The intermittent nature of several sustainable energy sources such as solar and wind energy has ignited the demand of electrochemical energy storage devices in the form of batteries and electrochemical capacitors. The future generation of electrochemical capacitors will in large part depend on the use of pseudocapacitive materials in one or both electrodes. Developing pseudocapacitors to have both high energy and power density is crucial for future energy storage systems. This dissertation evaluates two different material systems to achieve high energy density pseudocapacitive energy storage. This research presents the successful preparation and application of ternary NiCo2S4, which is based on the surface redox mechanism, in the area of pseudocapacitive energy storage. Attention has been paid to understanding its basic physical properties which can impact its electrochemical behavior. Well-defined single- and double-shell NiCo2S4 hollow spheres were fabricated for pseudocapacitor applications, showing much improved electrochemical storage performance with good energy and power densities, as well as excellent cycling stability. To overcome the complexity of the preparation methods of NiCo2S4 nanostructures, a one-step approach was developed for the first time. Asymmetric pseudocapacitors using NiCo2S4 as cathode and graphene as anode were also fabricated to extend the operation voltage in aqueous electrolyte, and thus enhance the overall capacity of the cells. Furthermore, high-performance on-chip pseudocapacitive energy storage was demonstrated using NiCo2S4 as electrochemically active materials. This dissertation also involves another material system, intercalation pseudocapacitive VO2 (B), that displays a different charge storage mechanism from NiCo2S4. By constructing high-quality, atomically-thin two-dimensional (2D) VO2 (B) sheets using a general monomer-assisted approach, we demonstrate that a rational design of atomically thin, 2D nanostructures of atypically layered systems can greatly lower the interaction energy and Li+ diffusion barrier, and it can completely suppress the crystal transformation during the charge-discharge process. As a result, we have successfully enabled the kinetically sluggish step to proceed at room temperature. We show that even at charge-discharge rates as fast as 100C (36 s), these 2D electrodes still offer a high capacity of 140 mAh g-1 due to the rapid Li+ ion diffusion in these 2D sheets. These results discussed in this part conclusively show that the ultrathin 2D geometry of atypically layered or non-layered materials could lead to significantly enhanced pseudocapacitive performance.

Emerging transparent semiconducting oxide (TSO) materials have achieved their initial commercial success in the display industry. Due to the advanced electrical performance, TSOs have been adopted either to improve the performance of traditional displays or to demonstrate the novel transparent and flexible displays. However, due to the lack of feasible p-type TSOs, the applications of TSOs is limited to unipolar (n-type TSOs) based devices. Compared with the prosperous n-type TSOs, the performance of p-type counterparts is lag behind. However, after years of discovery, several p-type TSOs are confirmed with promising performance, for example, tin monoxide (SnO). By using p-type SnO, excellent transistor field-effect mobility of 6.7 cm2 V-1 s-1 has been achieved. Motivated by this encouraging performance, this dissertation is devoted to further evaluate the feasibility of integrating p-type SnO in p-n junctions and complementary metal oxide semiconductor (CMOS) devices. CMOS inverters are fabricated using p-type SnO and in-situ formed n-type tin dioxide (SnO2). The semiconductors are simultaneously sputtered, which simplifies the process of CMOS inverters. The in-situ formation of SnO2 phase is achieved by selectively sputtering additional capping layer, which serves as oxygen source and helps to balance the process temperature for both types of semiconductors. Oxides based p-n junctions are demonstrated between p-type SnO and n-type SnO2 by magnetron sputtering method. Diode operating ideality factor of 3.4 and rectification ratio of 103 are achieved. A large temperature induced knee voltage shift of 20 mV oC-1 is observed, and explained by the large band gap and shallow states in SnO, which allows minor adjustment of band structure in response to the temperature change. Finally, p-type SnO is used to demonstrating the hybrid van der Waals heterojunctions (vdWHs) with two-dimensional molybdenum disulfide (2D MoS2) by mechanical exfoliation. The hybrid vdWHs show excellent rectifying performance. Due to the ultra-thin nature of MoS2, the operation of hybrid vdWHs is gate-tunable, and we further discover such gate-tunability depends on the layer number of MoS2, i.e., the screening effect. The detailed study in such hybrid vdWHs provides valuable information for understanding the switching performance of junctions contain 2D materials.

The recent discovery of layered transition metal carbides (MXenes) is one of the most important developments in two-dimensional (2D) materials. Preliminary theoretical and experimental studies suggest a wide range of potential applications for MXenes. The MXenes are prepared by chemically etching ‘A’-layer element from layered ternary metal carbides, nitrides and carbonitrides (MAX phases) through aqueous acid treatment, which results in various surface terminations such as hydroxyl, oxygen or fluorine. It has been found that surface terminations play a critical role in defining MXene properties and affects MXene performance in different applications such as electrochemical energy storage, electromagnetic interference shielding, water purification, sensors and catalysis. Also, the electronic, thermoelectric, structural, plasmonic and optical properties of MXenes largely depend upon surface terminations. Thus, controlling the surface chemistry if MXenes can be an efficient way to improve their properties. This research mainly aims to perform surface modifications of two commonly studied MXenes; Ti2C and Ti3C2, via chemical, thermal or physical processes to enhance electrochemical energy storage properties. The as-prepared and surface modified MXenes have been studied as electrode materials in Li-ion batteries (LIBs) and supercapacitors (SCs). In pursuit of desirable MXene surface, we have developed an in-situ room temperature oxidation process, which resulted in TiO2/MXene nanocomposite and enhanced Li-ion storage. The idea of making metal oxide and MXene nanocomposites was taken to the next level by combining a high capacity anode materials – SnO2 – and MXene. By taking advantage of already existing surface functional groups (–OH), we have developed a composite of SnO2/MXene by atomic layer deposition (ALD) which showed enhanced capacity and excellent cyclic stability. Thermal annealing of MXene at elevated temperature under different atmospheres was carried out and detailed surface chemistry was studied to analyze the change in surface functional groups and its effect on electrochemical performance. Also, we could replace surface functional groups with desirable heteroatoms (e.g., nitrogen) by plasma processing and studied their effect on energy storage properties. This work provides an experimental baseline for surface modification of MXene and helps to understand the role of various surface functional groups in MXene electrode electrochemical performance.

Sodium-ion batteries (SIBs) are considered as a promising alternative to lithium-ion batteries (LIBs) for large-scale renewable energy storage units due to the abundance of sodium resource and its low cost. However, the development of anode materials for SIBs to date has been mainly limited to some traditional anodes for LIBs, such as carbonaceous materials. SnSe2 is a member of two dimensional layered transition metal dichalcogenide (TMD) family, which has been predicted to have high theoretical capacity as anode material for sodium ion batteries (756 mAh g-1), thanks to its layered crystal structure. Yet, there have been no studies on using SnSe2 as Na ion battery anode. In this thesis, we developed a simple synthesis method to prepare pure SnSe2 nanosheets, employing N2 saturated NaHSe solution as a new selenium source. The SnSe2 2D sheets achieve theoretical capacity during the first cycle, and a stable and reversible specific capacity of 515 mAh g-1 at 0.1 A g-1 after 100 cycles, with excellent rate performance. Among all of the reported transition metal selenides, our SnSe2 sample has the highest reversible capacity and the best rate performances. A combination of ex-situ high resolution transmission electron microscopy (HRTEM) and X-ray diffraction was used to study the mechanism of sodiation and desodiation process in this SnSe2, and to understand the reason for the excellent results that we have obtained. The analysis indicate that a combination of conversion and alloying reactions take place with SnSe2 anodes during battery operation, which helps to explain the high capacity of SnSe2 anodes for SIBs compared to other binary selenides. Density functional theory was used to elucidate the volume changes taking place in this important 2D material.

As the world strives to adapt to the increasing demand for electrical power, sustainable energy sources are attracting significant interest. Around 60% of energy utilized in the world is wasted as heat. Different industrial processes, home heating, and exhausts in cars, all generate a huge amount of unused waste heat. With such a huge potential, there is also significant interest in discovering inexpensive technologies for power generation from waste heat. As a result, thermoelectric materials have become important for many renewable energy research programs. While significant advancements have been done in improving the thermoelectric properties of the conventional heavy-element based materials (such as Bi2Te3 and PbTe), high-temperature applications of thermoelectrics are still limited to one materials system, namely SiGe, since the traditional thermoelectric materials degrade and oxidize at high temperature. Therefore, oxide thermoelectrics emerge as a promising class of materials since they can operate athigher temperatures and in harsher environments compared to non-oxide thermoelectrics. Furthermore, oxides are abundant and friendly to the environment. Among oxides, crystalline SrTiO3 and ZnO are promising thermoelectric materials. The main objective of this work is therefore to pursue focused investigations of SrTiO3 and ZnO thin films and superlattices grown by pulsed laser deposition (PLD), with the goal of optimizing their thermoelectric properties by following different strategies. First, the effect of laser fluence on the thermoelectric properties of La doped epitaxial SrTiO3 films is discussed. Films grown at higher laser fluences exhibit better thermoelectric performance. Second, the role of crystal orientation in determining the thermoelectric properties of epitaxial Al doped ZnO (AZO) films is explained. Vertically aligned (c-axis) AZO films have superior thermoelectric properties compared to other films with different crystal orientations. Third, additional B-site doping of A-site doped SrTiO3 films leads to a prominent reduction in the lattice thermal conductivity without limiting the electrical transport, and hence an improvement in the figure of merit is noticed. Fourth and last, the enhancement of thermoelectric properties of thermally robust, high quality SrTiO3-based superlattices is discussed. Beside the randomly distributed oxygen vacancies and extrinsic dopants, the structure of SrTiO3-based superlattices increases the scattering of phonons at the interfaces between the alternative layers, and hence reducing the thermal conductivity, which leads to a notable enhancement in the figure of merit.

The demand for energy storage technologies is rapidly increasing in portable electronics, transportation, and renewable energy systems. Thus, the objective of this research is to develop and enhance the performance of Ni-based electrochemical supercapacitors by optimizing synthesis conditions and design of the electrode materials. Conventional and on-chip supercapacitors were developed with notable performance enhancement. For conventional supercapacitors, a uniform and conformal coating process was developed to deposit Ni(OH)2 nanoflakes on carbon microfibers in-situ by a simple chemical bath deposition at room temperature. The microfibers conformally-coated with Ni(OH)2 make direct physical contacts with essentially every single nanoflakes, leading to more efficient electron transport. Using this strategy, we have achieved devices that exhibit five times higher specific capacitance compared to planar (non-conformal) Ni(OH)2 nanoflakes electrodes prepared by drop casting of Ni(OH)2 on the carbon microfibers (1416 F/g vs. 275 F/g). For on-chip storage applications, microfabricated supercapacitors were developed using a combination of top-down photolithography and bottom-up CBD. The resulting Ni(OH)2 micro-supercapacitors show high-rate redox activity up to 500 V/s and an areal cell capacitance of 16 mF/cm2 corresponding to a volumetric stack capacitance of 325 F/cm3. This volumetric capacitance is 2-fold higher than carbon and metal oxide based micro-supercapacitors. Furthermore, these micro-supercapacitors show a maximum energy density of 21 mWh/cm3, which is superior to the Li-based thin film batteries. To enhance cycling stability, Ni-Cu-OH and Ni-Co-OH ternary electrodes have been prepared with different Ni:Cu and Ni:Co ratios by CBD at room temperature on carbon microfibers. It is observed that the electrodes with Ni:Cu and Ni:Co composition ratio of 100:10 results in an optimum capacitance and cycling stability. For the optimum composition, Ni-Co-OH with graphene and carbon nanofibers electrode was tested, with resultant improvement in electrode potential window, equivalent series resistance, and cyclic stability. To further increase energy density, Ni(OH)2//Graphene asymmetric supercapacitor were fabricated with areal capacitance of 253 mF/cm2 at 5 mA/cm2 which is higher than NiO//rGO prepared by hydrothermal method. Ni-Co-OH/G-CNF//Graphene asymmetric supercapacitor results in a maximum power of 23 mW within an operating voltage of 2.2 V which are higher than of Ni(OH)2//Graphene (15.94 mW within 1.8 V). Our asymmetric supercapacitors have flexible-electrodes, low-cost fabrication process and environmentally friendly materials.

With the projected growth of the flexible and plastic electronics industry, there is renewed interest in the research community to develop high performance all-polymeric memory which will be an essential component of any electronic circuit. Some of the efforts in polymer memories are based on different mechanisms such as filamentary conduction, charge trapping effects, dipole alignment, and reduction-oxidation to name a few. Among these the leading candidate are those based on the mechanism of ferroelectricity. Polymer ferroelectric memory can be used in niche applications like smart cards, RFID tags, sensors etc. This dissertation will focus on novel material and device engineering to fabricate high performance low temperature polymeric ferroelectric memory for flexible electronics. We address and find solutions to some fundamental problems affecting all polymer ferroelectric memory like high coercive fields, fatigue and thermal stability issues, poor breakdown strength and poor p-type hole mobilities. Some of the strategies adopted in this dissertation are: Use of different flexible substrates, electrode engineering to improve charge injection and fatigue properties of ferroelectric polymers, large area ink jet printing of ferroelectric memory devices, use of polymer blends to improve insulating properties of ferroelectric polymers and use of oxide semiconductors to fabricate high mobility p-type ferroelectric memory. During the course of this dissertation we have fabricated: the first all-polymer ferroelectric capacitors with solvent modified highly conducting polymeric poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) [PEDOT:PSS] electrodes on plastic substrates with performance as good as devices with metallic Platinum-Gold electrodes on silicon substrates; the first all-polymer high performance ferroelectric memory on banknotes for security applications; novel ferroelectric capacitors based on blends of ferroelectric poly(vinylidene fluoride trifluoroethylene) [P(VDF-TrFE)] and highly insulating dielectric poly(p-phenylene oxide) [PPO] with drastically improved fatigue and thermal stability; novel all-polymer ferroelectric diodes based on blends of ferroelectric [P(VDF-TrFE)] and n-type semiconducting [6,6]-phenyl-C61-butyric acid methyl ester [PCBM] with resistive switching properties and the first hybrid p-type ferroelectric memory with transparent tin monoxide [SnO] on plastic substrates with record mobilities.

Nanostructured materials provide new and exciting approaches to the development of supercapacitor electrodes for high-performance electrochemical energy storage applications. One of the biggest challenges in materials science and engineering, however, is to prepare the nanomaterials with desirable characteristics and to engineer the structures in proper ways. This dissertation presents the successful preparation and application of very promising materials in the area of supercapacitor energy storage, including manganese dioxide and its composites, polyaniline and activated carbons. Attention has been paid to understanding their growth process and performance in supercapacitor devices. The morphological and electrochemical cycling effects, which contribute to the understanding of the energy storage mechanism of MnO2 based supercapacitors is thoroughly investigated. In addition, MnO2 based binary (MnO2-carbon nanocoils, MnO2-graphene) and ternary (MnO2-carbon nanotube-graphene) nanocomposites, as well as two novel electrodes (MnO2-carbon nanotube-textile and MnO2-carbon nanotube-sponge) have been studied as supercapacitor electrode materials, showing much improved electrochemical storage performance with good energy and power densities. Furthermore, a general chemical route was introduced to synthesize different conducting polymers and activated carbons by taking the MnO2 nanostructures as reactive templates. The electrochemical behaviors of the polyaniline and activated nanocarbon supercapacitors demonstrate the morphology-dependent enhancement of capacitance. Excellent energy and power densities were obtained from the template-derived polyaniline and activated carbon based supercapacitors, indicating the success of our proposed chemical route toward the preparation of high performance supercapacitor materials. The work discussed in this dissertation conclusively showed the significance of the preparation of desirable nanomaterials and the design of effective nanostructured electrodes for supercapacitor energy storage applications.

Transparent oxide electronics have emerged as promising materials to shape the future of electronics. While several n-type oxides have been already studied and demonstrated feasibility to be used as active materials in thin film transistors, high performance p-type oxides have remained elusive. This dissertation is devoted to the study of transparent p-type oxide semiconductor tin monoxide and its use in the fabrication of field effect devices. A complete study on the deposition of tin monoxide thin films by direct current reactive magnetron sputtering is performed. Carrier density, carrier mobility and conductivity are studied over a set of deposition conditions where p-type conduction is observed. Density functional theory simulations are performed in order to elucidate the effect of native defects on carrier mobility. The findings on the electrical properties of SnO thin films are then translated to the fabrication of thin films transistors. The low processing temperature of tin monoxide thin films below 200 oC is shown advantageous for the fabrication of fully transparent and flexible thin film transistors. After careful device engineering, including post deposition annealing temperature, gate dielectric material, semiconductor thickness and source and drain electrodes material, thin film transistors with record device performance are demonstrated, achieving a field effect mobility >6.7 cm2V-1s-1. Device performance is further improved to reach a field effect mobility of 10.8 cm2V-1s-1 in SnO nanowire field effect transistors fabricated from the sputtered SnO thin films and patterned by electron beam lithography. Downscaling device dimension to nano scale is shown beneficial for SnO field effect devices not only by achieving a higher hole mobility but enhancing the overall device performance including better threshold voltage, subthreshold swing and lower number of interfacial defects. Use of p-type semiconductors in nonvolatile memory applications is then demonstrated by the fabrication of hybrid ferroelectric field effect transistors composed of organic ferroelectric layer polyvinylidene fluoride trifluoroethylene and inorganic p-type semiconductor tin monoxide. Both rigid and flexible devices are demonstrated, showing the advantages of low temperature oxides over polymer semiconductors by achieving much better performance, such as order of magnitude higher hole mobility.

Tin dioxide (SnO2) is considered one of the most promising anode materials for Lithium ion batteries (LIBs), due to its large theoretical capacity and natural abundance. However, its low electronic/ionic conductivities, large volume change during lithiation/delithiation and agglomeration prevent it from further commercial applications. In this thesis, we investigate modified SnO2 as a high energy density anode material for LIBs. Specifically two approaches are presented to improve battery performances. Firstly, SnO2 electrochemical performances were improved by surface modification using Atomic Layer Deposition (ALD). Ultrathin Al2O3 or HfO2 were coated on SnO2 electrodes. It was found that electrochemical performances had been enhanced after ALD deposition. In a second approach, we implemented a layer-by-layer (LBL) assembled graphene/carbon-coated hollow SnO2 spheres as anode material for LIBs. Our results indicated that the LBL assembled electrodes had high reversible lithium storage capacities even at high current densities. These superior electrochemical performances are attributed to the enhanced electronic conductivity and effective lithium diffusion, because of the interconnected graphene/carbon networks among nanoparticles of the hollow SnO2 spheres.