Organic-inorganic hybrid perovskites (OIHPs), which are promising materials for electronic and optoelectronic applications (1-10), have made into layered organic-inorganic hybrid perovskites (LOIHPs). These LOIHPs have been applied to thin-film transistors, solar cells and tunable wavelength phosphors (11-18). It is known that devices fabricated with single crystal exhibit the superior performance, which makes the growth of large-sized single crystals critical for future device applications (19-23). However, the difficulty in growing large-sized LOIHPs single crystal with superior electrical properties limits their practical applications. Here, we report a method to grow the centimeter-scaled LOIHP single crystal of [(HOC2H4NH3)2PbI4], demonstrating the potentials in mass production. After that, we reveal anisotropic electrical and optoelectronic properties which proved the carrier propagating along inorganic framework. The carrier mobility of in-inorganic-plane (in-plane) devices shows the average value of 45 cm2 V–1 s–1 which is about 100 times greater than the record of LOIHP devices (15), showing the importance of single crystal in device application. Moreover, the LOIHP single crystals show its ultra-short carrier lifetime of 42.7 ps and photoluminescence quantum efficiency (PLQE) of 25.4 %. We expect this report to be a start of LOIHPs for advanced applications in which the anisotropic properties are needed (24-25), and meets the demand of high-speed applications and fast-response applications.

As the internet-of-things hardware integration continues to develop and the requirements for electronics keep diversifying and expanding, the necessity for specialized properties other than the classical semiconductor performance becomes apparent. The success of emerging semiconductor materials depends on the manufacturability and cost as much as on the properties and performance they offer. Solution-based semiconductors are an emerging concept that offers the advantage of being compatible with large-scale manufacturing techniques and have the potential to yield high-quality electronic devices at a lower cost than currently available solutions. In this work, patterns of high-quality MAPbBr3 perovskite single crystals in specific locations are achieved through the modification of the substrate properties and solvent engineering. The fabrication of the substrates involved modifying the surface adhesion forces through functionalization with self-assembled monolayers and patterning them by photolithography processes. Spin coating and blade coating were used to deposit the perovskite solution on the modified silicon substrates. While single crystal perovskites were obtained with the modification of substrates alone, solvent engineering helped with improving the Marangoni flows in the deposited droplets by increasing the contact angle and lowering the evaporation rate, therefore controlling and improving the shape of the grown perovskite crystals. The methodology is extended to other types of perovskites such as the transparent MAPbCl3 and the lead-free MABi2I9, demonstrating the adaptability of the process. Adapting the process to electrode arrays opened up the path towards the fabrication of optoelectronic devices including photodetectors and field-effect transistors, for which the first iterations are demonstrated. Overall, manufacturing and integration techniques permitting the fabrication of single crystalline devices, such as the method in this thesis work, are fundamental in pushing hybrid perovskites towards commercialization.

Metal-Organic Frameworks (MOFs) represent an emerging new class of functional crystalline solid-state materials. In the early discovery of this now rapidly growing class of materials significant challenges were often encountered. However, MOFs today, with its vast structural modularity, reflected by the huge library of the available chemical building blocks, and exceptional controlled porosity, stand as the most promising candidate to address many of the overbearing societal challenges pertaining to energy and environmental sustainability. A variety of design strategies have been enumerated in the literature which rely on the use of predesigned building blocks paving the way towards potentially more predictable structures. The two major design strategies presented in this work are the molecular building block (MBB) and supermolecular building block (SBB) -based approaches for the rationale assembly of functional MOF materials with the desired structural features. In this context, we targeted two highly connected MOF platforms, namely rht-MOF and shp-MOF. These two MOF platforms are classified based on their topology, defined as the underlying connectivity of their respective net, as edge transitive binodal nets; shp being (4,12)-connected net and rht being (3,24)-connected net. These highly connected nets were deliberately targeted due to the limited number of possible nets for connecting their associated basic building units. Two highly porous materials were designed and successfully constructed; namely Y-shp-MOF-5 and rht-MOF-10. The Y-shp-MOF-5 features a phenomenal water stability with an exquisite behavior when exposed to water, positioning this microporous material as the best adsorbent for moisture control applications. The shp-MOF platform proved to be modular to ligand functionalization and thus imparting significant behavioral changes when hydrophilic and hydrophobic functionalized ligands were introduced on the resultant MOF. On the other hand, rht-MOF-10 constituting of 24-connected transition metal based-SBB was successfully synthesized and activated using a modified supercritical CO2 drying technique. This allowed access to over 90 % of the total pore volume (1.95cm3/g). High pressure gas sorption measurements of CH4, CO2 and O2 showed that this material has a gravimetric uptake that ranks close to the best materials enlisted for the storage of these corresponding gases.

Halide perovskites have recently emerged as the state-of-the-art semiconductors with the unique combination of outstanding optoelectronic properties and facile solution synthesis. Within only a decade of research, they have witnessed a remarkable success in photovoltaics and shown great potential for applications in light-emitting devices, photodetectors, and high-energy sensors. Yet, the majority of current perovskite-based devices still rely on polycrystalline thin films which, as will be discussed in Chapter 2, exhibit inferior charge transport characteristics and increased tendency to chemical degradation compared to their single-crystalline analogues. In this regard, unburdened from the effects of grain boundaries, single crystals demonstrate the upper limits of semiconductor performance. Their study is, thus, important from both fundamental and practical aspects, which present the major objectives of this dissertation. In Chapter 3, we study the intrinsic charge transport and recombination characteristics of single crystals of formamidinium lead halide perovskites. While, in Chapter 4, we investigate the mechanistic origins of rapid synthesis of halide perovskite single crystals by inverse temperature crystallization. Understanding the nucleation and growth mechanisms of halide perovskites enables us to design strategies toward integrating their single crystals into device applications. Namely, in Chapters 5 and 6, we demonstrate crystal engineering approaches for tailoring the thicknesses and facets of halide perovskite single crystals to make them suitable for, respectively, vertical and planar architecture optoelectronic devices. The findings of this dissertation are expected to benefit future studies on fundamental characterization of halide perovskites, as well as motivate researchers to develop perovskite-based optoelectronic devices with better crystallinity, performance and stability.

A strategy based on reticulating metal ions and organic ligands into atomically precise gold and silver nanoclusters (NCs) with high monodispersity has been advanced to a point that allows the design of NCs with strict stoichiometries, functionalities and valence. Of the Ag NCs discovered, Ag44 is the most studied, not only due to its high absorption that transcends the visible spectrum suitable for photovoltaics but also because of its long excited state lifetime, as revealed by nanosecond transient absorption spectroscopy. A major principle discovered in this dissertation is the ability to produce Ag44 in scalable amounts and with high stability in addition to modulation of the functional groups of the organic ligands via a fast and complete ligand exchange process. This new discovery has led to the development of synthetic designs in which new sizes were obtained by varying the reaction parameters (e.g., ligands functionality, reaction temperature and time), namely, Ag29 using dithiols and phosphines. The synthesized NCs possess tetravalent functionalities that facilitate their crystallization and characterization. Furthermore, Ag29 glows red and is therefore a possible candidate for sensing and imaging applications.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19311号 / 工博第4108号 / 新制||工||1633(附属図書館) / 32313 / 京都大学大学院工学研究科電子工学専攻 / (主査)教授 川上 養一, 教授 髙岡 義寛, 教授 藤田 静雄 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Metal halide perovskite semiconductors offers bright future for optoelectronic applications due to their excellent optical and electrical properties and their low-cost solution-based facile fabrication. The most of the perovskite application are based on the defective polycrystalline films and they offer inadequate moisture/thermal chemical stability. Therefore, this dissertation is dedicated to find new strategies to deploy the single-crystal perovskites to photovoltaics and new methods to reduce the moisture/thermal instability of inorganic perovskite light-emitters. In first part of this dissertation, we aimed to reveal the potential of the single crystal in photovoltaics. Single-crystal semiconductors can outperforms their polycrystalline forms in terms of photovoltaic performance due to their better structural quality and less electronic traps. However, the most efficient perovskite solar cells are based on polycrystalline films. While single crystals can perform beyond the limits of polycrystalline films, their synthesis and device integration are complex. Therefore, we aimed to create new synthetic methods to unveil the potential of the single-crystal perovskites in photovoltaics. We developed new strategies leading the perovskite single crystals to go beyond 20% power conversion efficiency in Chapter 2. Also fundamental limits of the perovskite single crystals are investigated in Chapter 3 by fabricating single crystal cells with varying thicknesses, and the electron diffusion length is calculated to be 520 μm. In Chapter 4, we propose surface modification and compositional engineering techniques to bring the perovskite single crystal photovoltaic one step beyond of the previous point by reaching 21.9% and 22.8% efficiencies, respectively. In the second part of this dissertation (Chapter 5), a novel synthetic method is offered to achieve highly stable light-emitting perovskite-related materials since the fast degradation of perovskites in the presence of water and moisture is a challenge for perovskite-based technologies and hinders the material’s potential. We demonstrated that these a direct transformation of 3D CsPbBr3 films to CsPb2Br5 exhibiting excellent stability against humidity and heat while keeping the high photoluminescence quantum yield. We believe the strategies offered in this dissertation will open an avenue in photovoltaic and light emitting applications, and can be utilized in new optoelectronic applications in future.

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<p> The properties and device applications of silicon thin films vacuum evaporated both onto single crystal silicon and onto silicon dioxide substrates have been investigated. </p> <p> The feasibility of obtaining device quality homoepitaxial silicon thin films by vacuum evaporation onto non heat-treated substrates having temperatures of 700°C has been demonstrated. A new technique, that of gas-doping, has been developed and has been shown to be capable of reproducibly introducing controlled concentrations of doping impurities in the range applicable to device fabrication into the deposited layers. The combined deposition-doping technique has been employed in the production of silicon layers containing impurity steps more abrupt than may be obtained by conventional fabrication techniques. </p> <p> The electrical properties of the vacuum evaporated homoepitaxial silicon layers have been shown to be comparable in most respects to those of bulk high purity single crystal silicon. The characteristics of rectifying and of varactor diodes prepared by the technique of vacuum evaporation combined with gas doping have been considered. </p> <p> Silicon films evaporated onto Si02 substrates have been shown to possess structures ranging from amorphous through randomly oriented polycrystalline to oriented polycrystalline as the substrate temperature is increased from 25°C to 850°C. The electrical characteristics of doped polycrystalline films obtained both by vacuum evaporation combined with gas doping and by the diffusion-annealing of amorphous films have been shown to be comparable with those reported for similar material deposited by chemical techniques. The experimentally observed properties of the disordered material have been qualitatively explained employing an inhomogeneous film model. The suitability of thin films of doped polycrystalline silicon on sio2 substrates for the production of high value resistors for monolithic integrated circuits has been considered. </p> / Thesis / Doctor of Philosophy (PhD)

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