Yes / Physical properties of scaffolds such as nanofibers and aligned structures have been reported to exert profound effects on the growth and differentiation of stem cells due to their homing-effect features and contact guidance. However, the biological function of aligned nanofiber utilized as bone-scaffold has not been rigorously characterized. In the present study, aligned electrospun cellulose/CNCs nanocomposite nanofibers (ECCNNs) loaded with bone morphogenic protein-2 (BMP-2) were used for the first time to investigate (1) in vitro osteogenic differentiation of human mesenchymal stem cells (BMSCs) and (2) in vivo collagen assembly direction and cortical bone regeneration. Aligned ECCNNs scaffolds loaded with BMP-2 possess good biological compatibility. The growth orientation of BMSCs followed the underlying aligned nanofibers morphology, accompanied with increased alizarin red stain, ALP activity and calcium content in vitro while, a rabbit calvaria bone defect model was used in an in vivo study. / This work was supported by Natural Science Foundation of China (NSFC) grants (31500789, 51433006, 51473100, 81870758 and 31871464), Chongqing Yuzhong District science and technology plan project grants (20170124), Chongqing Research Program of Basic Research and Frontier Technology (cstc2018jcyjAX0807, cstc2017jcyjBX0019 and cstc2017jcyjAX0020), Temple University Kornberg School of Dentistry research start-up funds, the RCUK China-UK Science Bridges Program through the Medical Research Council and the Engineering and Physical Sciences Research Council and Program for Innovation Team 1015 Building at Institutions of Higher Education (No. 1016 CXTDG201602006) funded by the Chongqing Municipal 1017 Education Commission of China in 2016

Synthetic plastics are intrinsic to modern human existence. Unfortunately, many challenges exist related to the accumulation of plastic waste, including greenhouse gas emissions, contamination of natural environments, and entrance into the food chain through microplastics. Therefore, new polymers are being developed that both compete with the capabilities and costs of petroleum-based plastics and have assured biodegradability. Through decades of research, plant oils have emerged as one of the leading options for alternative starting materials because of their feasibility for use in polymerization reactions, wide availability, renewability, and cost-effectiveness. In this work, cottonseed oil (CSO) and soybean oil (SBO) are successfully utilized to synthesize polymers with a range of promising properties. A nanocomposite was produced by incorporating cellulose nanocrystals (CNCs) into an epoxidized CSO (ECSO) polymer matrix. A significant improvement in properties such as tensile stiffness and strength, without any substantial decrease in extensibility or thermal integrity has been observed. This demonstrated that CNCs can be used to tune the CSO- based polymer properties. Enzymes are excellent alternatives to traditional catalysts as they eliminate the necessity of elevated reaction temperatures and pressures. Epoxidized SBO (ESBO) was polymerized using immobilized candida antarctica lipase B (Novozyme N435). The resulting polymer was inhomogeneous, with soluble waxy and insoluble solid components. Analyses of the soluble component indicated the formation of a multi-branched polymer, showing that a greener system may be used to produce ESBO-based polymers. It is necessary to test the biodegradability of biobased polymers to confirm their validity as alternatives to traditional plastics. Degradation of the CNC-incorporated CSO-based network polymer was characterized by submersing specimens into various aqueous media, including artificial seawater and saltwater, to simulate realistic end-of-use scenarios. Decomposition occurred due to hydrolysis of the many ester linkages within the polymer structure. The presence of CNCs appeared to enhance the rate of degradation. Overall, the hydrolytic susceptibility of the CSO-based network polymer was observed as enhanced by incorporating CNCs. In summary, this work demonstrates the viability of using plant oils and CNCs to produce biodegradable polymers with a range of properties, thus aiding in the effort to replace traditional plastics.

Chalcogenide perovskites with a distorted ABX3 structure (A: Ca, Ba, Sr; B: Zr, Hf; X: S, Se) are a prominent focus in optoelectronic materials. One of these is BaZrS3 which has garnered significant attention in perovskite materials due to its distinctive distorted perovskite structure and valuable optical properties that are viable for a single-junction solar cell and present a compelling option for tandem solar cell configurations. Another promising material is SrZrS3 which exists in two phases: needle-like non-perovskite α-SrZrS3 and distorted perovskite β-SrZrS3. The distorted perovskite phase shows promising luminescence properties in bulk, making it potentially viable for LED applications. In this work, we show that the non-perovskite α-SrZrS3 was accessed through colloidal synthesis at 330 °C and 365 °C by increasing concentrations of precursors. In order to favor the perovskite phase, we conducted alloying experiments incorporating varying percentages of doped Sr2+ into BaZrS3 to first synthesize a distorted perovskite Ba(1-x)SrxZrS3. Through varying percentages and varying reaction conditions such as temperature, time of reaction, and doping concentrations, we aim to optimize the synthesis of colloidal Ba(1-x)SrxZrS3 nanocrystals.

This thesis explores how the carrier dynamics within semiconductor nanocrystals can be directly engineered through specific core-shell design. Emphasis is placed on how material characteristics, such as strain or alloying at a core-shell interface, can influence the exciton energies and the recombination dynamics within semiconductor nanocrystals. This study synthesises type-II heterojunction ZnTe/ZnSe core-shell nanocrystals via a diethyl zinc-free synthesis method, producing small size distributions and quantum yields as high as 12%. It was found that the 7% lattice mismatch between the core and shell materials places limitations on the range of structures in which coherent growth is achieved. By developing compositional and strained atomistic core-shell models a variety of physical and optical properties could be simulated and has led to a clear picture of the core-shell architecture to be built. This characterisation provides evidence that the low bulk modulus ZnTe cores are compressed by the higher bulk modulus smaller lattice constant ZnSe shells. Further studies show how strain is manifested in structures with 'sharp' core-shell interfaces and how intentional alloying the interface can influence the growth and exciton energies. A (2-6)-band effective mass model was able to distinguish between the as-grown 'sharp' and 'alloyed' interfaces which indicated that strain accentuates the redshift of the excitonic state whilst reduced strain within an alloyed interface sees a reduced redshift. Single nanocrystal spectroscopy investigations of brightly emitting single graded alloyed nanocrystals and of a size series of commercially available CdSe/ZnS nanocrystals showed almost no fluorescence intermittency (nearly 'non-blinking'). These investigations also identified trion recombination as the main mechanism within the blinking 'off' state. Ultimately this thesis adds to the growing understanding of how specific core-shell architectures manipulate the electronic structure and develops techniques to identify specific material characteristics and how these characteristics influence the physical and optical properties within semiconductor nanocrystals.

Iron oxide nanoparticles (NPs) are promising materials for use in many applications, including new cancer treatments and in cleaning water, because they exhibit size-dependent magnetic and absorptive properties. NP properties are caused by structural attributes of the NPs, like surface disorder and cation vacancies. However, NP synthetic methods also impact structure, therefore properties, of NPs. Furthermore, the synthetic method is often changed in order to change the core diameter of NPs. Determining if properties are caused by the dimensions of the NP is impossible if there are also structural features present in the NP caused by the synthetic method, like grain boundaries or polycrystalline shells. In Chapter II of this dissertation, we show a new continuous growth synthesis of spinel iron oxide where the diameter of NPs is changed by the amount of precursor added to the reaction, meaning the only structural feature changing between the NPs is size. Continuous growth, therefore, can be used to probe the impact that size has on NP structure and properties. We report that saturation magnetization of NPs produced from continuous growth is size-dependent and higher in magnitude than NPs of the same core diameter made by other syntheses. In chapter III of this dissertation we determine nanoscale structure by Pair Distribution Function (PDF) analysis of Total X-ray Scattering data of NPs isolated from the reaction with core diameters between 3-10 nm. In Chapter IV of this dissertation we monitored the growth of NPs in situ with Total X-ray Scattering to gain insight on the structures of NPs while forming. In situ measurements of Total X-ray Scattering data gave insights into how precursor oxidation state influences the structures formed during formation of NPs, with more oxidized precursor giving a more oxidized product and a reduced precursor yielding a more reduced product even though the NPs formed by either method are indistinguishable by ex situ analysis. This dissertation includes previously published and unpublished co-authored material. / 2021-04-30

Some interesting electronic and dynamic properties of semiconductor nanocrystal heterostructures have been investigated using various spectroscopic methods. Semiconductor nanocrystal heterostructures were prepared using colloidal synthesis techniques. Ultrafast transient absorption spectroscopy was used to monitor the relaxation of hot electrons in CdS/HgS/CdS quantum dot quantum wells. Careful analysis of the hot electron relaxation in CdS/HgS/CdS quantum dot quantum wells reveals an energy dependent relaxation mechanism involving electronic states of varying CdS and HgS composition. The composition of the electronic states, combined with the layered structure of the nanocrystal permits the assignment of CdS localized and HgS localized excited states. The dynamic effect of surface passivation is then shown to have the strongest influence on excited states that are localized in the HgS layer. New quantum dot quantum well heterostructures of different sizes and compositions were also prepared and studied. The dynamic properties of CdS/CdSe/CdS colloidal quantum wells suggest simultaneous relaxation of excited electrons within the CdS core and CdSe shell on the sub-picosecond time scale. Despite the very different electronic structure of CdS/CdSe/CdS compared to CdS/HgS/CdS, the time scales of the relaxation and electron localization were very similar. Enhancement of trap luminescence was observed when CdS quantum dots were coated with silver. The mechanism of the enhancement was investigated using time-resolved spectroscopic techniques.

Deposition of noble metal and semiconductor nanocrystalline thin films has received much attention. CdS and CdSe are important semiconductors used in optical devices. A wet chemical route which uses the interface of two immiscible liquids to control the growth and deposition of nanocrystalline thin films forms the basis of the current study. In this method, a metal precursor dissolved in toluene or decane is held in contact with a water layer containing a reducing or sulphiding agent. The reaction proceeds at the interface of the liquids and results in deposits adhering to the interfacial region. The products of such reactions typically consist of nanocrystals forming a thin film. Stable sols of Au, Ag were found to metathesize on contact with alkylamine in oil to form monolayer films that spread across large areas at the water/oil interface. The nature and properties of interfacial thin films depend on the alkylamine. Nanocrystalline thin films consisting of CdS adhering to the interface starting with a polydispersed aqueous sol of crystallites and alkylamine were obtained. The optical band gaps of the films formed are dependent on the alkylamine chain length, with the shortest chain yielding the largest gap. A systematic increase in particle diameters following adsorption is responsible for changes in the electronic structure of films. The formation of nanocrystalline films of CdS adhering at the interface using a toluene solution of cadmium diethyldithiocarbamate and aqueous Na2S solution, in the presence of tetraoctylammonium bromide (TOAB) in the aqueous phase, was investigated under various reaction parameters, while CdSe was obtained using Na2SeSO3 solution and the influences of deposition temperature and solution concentration were studied. A ternary water/decane/2-butoxyethanol /salt system was used to grow deposits of CdSe and CdS. Nanostructured thin films were obtained at the upper interface of the ternary system, between the emulsive middle layer and oil rich top phase. The influence of deposition conditions such as precursor concentrations and temperature, as well as the nature of the medium on the properties of the deposits was studied. Deposits grown using the ternary system were compared with those obtained using water/decane and water/toluene systems. Reaction parameters such as temperature, solution concentration and the size of CdS and CdSe were controlled. A thin film of CdS and CdSe nanocrystals was formed at the interface. The grain size was found to be dependent on reaction temperature and solution concentration, with higher temperatures and solution concentration resulting in larger grains. The nature of thin films obtained at the interface of two immiscible liquids and of a water/decane/2-butoxyethanol/salt ternary system were studied using Scanning and Transmission electron microscopy, X-ray diffraction and UV-visible spectroscopy.

The properties of bulk 3D materials of metals or semiconductors are manifested with various length scales(e.g., Bohr excitonic radius, magnetic correlation length, mean free path etc.) and are important in controlling their properties. When the size of the material is smaller than these characteristics length scales, the confinement effects operate reflecting changes in their physical behavior. Materials with such confinement effects can be designated as low dimensional materials. There are exceedingly large numbers of low dimensional materials and the last half a century has probably seen the maximum evolution of such materials in terms of synthesis, characterization, understanding and modification of their properties and applications. The field of” nanoscience and nanotechnology”, have become a mature field within the last three decades where, for certain application, synthesis of materials of sizes in the nanometer range can be designed and controlled. Interface plays a very important role in controlling properties of heterogeneous material of every dimensionality. For example, the interface forms in 2D thin films or interface of heterogeneous nanoparticles(0D). In recent times, a large number of remarkable phenomena have triggered understanding and controlling properties arises due to nature of certain interface. In the field of nanoparticles, it is well known that the photoluminescence property depends very strongly on the nature of interface in heterostructured nanoparticles. In the recent time a large variety of heterostructured nanoparticles starting from core-shell to quantum dot-quantum well kind has been synthesized to increase the photoluminescence efficiency up to 80%. Along with improvement of certain properties due to heterostructure formation inside the nanoparticles, the techniques to understand the nature of those interfaces have improved side by side. It has been recently shown that variable energy X-ray Photoemission Spectroscopy (XPS) can be employed to understand the nature of interfaces (internal structure) of such heterostructure nanoparticles in great detail with high accuracy. While most of the previous studies of variable energy XPS, uses photonenergies sensitive to smaller sized particle, we have extended the idea of such nondestructive approach of understanding the nature of buried interfaces to bigger sized nanoparticles by using photon energy as high as 8000eV, easily available in various 3rd generation synchrotron centers. The nature of the interface also plays an important role in multilayer thin films. Major components of various electronic devices, like read head memory devices, field effect transistors etc., rely on interface properties of certain multilayer thin film materials. In recent time wide range of unusual phenomenon such as high mobility metallic behavior between two insulating oxide, superconductivity, interface ferroelectricity, unusual magnetism, multiferroicity etc. has been observed at oxide interface making it an interesting field of study. We have shown that variable energy photoemission spectroscopy with high photon energies, can be a useful tool to realize such interfaces and controlling the properties of multilayered devices, as well as to understand the origin of unusual phenomenon exists at several multilayer interfaces. Chapter1 provides a brief description of low dimensional materials, overall perspective of interesting properties in materials with reduced dimensionality. We have emphasized on the importance of determining the internal structure of buried interface of different dimensionalities. We have given a brief overview and importance of different interfaces that we have studied in the subsequent chapters dealing with specific interfaces. Chapter 2 describes experimental and theoretical methods used for the study of interface and self-assembly reported in this thesis. These methods are divided into two categories. The first section deals with different experimental techniques, like, UV-Visible absorption and photoluminescence spectroscopy, X-Photoelectron Spectroscopy(XPS), X-Ray diffraction, Transmission Electron Microscopy(TEM) etc. This section also includes brief overview on synchrotron radiation and methods used for detail analysis of interface structure using variable energy XPS. In the second part of this chapter, we have discussed theoretical methods used in the present study. \ In Chapter 3A we have combined low energy XPS, useful to extract information of the surface of the nanoparticles, with high energy XPS, important to extract bulk information and have characterized the internal structure of nanoparticle system of different heterogeneity. We have chosen two important heterostructure systems namely, inverted core-shell(CdScore-CdSeshell) type nanoparticles and homogeneous alloy(CdSeS)type nanoparticles. Such internal structure study revealed that the actual internal structure of certain nanomaterial can be widely different from the aim of the synthesis and knowledge of internal structure is a prerequisite in understanding their property. We were able to extend the idea of variable energy XPS to higher energy limit. Many speculations have been made about the probable role of interface in controlling properties, like blinking behavior of bigger sized core-shell nanoparticles, but no conclusive support has yet been given about the nature of such interface. After successfully extending the technique to determine the internal structure of heterostructured nanoparticles to very high photon energy region, we took the opportunity to determine the internal structure of nanoparticles of sizes as large as 12nm with high energy photoemission spectroscopy for the first time. In Chapter 3B we emphasize on the importance of interface structure in controlling the behavior of bigger sized nanoparticles systems, the unsettled issues regarding their internal structure, and described the usefulness of high energy XPS in elucidating the internal structure of such big particles with grate accuracy to solve such controversies. The existence of high density storage media relies on the existence of highly sensitive magnetic sensors with large magnetoresistance. Today almost all sensor technologies used in modern hard disk drives rely on tunnel magnetoresistance (TMR) CoFeB-MgO-CoFeB structures. Though device fabrication is refined to meet satisfactory quality assurance demands, fundamental understanding of the refinement in terms of its effect on the nature of the interfaces and the MgO tunnel barrier leading to improved TMR is still missing. Where, the annealing condition required to improve the TMR ratio is itself not confirmatory its effect on the interface structure is highly debatable. In particular, it has been anticipated that under the proposed exotic conditions highly mobile B will move into the MgO barrier and will form boron oxide. In Chapter 4 we are able to shed definite insights to heart of this problem. We have used high energy photoemission to investigate a series of TMR structures and able to provide a systematic understanding of the driving mechanisms of B diffusion in CoFeBTMR structures. We have solved the mix-up of annealing temperature required and have shown that boron diffusion is limited merely to a sub-nanometer thick layer at the interface and does not progress beyond this point under typical conditions required for device fabrication. We have given a brief overview on the evolution of magnetic storage device and have described various concepts relevant for the study of such systems. The interface between two nonmagnetic insulators LaAlO3 and SrTiO3 has shown a variety of interface phenomena in the recent times. In spite of a large number of high profile studies on the interface LaAlO3 and SrTiO3 there is still a raging debate on the nature, origin and the distribution of the two dimensional electron gas that is supposed to be responsible for its exotic physical properties, ranging from unusual transport properties to its diverse ground states, such as metallic, magnetic and superconducting ones, depending on the specific synthesis. The polar discontinuity present across the SrTiO3-LaAlO3 interface is expected to result in half an electron transfer from the top of the LaAlO 3 layer to each TiofSrTiO3 at the interface, but, the extent of localization that can make it behave like delocalized with very high mobility as well as localized with magnetic moments is not yet clear. In Chapter 5 we have given a description of this highly interesting system as well as presented the outcome of our depth resolved XPS investigation on several such samples synthesized under different oxygen pressure. We were able to describe successfully the distribution of charge carriers. While synthesizing and understanding properties of nanoparticles is one issue, using them for device fabrication is another. For example, to make a certain device often requires specific arrangements of nanoparticles in a suitable substrate. Self-assembly formation can be a potential tool in these regards. Just like atom or ions, both nano and colloidal particles also assemble by themselves in ordered or disordered structure under certain conditions, e.g., the drying of a drop of suspension containing the colloid particles over a TEM grid. This phenomenon is known as self-assembly. Though, the process of assembly formation can be a very easy and cost-effective technique to manipulate the properties in the nano region, than the existing ones like lithography but, the lack of systematic study and poor understanding of these phenomena at microscopic level has led to a situation that, there is no precise information available in literature to say about the nature of such assembly. In Chapter 6 we have described experiments that eliminate the dependence of the self-assembly process on many complicating factors like substrate-particle interaction, substrate-solvent interaction etc., making the process of ordering governed by minimum numbers of experimental parameter that can be easily controlled. Under simplified conditions, our experiments unveil an interesting competition between ordering and jamming in drying colloid systems similar to glass transition phenomenon Resulting in the typical phase behavior of the particles. We establish a re-entrant behavior in the order-disorder phase diagram as a function of particle density such that there is an optimal range of particle density to realize the long-range ordering. The results are explained with the help of simulations and phenomenological theory. In summary, we were able to extend the idea of variable energy XPS to higher energy limit advantageous for investigating internal structure of nonmaterial of various dimensionalities and sizes. We were able to comprehend nature of buried interface indicating properties of heterostructures quantum dots and thin films. Our study revealed that depth resolved XPS combined with accessibility of high and variable energies at synchrotron centers can be a very general and effective tool for understanding buried interface. Finally, we have given insight to the mechanism of spontaneous ordering of nanoparticles over a suitable substrate.

Size and Shape Controlled Synthesis and Superparamagnetic Properties of Spinel Ferrites Nanocrystals Qing Song 216 pages Directed by Dr. Z. John Zhang The correlationship between magnetic properties and magnetic couplings is established through the investigations of various cubic spinel ferrite nanocrystals. The results of this thesis contribute to the knowledge of size and shape controlled synthesis of various spinel ferrites and core shell architectured nanocrystals as well as the nanomagnetism in spinel ferrites by systematically investigating the effects of spin orbital coupling, magnetocrystalline anisotropy, exchange coupling, shape and surface anisotropy upon superparamagnetic properties of spinel ferrite nanocrystals. A general synthetic method is developed for size and shape control of metal oxide nanocrystals. The size and shape dependent superparamagnetic properties are discussed. The relationship between spin orbital coupling and magnetocrystalline anisotropy is studied comparatively on variable sizes of spherical CoFe2O4 and Fe3O4 nanocrystals. It also addresses the effect of exchange coupling between magnetic hard phase and soft phase upon magnetic properties in core shell structured spinel ferrite nanocrystals. The role of anisotropic shapes of nanocrystals upon self assembled orientation ordered superstructures are investigated. The effect of thermal stability of molecular precursors upon size controlled synthesis of MnFe2O4 nanocrystals and the size dependent superparamagnetic properties are described.

Nowadays ferromagnetism is often found in potential diluted magnetic semiconductor systems. However, many authors question the origin of this ferromagnetism, i.e. if the observed ferromagnetism stems from ferromagnetic precipitates rather than from carriermediated magnetic coupling of ionic impurities, as required for a diluted magnetic semiconductor. In this thesis, this question will be answered for transition-metal implanted ZnO single crystals. Magnetic secondary phases, namely metallic Fe, Co and Ni nanocrystals, are formed inside ZnO. They are - although difficult to detect by common approaches of structural analysis - responsible for the observed ferromagnetism. Particularly Co and Ni nanocrystals are crystallographically oriented with respect to the ZnO matrix. Their structure phase transformation and corresponding evolution of magnetic properties upon annealing have been established. Finally, an approach, pre-annealing ZnO crystals at high temperature before implantation, has been demonstrated to sufficiently suppress the formation of metallic secondary phases.