescence yields. By using the proper absorption and scattering formalisms to simulate each technique, we were able to explain the differences between the experimental spectra obtained from each. We explain fluorescence yield deviations using an analysis based on the spin configuration of different states, suggesting that the technique can be further extended as a quantitative spin state probe. These results could have significant implications for the field of soft x-ray absorption spectroscopy.

abstract: Nanowires (NWs) have attracted many interests due to their advance in synthesis and their unique structural, electrical and optical properties. NWs have been realized as promising candidates for future photonic platforms. In this work, erbium chloride silicate (ECS), CdS and CdSSe NWs growth by vapor-liquid-solid mechanism and their characterization were demonstrated. In the ECS NWs part, systematic experiments were performed to investigate the relation between growth temperature and NWs structure. Scanning electron microscopy, Raman spectroscopy, X-ray diffraction and photoluminescence characterization were used to study the NWs morphology, crystal quality and optical properties. At low growth temperature, there was strong Si Raman signal observed indicating ECS NWs have Si core. At high growth temperature, the excess Si signal was disappeared and the NWs showed better crystal quality and optical properties. The growth temperature is the key parameter that will induce the transition from Si/ECS core-shell NWs structure to solid ECS NWs. With the merits of high Er concentration and long PL lifetime, ECS NWs can serve as optical gain material with emission at 1.5 μm for communications and amplifiers. In the CdS, CdSSe NWs part, the band gap engineering of CdSSe NWs with spatial composition tuning along single NWs were demonstrated. The first step of realizing CdSSe NWs was the controlled growth of CdS NWs. It showed that overall pressure would largely affect the lengths of the CdS NWs. NWs with longer length can be obtained at higher pressure. Then, based on CdS NWs growth and by adding CdSe step by step, composition graded CdSSe alloy NWs were successfully synthesized. The temperature control over the source vapor concentration plays the key role for the growth. / Dissertation/Thesis / M.S. Electrical Engineering 2012

Philosophiae Doctor - PhD / The main aim of this study was to prepare band gap-engineered graphene quantum dot (GQD) structures which match the different energies of the visible region in the solar spectrum. These band gap-engineered graphene quantum dot structures were used as donor materials in rainbow Schottky junction solar cells, targeting all the energies in the visible region of the solar spectrum for improved solar-to-electricity power conversion efficiency. Structural characterisation of the prepared nanomaterials under solid-state nuclear magnetic resonance spectroscopy (SS-NMR) showed appearance of bands at 40 ppm due to the presence of sp3 hybridised carbon atoms from the peripheral region of the GQD structures. Other bands were observed at 130 ppm due to the presence of polycyclic aromatic carbon atoms from the benzene rings of the GQD backbone, and around 180 ppm due to the presence of carboxylic acid carbons from oxidation due to moisture. Fourier-transform infrared resonance (FTIR) spectroscopy further confirmed the presence of aromatic carbon atoms and oxidised carbons due to the presence of C=O, C=C and -OH functional groups, concurrent with SS-NMR results. / 2023-12-01

Monolayer molybdenum disulfide (MoS2) is a three-atom-thick direct band gap semiconductor, which has received considerable attention for use as a channel material in atomically thin transistors, photodetectors, excitonic LED’s, and many other potential applications. It is also a mechanically exceptional material with a large stiffness and flexibility, and can withstand very large strains (11%) before rupture. In this dissertation we investigated the mechanics of the stiffness and adhesion forces in atomically thin MoS2 membranes, and how biaxial strains can be used to induce large modulations in the band structure of the material. First, we used chemical vapor deposition (CVD) to grow MoS2 crystals that are highly impermeable to gas, and used a pressure difference across suspended membranes to induce large biaxial strains. We demonstrated the continuous and reversible tuning of the optical band gap of suspended monolayer membranes by as much as 500 meV, and induced strains of as much as 5.6% before rupture. We observed the effect of strain on the energy and intensity of the peaks in the photoluminescence (PL) and Raman spectra and found their linear strain tuning rates, then report evidence for the strain tuning of higher level optical transitions. Second, we determined the Young’s modulus and works of separation and adhesion of MoS2 membranes, and found that adhesion hysteresis is an important effect in determining the behavior of our systems. Finally, we investigated the use of atomically thin materials as nanofiltration membranes, by perforating the material with nanopores which selectively permit the transport of smaller molecules while rejecting larger ones. We studied ion transport through nanopores in graphene membranes and demonstrate that in-situ atomic force microscope measurements in liquid are a powerful way to reveal occlusions and contaminants around the pores - work which will aid future researchers in further unveiling the properties of these fascinating systems.

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第20460号 / 人博第810号 / 新制||人||194(附属図書館) / 28||人博||810(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 田部 勢津久, 教授 加藤 立久, 教授 吉田 寿雄 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

This investigation examines band gap engineering of the GaAsN alloy by means of plasma ion implantation. The strong redshift of the alloy's band gap is suitable for telecommunication applications and thus stimulated much interest in recent years. Nitrogen (N) ion implantation into gallium arsenide (GaAs) results in a thin shallow N-rich layer below the surface. However, the violent implantation process also modifies the concentrations of gallium and arsenide. The core of this thesis is a novel method for prediction of the band gap from the conditions in the processing plasma.<p>The first important variable, the number of implanted ions, is obtained from the Lieberman model for the current during high-voltage Plasma Ion Implantation (PII). A review of the model's assumptions is provided as well as a comprehensive discussion of the implantation which includes error boundaries. The predicted and measured ion currents agree within error boundaries. The number of implanted ions can therefore be obtained from the prediction.<p>The distribution of the implanted ions was subsequently explored by simulations such as TRIM and TRIDYN. It was found that the nitrogen content in GaAs is limited by the sputtering of the surface atoms. Furthermore, the content of gallium increases near the surface while the content of arsenic decreases. The predicted ratios of the constituents in the implanted layer is such that the alloy cannot form by ion implantation alone; it could be reconciled by annealing.<p>Preliminary samples were produced and tested for the formation of the GaAsN alloy by Raman spectroscopy. No evidence for bonds between N and either Ga or As was found in the as-implanted samples. The thesis concludes with a discussion of the necessary steps to synthesize the GaAsN alloy.

This investigation examines band gap engineering of the GaAsN alloy by means of plasma ion implantation. The strong redshift of the alloy's band gap is suitable for telecommunication applications and thus stimulated much interest in recent years. Nitrogen (N) ion implantation into gallium arsenide (GaAs) results in a thin shallow N-rich layer below the surface. However, the violent implantation process also modifies the concentrations of gallium and arsenide. The core of this thesis is a novel method for prediction of the band gap from the conditions in the processing plasma.<p>The first important variable, the number of implanted ions, is obtained from the Lieberman model for the current during high-voltage Plasma Ion Implantation (PII). A review of the model's assumptions is provided as well as a comprehensive discussion of the implantation which includes error boundaries. The predicted and measured ion currents agree within error boundaries. The number of implanted ions can therefore be obtained from the prediction.<p>The distribution of the implanted ions was subsequently explored by simulations such as TRIM and TRIDYN. It was found that the nitrogen content in GaAs is limited by the sputtering of the surface atoms. Furthermore, the content of gallium increases near the surface while the content of arsenic decreases. The predicted ratios of the constituents in the implanted layer is such that the alloy cannot form by ion implantation alone; it could be reconciled by annealing.<p>Preliminary samples were produced and tested for the formation of the GaAsN alloy by Raman spectroscopy. No evidence for bonds between N and either Ga or As was found in the as-implanted samples. The thesis concludes with a discussion of the necessary steps to synthesize the GaAsN alloy.

Solarzellen auf Basis von hybriden Perowskiten, wie zum Beispiel Methylammoniumbleitriiodid (CH3NH3PbI3), stellen eine der vielversprechendsten Solarzellenkonzepte dar. Dabei wurden Wirkungsgrade über 20 % gezeigt. Perowskite werden durch verschiedene lösungsbasierte Techniken abgeschieden. Daher konzentriert sich der erste Teil dieser Dissertation auf die Bildung von hybriden Perowskiten in der Lösung, während der zweite Teil der Stabilität von hybriden Perowskiten gewidmet ist. Im ersten Teil, wird die Bildung von Polyiodidplumbaten aus PbI2 in Lösung nachgewiesen. Die Bildung dieser Polyiodidplumbate konnte unabhängig von dem gewählten Lösungsmittel sowie unabhängig von der Beigabe von Methylammoniumiodid (CH3NH3I) beobachtet werden. Die Polyiodidplumbate zeigten, ähnlich wie CH3NH3PbI3, ein Photolumineszenzmaximum bei einer Wellenlänge von 760 nm, was auf einen gemeinsamen Ursprung des angeregten Zustands in PbI2-Komplexen und CH3NH3PbI3 hindeutet. Im zweiten Teil wurden darüber hinaus die Lichtbeständigkeit sowie die thermische und kompositionelle Stabilität untersucht. Die Untersuchung der thermischen Stabilität hat gezeigt, dass Tempern bei T <190 °C zu einer Verbesserung der Morphologie und der optoelektronischen Eigenschaften führt. Oberhalb einer Temperatur von 190 °C kam es dabei zur Zersetzung des Materials. Die Stabilität der Komposition wurde anhand von CsPb(I[1-x]Br[x])3-Perowskiten untersucht. Die Herstellung von Perowskiten mit einer großen Bandlücke war zunächst nicht möglich, da es bei den dafür notwendigen Kompositionen (0,3<x<1) zur Phasentrennung kommt. Im Gegensatz dazu konnte durch den Zusatz von Ethylendiammoniumdiodid (EDDI) zu CH3NH3PbI3 die Bandlücke zwischen 1,6 und 1,8 eV variiert werden. Die Lichtstabilität von CH3NH3PbI3, CH(NH2)2PbI3 sowie gemischt Perowskiten wurde mittels in-situ Infrarotspektroskopie analysiert. Die Zersetzung des Materials war durch die lichtinduzierte Spaltung der N-H-Bindungen bei hv ≥ 2,72 eV gekennzeichnet. / Hybrid perovskites such as methylammonium lead iodide, CH3NH3PbI3, are one of the most promising absorber materials for photovoltaic energy conversion with demonstrated power conversion efficiencies beyond 20 %. In addition, hybrid perovskites can be deposited by various solution-based fabrication techniques. Therefore, the first part of this dissertation is focused on the formation of hybrid perovskites in the precursor solution, while the second part is dedicated to the study of the stability of hybrid perovskites. In the first part of this thesis, the formation of polyiodide plumbates between molecules of PbI2 was detected. Importantly, the formation of polyiodide plumbates was observed independently of the solvent choice or the presence of CH3NH3I. The polyiodide plumbates exhibited a photoluminescence peak located at 760 nm, similarly to CH3NH3PbI3, which suggests a common origin of the excited state in PbI2 complexes and CH3NH3PbI3. In the second part of this thesis, the thermal, compositional, and photostability of perovskite thin films were evaluated. The study of the thermal stability has shown that post-annealing at T < 190 °C leads to the improvement of morphology and optoelectronic properties. Above 190 °C, CH3NH3PbI3 was found to degrade. Next, the compositional stability of mixed CsPb(I[1-x]Br[x])3 perovskites was investigated. A fundamental miscibility gap between 0.3 < x <1 was demonstrated, that impedes the preparation of high band-gap perovskites. To overcome this intrinsic instability, a new approach for band-gap engineering was developed. An addition of ethylenediammonium diiodide (EDDI) allowed to alter the band gap of CH3NH3PbI3 from 1.6 to 1.8 eV. Finally, the influence of light on the stability of hybrid perovskites was studied. A degradation of CH3NH3PbI3, CH(NH2)2PbI3, as well as mixed perovskites, was observed through photo-dissociation of N-H bonds with hν ≥ 2.72 eV by means of in-situ Fourier-transform infrared spectroscopy.

This dissertation presents a comprehensive study of the intrinsic room temperature ferromagnetism, RTFM, in technologically important thin films of ZnO, MgO, Mg@ZnO, the so-called d0–magnets that do not contain any intrinsic magnetic elements. We also present the first report on magnetism in Mn doped MgO films fabricated by dc magnetron sputtering. We have just published (April 2013 ‘on-line’) a state of the art review entitled ‘p-type ZnO Theory, growth, properties, and devices’ in the prestigious journal ‘Progress in Materials Science’, summarizing the recent advances of the studies on p-type ZnO thin films and pointing out the major challenges that remain in the field. The experimental work then focuses on the magnetic properties of band gap engineered Mg@ZnO films exploiting the fact that by substitutional doping of Mg for Zn in ZnO it is possible to tailor new materials with bandgap energy in the range 3.3 eV to 7.2 eV, thus extending the possibilities for new magnetic and optical device applications. In addition, we show that by doping Mn in MgO its magnetic properties can be enhanced to saturation values as high as 38.5 emu/cm3 in a 92 nm thick film. These studies involve extensive characterization of the high quality films in the thickness range of nanometers, using SQUID magnetometer for magnetic properties, XRD for structural analysis, Dual beam HRSEM/FIB and AFM for accurate film cross-sectioning and surface morphology, EDXS for elemental analysis, UV-VIS NIR for measuring the band gap of MgxZn(1-x)O films, Mg K-edge NEXAFS experiment in order to understand electronic structure of specific cations present in the thin films The origin of the observed room temperature feerromaganetism is attributed to cation vacancies and its consequences on the polarization about these vacancies in the oxides... ZnO films are promising materials for optoelectronic device applications, and the fabrications of high quality p-type ZnO and p–n junction are the key steps to realize these applications. However, reliable p-type doping of the material remains a major challenge because of the self-compensation from native donor defects (VO and Zni) and/or hydrogen incorporation. Considerable efforts to obtain p-type ZnO by doping different elements with various techniques have resulted in remarkable progress in the field both from theoretical and experimental point of view. In our paper, we discuss p-type ZnO materials: theory, growth, properties and devices, comprehensively. We first discuss the native defects in ZnO. Among the native defects in ZnO, VZn and Oi act as acceptors. We then present the theory of p-type doping in ZnO, and summarize the growth techniques for p-type ZnO and the properties of p-type ZnO materials. Experimentally, besides the intrinsic p-type ZnO grown at O-rich ambient, p-type ZnO (MgZnO) materials have been prepared by various techniques using Group-I, IV and V elements. We pay a special attention to the band gap of p-type ZnO by band gap engineering and room temperature ferro magnetism observed in p-type ZnO. Finally, we summarize the devices based on p-type ZnO materials. In presenting the current studies, we first focus on the sputtering process in order to produce high quality films. From a comparative study of RTFM, in MgO films deposited by sputtering from 99.999% pure metallic Mg, Vs MgO targets respectively on glass/Si substrates under identical ambience during deposition it is found that the metallic targets give the best magnetic properties (e.g: with maximum Ms values of ~13.75 emu/g vs ~ 4.2 emu/g respectively on Si substrates.(supplement 2). Furthermore, the Ms values are strongly film thickness dependent with Mg target while it is weakly so for films from MgO target. Also, the as deposited MgO films using metallic Mg target are found to be amorphous, while it is nanocrystalline when the films are sputtered off MgO targets. The overall Ms values are found to be dependent on the oxygen content in the atmosphere during deposition, increasing to 2.69 emu/g at a oxygen partial pressure of 40% of the total working gas pressure. On annealing to nanocrystallize these films in the temperature range 600 to 8000C strong XRD peaks corresponding to (200) orientation are observed, and Ms values decrease proportionately. (supplement 3). With the above information on studies for optimizing the effect of sputtering gas, film thickness, and oxygen partial pressure, PO2, comprehensive investigations on band gap engineering and magnetism in MgxZn(1-x)O co-sputtered thin films from Mg and Zn targets are then closely examined. The optical band gap calculated from absorption spectra shows that the band gaps of Mg-doped ZnO thin films increased linearly from 3.33 to 4.074 eV. Our studies indicate that both the magnetic properties and the band gap of the film can be tailored by tuning the film thickness and PO2 in the working gas. In summary, RTFM ordering in the thin films originates from cation vacancies which couple ferromagnetically and establish long range magnetic order. The ferromagnetic ordering in these materials is shown to arise from defects situated at the cation sites. Electronic structure studies of some selected films disclose that the unoccupied O 2p states exist and this unoccupied state results from cation vacancy (VMg). / <p>QC 20130524</p>