This study presents a new way for new 3D energy harvesting energy with vertically aligned nanorods arrays. ZnO nanoparticles array on Au/Cr/Si substrate are directly patterned by electrospray. First, gel solutions with zinc acetate, monoethanolamine and 2-methoxyethanol as the precursor by sol-gel technology were formulated. Then, the solutions were stirred to become clear and homogeneous liquid. Second, the precursor solutions were prepared by electrospray, where a Taylor cone was formed to produce ZnO nanoparticles. Then the ZnO nanoparticles were annealed as seed layers for nanorods. By varying the property of the ZnO solution, needle with collector distance, applied voltage, annealing temperature and molar ratio were discussed. After annealing, the orientation of the ZnO nanorods depend on the crystalline orientation of ZnO nanoparticles. The ZnO nanorods were obtained at a temperature of 90 ¢XC by aqueous solution method. The experimental parameters of lengths, diameters, and pH level of the reaction medium of the Zno nanorod were observed and controlled. The physical structures of ZnO were characterized by X-ray diffraction (XRD) and Field Emission Scanning Electron Microscopy (FESEM) analyses. The results show that the ZnO nanoparticles become more intensity with increasing in annealing temperature. The SEM analysis reveals that the ZnO nanorods have diameters about 100-400 nm and length about 200-1200 nm. Finally, Pt electrode atop as Schottky contacts were packed to fabricate nanogenerator with ZnO nanorods. Then the nanogenerator was driven by ultrasonic wave vibration. The wave drives the electrode up and down to vibrate the nanorods, and its voltage and current were also characterized. The measurement results show the maximum power is 0.004х10-8 W during the operation frequency of 42 kHz.

<p>One-dimensional ZnO nanostructures have great potential applications in the fields of optoelectronic and sensor devices. Therefore, it is really important to realize the controllable growth of one-dimensional ZnO nanostructures and investigate their properties. The main points for this thesis are not only to successfully realize the controllable growth of ZnO nonawires, nanorods and quantum dots (QDs), and also investigate the structure and optical properties in detail by the methods of scan electron microscope(SEM), transmission electron microscope(TEM), resonant Raman, photoluminescence(PL) and low-temperature time resolved PL spectrum.</p><p>to grown ZnO nanorod arrays (ZNAs) on Si substrates. Firstly, the effects of ZnO nanoparticles, pH value of chemical solution, angel θ between substrate and beaker bottom on the structures of the samples were symmetrically investigated and the optimized growth condition to grow ZNAs can be concluded as follows: seed layer of ZnO nanoparticles, pH=6 and <em>θ</em>=70°. On the basis of these, the diameter of ZNAs was well controlled from 150nm~40nm through adjusting the diameter and density of the ZnO nanoparticles pretreated on the Si substrates. The experimental results indicated that both diameter and density of ZnO nanoparticles on the substrates determined the diameter of ZNAs. But when the density is higher than the critical value of 2.3×10⁸cm^-2, the density will become the dominant factor to determine the diameter of ZNAs.</p><p>One the other hand, the optical properties of ZNAs were investigated in detail. The Raman and photoluminescence (PL) results showed that after an annealing treatment around 500oC in air atmosphere, the crystal structure and optical properties became much better due to the decrease of surface defects. The resonant Raman measurements excited by 351.1nm not only revealed that the surface defects play a significant role in the as-grown sample, but also suggested that the strong intensity increase of some Raman scatterings was due to both outgoing resonant Raman scattering effect and deep level defects scattering contribution for ZnO nanorods annealed from 500°C to 700°C. It is the first time to the best of our knowledge that the Raman measurements can be used to monitor the change of surface defects and deep level defects in the CBD grown ZnO nanorods. We have also presented, for the first time, a time resolved PL study in CBD grown ZnO nanorods with different diameters. The results show that the decay time of the excitons in the nanorods strongly depends on the diameter of the nanorods. The altered decay time is mainly due to the surface recombination process. The effective time constant related to the surface recombination velocity was deduced. A thermal treatment under 500°C will suppress the surface recombination channel, resulting in an improvement of the optical quality for the ZnO nanorods.</p><p>This thesis not only provides the effective way to control the size of ZNAs, but also obtains some beneficial results in aspects of their optical properties, which builds theoretical and experimental foundation for much better and broader applications of one-dimensional ZnO nanostructures.</p>

One-dimensional ZnO nanostructures have great potential applications in the fields of optoelectronic and sensor devices. Therefore, it is really important to realize the controllable growth of one-dimensional ZnO nanostructures and investigate their properties. The main points for this thesis are not only to successfully realize the controllable growth of ZnO nonawires, nanorods and quantum dots (QDs), and also investigate the structure and optical properties in detail by the methods of scan electron microscope(SEM), transmission electron microscope(TEM), resonant Raman, photoluminescence(PL) and low-temperature time resolved PL spectrum. to grown ZnO nanorod arrays (ZNAs) on Si substrates. Firstly, the effects of ZnO nanoparticles, pH value of chemical solution, angel θ between substrate and beaker bottom on the structures of the samples were symmetrically investigated and the optimized growth condition to grow ZNAs can be concluded as follows: seed layer of ZnO nanoparticles, pH=6 and θ=70°. On the basis of these, the diameter of ZNAs was well controlled from 150nm~40nm through adjusting the diameter and density of the ZnO nanoparticles pretreated on the Si substrates. The experimental results indicated that both diameter and density of ZnO nanoparticles on the substrates determined the diameter of ZNAs. But when the density is higher than the critical value of 2.3×108cm-2, the density will become the dominant factor to determine the diameter of ZNAs. One the other hand, the optical properties of ZNAs were investigated in detail. The Raman and photoluminescence (PL) results showed that after an annealing treatment around 500oC in air atmosphere, the crystal structure and optical properties became much better due to the decrease of surface defects. The resonant Raman measurements excited by 351.1nm not only revealed that the surface defects play a significant role in the as-grown sample, but also suggested that the strong intensity increase of some Raman scatterings was due to both outgoing resonant Raman scattering effect and deep level defects scattering contribution for ZnO nanorods annealed from 500°C to 700°C. It is the first time to the best of our knowledge that the Raman measurements can be used to monitor the change of surface defects and deep level defects in the CBD grown ZnO nanorods. We have also presented, for the first time, a time resolved PL study in CBD grown ZnO nanorods with different diameters. The results show that the decay time of the excitons in the nanorods strongly depends on the diameter of the nanorods. The altered decay time is mainly due to the surface recombination process. The effective time constant related to the surface recombination velocity was deduced. A thermal treatment under 500°C will suppress the surface recombination channel, resulting in an improvement of the optical quality for the ZnO nanorods. This thesis not only provides the effective way to control the size of ZNAs, but also obtains some beneficial results in aspects of their optical properties, which builds theoretical and experimental foundation for much better and broader applications of one-dimensional ZnO nanostructures.

The excellent in-plane strength and stiffness to-weight ratios, as well as the ease of manufacturing have made the carbon fiber reinforced polymer composites (CFRPs) suitable structural materials for variety of applications such as aerospace, automotive, civil, sporting goods, etc. Despite the outstanding performance of the CFRPs along their fibers direction (on-axis), they lack sufficient strength and performance in the out-of-plane and off-axis directions. Various chemical and mechanical methods were reported to enhance the CFRPs' out-of-plane performance. However, there are two major drawbacks for utilizing these approaches: first, most of these methods induce damage to the carbon fibers and, therefore, deteriorate the in-plane mechanical properties of the entire CFRP, and second, the methods with minimal deteriorating effects on the in-plane mechanical performance have their own limitations resulting in very confined mechanical performance improvements. These methods include integrating nano-sized reinforcements into the CFRPs' structure to form a hybrid or hierarchical CFRPs. In lieu to all the aforementioned approaches, a relatively novel method, referred to as graphitic structures by design (GSD), has been proposed. The GSD is capable of grafting carbon nanotubes (CNTs) onto the carbon fibers surfaces, providing high concentration of CNTs where they are most needed, i.e. the immediate fiber/matrix interface, and in-between the different laminae of a CFRP. This method shows promising improvements in the in-plane and out-of-plane performance of CFRPs. Zinc oxide (ZnO) nanorods are other nano-sized reinforcing structures which can hybridize the CFRPs via their radially growth on the surface of carbon fibers. Among all the reported methods for synthesizing ZnO nanorods, hydrothermal technique is the most straightforward and least destructive route to grow ZnO nanorods over carbon fibers. In this dissertation, the GSD-CNTs growth method and the hydrothermal growth of ZnO nanorods have been utilized to fabricate hybrid CFRPs. The effect of different ZnO nanorods growth morphologies, e.g. size distribution and alignment, on the in-plane tensile performance and vibration attenuation capabilities of the hybrid CFRPs are investigated via quasi-static tension and dynamical mechanical analysis (DMA) tests, respectively. As a result, the in-plane tensile strength of the hybrid CFRPs were improved by 18% for the composite based on randomly oriented ZnO nanorods over the carbon fibers. The loss tangent of the CFRPs, which indicates the damping capability, increased by 28% and 19% via radially and randomly grown ZnO nanorods, respectively. While there are several studies detailing the effects of dispersed nanofillers on the fracture toughness of FRPs, currently, there are no literature detailing the effect of surface GSD grown CNTs and ZnO nanowire -on carbon fiber- on the fracture toughness of these hybrid composites. This dissertation probes the effects of surface grown nano-sized reinforcements on the fracture toughness via double cantilever beam (DCB) tests on hybrid ZnO nanorod or CNT grafted CFRPs. Results show that the surface grown CNTs enhanced the Mode I interlaminar fracture toughness (GIc) of the CFRPs by 22% and 32%, via uniform and patterned growth morphologies, respectively, over the reference composite based on untreated carbon fiber fabrics. The dissertation also explains the basis of the improvements of the fracture toughness via finite element method (FEM). In particular, FEM was employed to simulate the interlaminar crack growth behavior of the hybrid CFRPs under Mode I crack opening loading conditions embodied by the DCB tests. These simulations revealed that the hybrid CFRP based on fibers with uniform surface grown MWCNTs exhibited 55% higher interlaminar strength compared to the reference CFRPs. Moreover, via patterned growth of MWCNTs, the ultimate crack opening resistance of the CFRPs improved by 20%. To mimic the experimental behavior of the various CFRPs, a new methodology has been utilized to accurately simulate the unstable crack growth nature of CFRPs. Several investigations reported the effects of adding nanomaterials-including CNTs- as a filler phase inside the matrix material, on the impact energy absorption of the hybrid FRPs. However, the impact mitigation performance of CFRPs based on ZnO nanorod grafted carbon fibers has not been reported. The dynamic out-of-plane energy dissipation capabilities of different hybrid composites were investigated utilizing high velocity (~90 m/s) impact tests. Comparing the results of the hybrid MWCNT/ZnO nanorod/CFRP with those of reference CFRP, 21% and 4% improvements were observed in impact energy absorption and tensile strain to failure of the CFRPs, respectively. In addition to elevated stiffness and strength, CFRPs should possess enough tolerance not only to monotonic loadings, but also to cyclic loadings to be qualified as alternatives to traditional structural metal alloys. Therefore, the fatigue life of CFRPs is of much interest. Despite the promising potential of incorporating nano-sized reinforcements into the CFRPs structure, not many studies reported on the fatigue behavior of hybrid CFRPs so far. In particular, there are no reported investigations to the effect of surface grown CNTs on the fatigue behavior of the hybrid CFRPs, due to fact that almost all the CNT growth techniques (except for the GSD method) deteriorated the in-plane performance of the hybrid CFRPs. The hybrid ZnO nanorod grafted CFRPs have not been investigated under fatigue loading as well. In this dissertation, different hybrid CFRPs were tested under tension-tension fatigue to reveal the effects of the different nano-reinforcements growth on the fatigue behavior of the CFRPs. A remarkable fatigue damage tolerance was observed for the CFRPs based on uniform and patterned grown CNT fibers. Almost two decades of fatigue life extension was achieved for CFRPs based on surface grown MWCNTs. / Ph. D. / Carbon fiber reinforced polymer composites (CFRPs) are light-weight materials with excellent strength and stiffness along the direction of the fibers. These great mechanical properties have made CFRPs suitable structural materials for variety of applications such as aerospace, automotive, civil, sporting goods, etc. Despite the outstanding performance of the CFRPs along their fibers direction (on-axis), they lack sufficient strength and performance in the out-of-plane and off-axis directions. Various chemical and mechanical methods were reported to enhance the CFRPs’ out-of-plane performance. However, there are two major drawbacks for utilizing these approaches: first, most of these methods induce damage to the carbon fibers and, therefore, deteriorate the in-plane mechanical properties of the entire CFRP, and second, the methods with minimal deteriorating effects on the in-plane mechanical performance have their own limitations resulting in very confined mechanical performance improvements. These methods include integrating nano-sized reinforcements into the CFRPs’ structure to form a hybrid or hierarchical CFRPs. In lieu to all the aforementioned approaches, a relatively novel method, referred to as graphitic structures by design (GSD), has been proposed. The GSD is capable of grafting carbon nanotubes (CNTs) onto the carbon fibers surfaces, providing high concentration of CNTs where they are most needed, i.e. the immediate fiber/matrix interface, and in-between the different layers of a CFRP. This method shows promising improvements in the in-plane and out-of-plane performance of CFRPs. Zinc oxide (ZnO) nanorods are other nano-sized reinforcing structures which can hybridize the CFRPs via their radially growth on the surface of carbon fibers. Among all the reported methods for synthesizing ZnO nanorods, hydrothermal technique is the most straightforward and least destructive route to grow ZnO nanorods over carbon fibers. In this dissertation, the GSD-CNTs growth method and the hydrothermal growth of ZnO nanorods have been utilized to fabricate hybrid CFRPs. The effect of different ZnO nanorods growth morphologies, e.g. size distribution and alignment, on the in-plane tensile performance and vibration damping capabilities of the hybrid CFRPs are investigated via tension and dynamical mechanical analysis (DMA) tests, respectively. As a result, the in-plane tensile strength of the hybrid CFRPs were improved by 18% for the composite based on randomly oriented ZnO nanorods over the carbon fibers. The loss tangent of the CFRPs, which indicates the damping capability, increased by 28% and 19% via radially and randomly grown ZnO nanorods, respectively. Fracture toughness is a measure for the capability of a material to withstand a load in the presence of damage (i.e. crack) in the material’s structure. While there are several studies detailing the effects of dispersed nanofillers on the fracture toughness of FRPs, currently, there are no literature detailing the effect of surface GSD grown CNTs and ZnO nanowire -on carbon fiber- on the fracture toughness of these hybrid composites. This dissertation probes the effects of surface grown nano-sized reinforcements on the fracture toughness via double cantilever beam (DCB) tests on hybrid ZnO nanorod or CNT grafted CFRPs. Results show that the surface grown CNTs enhanced the Mode I interlaminar fracture toughness (G_Ic) of the CFRPs by 22% and 32%, via uniform and patterned growth morphologies, respectively, over the reference composite based on untreated carbon fiber fabrics. The dissertation also explains the basis of the improvements of the fracture toughness via finite element method (FEM). In particular, FEM was employed to simulate the interlaminar crack growth behavior of the hybrid CFRPs under Mode I crack opening loading conditions embodied by the DCB tests. These simulations revealed that the hybrid CFRP based on fibers with uniform surface grown MWCNTs exhibited 55% higher interlaminar strength compared to the reference CFRPs. Moreover, via patterned growth of MWCNTs, the ultimate crack opening resistance of the CFRPs improved by 20%. To mimic the experimental behavior of the various CFRPs, a new methodology has been utilized to accurately simulate the unstable crack growth nature of CFRPs. Several investigations reported the effects of adding nanomaterials - including CNTs - as a filler phase inside the matrix material, on the impact energy absorption of the hybrid FRPs. However, the impact mitigation performance of CFRPs based on ZnO nanorod grafted carbon fibers has not been reported. The dynamic out-of-plane energy dissipation capabilities of different hybrid composites were investigated utilizing high velocity (~90 m/s) impact tests. Comparing the results of the hybrid MWCNT/ZnO nanorod/CFRP with those of reference CFRP, 21% and 4% improvements were observed in impact energy absorption and tensile strain to failure of the CFRPs, respectively. In addition to elevated stiffness and strength, CFRPs should possess enough tolerance not only to monotonic loadings, but also to cyclic loadings to be qualified as alternatives to traditional structural metal alloys. Therefore, the fatigue life (i.e. the number of loading cycles to failure) of CFRPs is of much interest. Despite the promising potential of incorporating nano-sized reinforcements into the CFRPs structure, not many studies reported on the fatigue behavior of hybrid CFRPs so far. In particular, there are no reported investigations to the effect of surface grown CNTs on the fatigue behavior of the hybrid CFRPs, due to fact that almost all the CNT growth techniques (except for the GSD method) deteriorated the in-plane performance of the hybrid CFRPs. The hybrid ZnO nanorod grafted CFRPs have not been investigated under fatigue loading as well. In this dissertation, different hybrid CFRPs were tested under tension-tension fatigue to reveal the effects of the different nano-reinforcements growth on the fatigue behavior of the CFRPs. A remarkable fatigue damage tolerance was observed for the CFRPs based on uniform and patterned grown CNT fibers. Almost two decades of fatigue life extension was achieved for CFRPs based on surface grown MWCNTs.

Recently, efforts have been made for self-powering the batteries and portable electronic devices by piezoelectric nanogenerators. The piezoelectric nanogenerators can work as a power source for nano-systems and also as an active sensor. The piezoelectric nanogenerator is a device that converts random mechanical energy into electrical energy by utilizing the semiconducting and piezoelectric properties. Also, the mechanical energy is always available in and around us for powering these nano devices. The aim of the present thesis work is to explore 1D and 2D ZnO nanostructures (nanorods and nanosheets) on metal alloy substrates for the development of piezoelectric nanogenerators in energy harvesting and sensors applications. Hydrothermal synthesis method was adopted for the growth of ZnO nanostructures. The nanogenerators were fabricated by using the optimized synthesis parameters and subsequently studied their performance for power generation and as an active speed sensor. These 1D and 2D nanostructures based nanogenerators have opened up a new window for the energy harvesting applications and sensors development. The thesis is divided into following six chapters. Chapter 1: This chapter gives a general introduction about energy harvesting devices such as nanogenerators, available energy sources, mechanical energy harvesting, ZnO material and the details on hydrothermal synthesis process. A brief literature survey on different applications of piezoelectric nanogenerators is also included. Chapter 2: A novel flexible metal alloy (Phynox) and its properties along with its applications are discussed in this chapter. Details on the synthesis of 1D ZnO nanorods on Phynox alloy substrate by hydrothermal method are presented. Further, the optimization of parameters such as growth temperature, seed layer annealing and substrate temperature effects on the synthesis of ZnO nanorods are discussed in detail. As-synthesized ZnO nanorods have been characterized using XRD, FE-SEM, TEM and XPS. Chapter 3: It reports on the fabrication of piezoelectric nanogenerator on Phynox alloy substrate as power generating device by harvesting the mechanical energy. Initially, the performance of the nanogenerator for power generation due to finger tip impacts was studied and subsequently its switching polarity test was also carried out. Output voltage measurements were carried out using the in-house developed experimental setup. Stability test was also carried out to see the robustness of the nanogenerator. Finally, the output voltage response of the nanogenerator was studied for its use as an active speed sensor. Chapter 4: Synthesis of Al doped 2D ZnO nanorsheets on Aluminum alloy (AA-6061) substrate by hydrothermal method is reported in this chapter. The optimized parameters such as growth temperature and growth time effects on the synthesis of ZnO nanosheets are discussed. As-synthesized ZnO nanosheets were characterized using XRD, FE-SEM, TEM and XPS. The Al doping in ZnO is confirmed by EDXS and XPS analysis. Chapter 5: Cost effective fabrication of Al doped 2D ZnO nanosheets based nanogenerator for direct current (DC) power generation is reported in this chapter. The performance of the nanogenerator for DC power generation due to finger tip impacts was studied and subsequently its switching polarity test was also carried out. Output voltage measurements were carried out using the in-house developed experimental setup. Stability test was also carried out to see the robustness of the nanogenerator. Finally, the DC output voltage response of the nanogenerator was studied for its use as an active speed sensor. Chapter 6: The first section summarizes the significant features of the work presented in this thesis. In the second section the scope for carrying out the further work is given.

The main objective of nanotechnology is to build self-powered nanosystems that are ultrasmall in size, exhibit super sensitivity, extraordinary multi functionality, and extremely low power consumption. As we all know that 21st century has brought two most important challenges for us. One is energy shortage and the other is global warming. Now to overcome these challenges, it is highly desirable to develop nanotechnology that harvests energy from the environment to fabricate self-power and low-carbon nanodevices. Therefore a self-power nanosystem that harvests its operating energy from the environment is an attractive proposition. This is also feasible for nanodevices owing to their extremely low power consumption. One advantageous approach towards harvesting energy from the environment is the utilization of semiconducting piezoelectric materials, which facilitate the conversion of mechanical energy into electrical energy. Among many piezoelectric materials ZnO has the rare attribute of possessing both piezoelectric and semiconducting properties. But most applications of ZnO utilize either the semiconducting or piezoelectric property, and now it’s time to fully employ the coupled semiconducting-piezoelectric properties to form  the basis for electromechanically coupled nanodevices. Since wurtzite zinc oxide (ZnO) is structurally noncentral symmetric and has the highest piezoelectric tensor among tetrahedrally bonded semiconductors, therefore it becomes a promising candidate for energy harvesting applications. ZnO is relatively biosafe and biocompatible as well, so it can be used at large scale without any harm to the living environment. The synthesis of another transition metal oxide known as Co3O4 is also important due to its potential usage in the material science, physics and chemistry fields. Co3O4 has been studied extensively due to low cost, low toxicity, the most naturally abundant, high surface area, good redox, easily tunable surface and structural properties. These significant properties enable Co3O4 fruitful for developing variety of nanodevices. Co3O4 nanostructures have been focused considerably in the past decade due to their high electro-chemical performance, which is essential for developing highly sensitive sensor devices. I started my work with the synthesis of ZnO nanostructures with a focus to improve the amount of harvested energy by utilizing oxygen plasma treatment. Then I grow ZnO nanorods on different flexible substrates, in order to observe the effect of substrate on the amount of harvested energy. After that I worked on understanding the mechanism and causes of variation in the resulting output potential generated from ZnO nanorods. My next target belongs to an innovative approach in which AFM tip decorated with ZnO nanorods was utilized to improve the output energy. Then I investigated Co3O4 nanostructures though the effect of anions and utilized one of the nanostructure to develop a fast and reliable pH sensor. Finally to take the advantage of higher degree of redox chemistry of NiCo0O4 compared to the single phase of nickel oxide and cobalt oxide, a sensitive glucose sensor is developed by immobilizing glucose oxidase. However, there were problems with the mechanical robustness, lifetime, output stability and environmental adaptability of such devices, therefore more work is going on to find out new ways and means in order to improve the performance of fabricated nanogenerators and sensors.

When materials approach the size of few nanometers, they show properties which are significantly different from their bulk counterpart. Such unique/improved properties make them potential candidate for several emerging applications. At the reduced dimension, controlling the shape of nanocrystals provides an effective way to tune several material properties. In this regard, wet chemical synthesis has been established as the ultimate route to synthesize nanocrystals at ultra-small dimensions with excellent control over the morphology. However, the use of surfactant poses a barrier into efficient realization of its application as it requires a clean interface for better performance. Exercise of available cleaning protocols to clean the surface often leads to coarsening of the nanoparticles due to their inherent high surface curvature. For anisotropic nanomaterials, rounding of the shape is an additional problem. Anchoring nanomaterials onto substrates provides an easy way to impart stability. In this thesis, ultrathin Au nanowires, that are inherently unstable, have been shown to grow over a wide variety of substrates by in-situ functionalization. Use of nanomaterials as device component holds promise into miniaturization of electronics. But device fabrication in such cases require manipulation of nanomaterials with enhanced control. Dielectrophoresis offers an easy way to assemble nanomaterials in between contact pads and hence evolved as a promising tool to fabricate device with a good level of precision. Herein, directed assembly of ultrathin Au nanowires by dielectrophoresis, has been shown as an efficient strategy to fabricate devices based on the wires. Combining more than one nanocrystal, to form a heterostructure, often has the advantage of synergism and/or multifunctionality. Therefore, synthesis of heterostructure is highly useful in enhancing and/or adding functionalities to nanomaterials. There are several routes available in literature for synthesis of heterostructures. Newer strategies are being evolved to further improve performance in an application specific way. In that regard, a good understanding of mechanism of formation is crucial to form the desired product with the required functionality. For example, Au due to high electron affinity has been known to undergo reduction rather than cation exchange with chalcogenides. In this thesis, it has been shown that the final product depends on the delicate balance of reaction conditions and the system under study using CdS-Au as the model system. In yet another case, PdO nanotubes have been shown to form, on reaction of PdCl2 with ZnO at higher starting ratio of the precursors. In-situ generation of HCl provides an effective handle for tuning of the product from the commonly expected hybrid to hollow. Graphene has evolved as a wonder material due to its wide range of practical applications. Its superior conductivity with high flexibility has made it an important material in the field of nanoelectronics. In this thesis, an interesting case of packed crumpled graphene has been shown to sense a wide variety of strain/pressure which has applications in day to day life. The study reported in the thesis is organized as follows: Chapter 1 presents a general introduction to nanomaterials followed by the review of the available strategies to synthesize various 1D nanomaterials. Subsequently, a section on the classification of hybrid followed by the different synthetic protocols adopted in literature to synthesize them, have been provided. A review on the available methodologies for directed assembly of nanomaterials has been presented. Chapter 2 provides a summary of the materials synthesized and the techniques used for characterization of the materials. A brief description of all the synthetic strategy adopted has been provided. The basic principle of all the characterization techniques used, has been explained. A section explaining the principle of dielectrophoresis has also been presented. Chapter 3 presents a general method to grow ultrathin Au nanowires over a variety of substrates with different nature, topography and rigidity/flexibility. Ultrathin nanowires of Au (~2 nm in diameter) are potentially useful for various catalytic, plasmonic and device applications. Extreme fragility on polar solvent cleaning was a limitation in realizing the applications. Direct growth onto substrate was an alternative but poor interfacial energy of Au with most commercial substrates lead to poor coverage. In this chapter, in-situ functionalization of the substrates have been shown to improve Au nucleation dramatically which lead to growth of dense, networked nanowires over large area. Catalysis and lithography-free device fabrication has been demonstrated. Using the same concept of functionalization, SiO2 coating of the nanowires have been shown. A comparative study of thermal stability of these ultrafine Au nanowires in the uncoated and coated form, has been presented. Chapter 4 demonstrates an ultrafast device fabrication strategy with Au nanowires using dielectrophoresis. While dense growth of Au nanowires is beneficial for some applications, it is not so for some others. For example, miniaturization of electronics require large number of devices in a small area. Therefore, there is a need for methods to manipulate nanowires so as to place them in the desired location for successful fabrication of device with them. In this chapter, dielectrophoresis has been used for assembling nanowires in between and at the sides of the contact pads. Alignment under different conditions lead to an understanding of the forces. Fabrication of a large number of devices in a single experiment has been demonstrated. Chapter 5 presents a simple route to synthesize CdS-Au2Sx hybrid as a result of cation-exchange predominantly. Au due to high electron affinity has been shown in literature to undergo reduction rather than cation exchange with CdS. In this chapter, it has been shown that cation exchange may be a dominant product. The competition between cation exchange and reduction in the case of CdS-Au system has been studied using EDS, XRD, XPS and TEM. Thermodynamic calculation along with kinetic analysis show that the process may depend on a delicate balance of reaction conditions and the system under study. The methodology adopted, is general and may be applied to other systems. Chapter 6 presents an one pot, ultrafast microwave route to synthesize PdO hollow/hybrid nanomaterials. The common strategy to synthesize hollow nanomaterials had been by nucleation of the shell material on the core and subsequent dissolution of the core. In this chapter, a one step method to synthesize hollow PdO nanotubes, using ZnO nanorods as sacrificial template, has been shown. By tuning the ratio of the PdCl2 (PdO precursor) to ZnO, ZnO-PdO hybrid could be obtained using the same method. The PdO nanotubes synthesized could be converted to Pd nanotubes by NaBH4 treatment. Study of thermal stability of the PdO nanotubes has been carried out. Chapter 7 demonstrates a simple strategy to sense a variety of strain/pressure with taped crumpled graphene. Detection of ultralow strain (10-3) with high gauge factor is challenging and poorly addressed in literature. Taped crumpled graphene has been shown to detect such low strain with high gauge factor (> 4000). An ultra-fast switching time of 20.4 ms has been documented in detection of dynamic strain of frequency 49 Hz. An excellent cyclic stability for >7000 cycles has been demonstrated. The same device could be used to detect gentle pressure pulses with consistency. Slight modification of the device configuration enabled detection of high pressure. Simplicity of the device fabrication allowed fabrication of the device onto stick labels which could be pasted on any surface, for instance, floor. Hard pressing, stamping with feet and hammering shocks do not alter the base resistance of the device, indicating that it is extremely robust. Sealed arrangement of the graphene allowed operation of the device under water in detection of water pressure. Presence of trapped air underneath the tape enabled detection of air pressure both below and above atmospheric pressure.

In recent years, organic photovoltaics (OPVs) have attracted considerable attention as a potential source of renewable energy over traditional materials due to their light weight, low production cost, mechanically stability and compatibility with flexible substrates in roll to roll processing for high volume production. In the OPVs interface plays an important role in determining the performance of the device. Interface signifies formation of efficient contact with electrode, film, and transport of free charge carrier, which results in better performance in the device. Interface engineering also helps in improving mechanical robustness of the device. Hence, understanding of interface, modification and its evaluation is important in fabrication of efficient device. In this thesis interface is modified such that the performance of the device can be improved (chapter 3 and chapter 4). In Chapter 5 and chapter 6 interface is modified such that device can be fabricated on uncommon substrate. Fabrication of device on uncommon substrates (fiber reinforced plastic and flexible glass substrate), has unique challenges. In chapter 5 and chapter 6, we look at how interface is modified to overcome the challenges associated and also understand the role of interface in improving the performance of device on such substrates is discussed. In Chapter 1 we discuss about working of organic solar cells and the challenges associated in device fabrication. Understanding of interface to overcome challenges associated is explained. It also covers brief introduction to the succeeding chapters discussed in the thesis and its recent developments. To understand the properties of interface and to analyze device performance various characterization techniques have been used are discussed in chapter 2. This chapter also covers the materials and general device fabrication techniques used in this thesis. In chapter 3, a narrow bandgap (NBG) polymer used as a near IR sensitizer in P3HT: PCBM blend. Since, P3HT with a band gap of ~1.9 eV, the commonly used p-type material absorbs approximately ~25 % of incident light. Hence, MP2 (NBG polymer) is used along with P3HT: PCBM in active layer to form a ternary blend, which helps in increased absorption. Basic properties of MP2 are evaluated using UV-visible spectroscopy, differential scanning calaorimetry(DSC), thermogravimetric analyser (TGA), gel permeation chromatography (GPC) and photoluminescence (PL) techniques. To evaluate enhanced absorption of ternary UV-visible spectroscopy is carried out. Charge transfer from one moiety to other in ternary blend is evaluated using PL and Ttime resolved microwave conductivity (TRMC). Morphology of the ternary is assessed using atomic force microscope (AFM) and structural characterization is carried out by X-ray diffraction (XRD). Performance of the device is evaluated by current-voltage (J-V) characterizations. Further improved performance is supported by external quantum efficiency (EQE). Charge extraction with linear increasing voltage (CELIV) of the device is done to evaluate the recombination mechanism in the device and to assess the performance of the device. One-dimensional (1D) ZnO nanostructures provide direct paths for charge transport, and also offer large interfacial area to make them an ideal electron transport layer. In chapter 4 highly aligned ZnO nanorods is used as electron transport layer in OPV. Growth of ZnO nanorods is two-step processes, growing seed layer and growing ZnO nanorods from hydrothermal process using an appropriate seed layer. Two different soft-chemical solution- growth methods (upward and downward) are developed to fabricate self-assembled, oriented ZnO nanorods. Substrate mounting, surface properties and optical transmittance are optimized by varying the nanorods growth conditions. Further the ZnO nanorods are UV ozone treated and its effect on performance of nanostructured buffer layer based device is evaluated. In Chapter 5 OPV is fabricated on an opaque FRP substrate. Fabrication of OPV device on opaque substrate plastic is unique and hence understanding various properties is vital. Such devices fabrication require bottom up approach, with transparent electrode as the top electrode and metal electrode on the surface of FRP. FRP has inherent rough surface of about few microns RMS roughness. In order to reduce the roughness of the substrate FRP was planarized. The planarized layer is chosen, such that it chemically binds with the substrate. The chemical interaction between substrate and planarizing coating is evaluated by FTIR and Raman spectroscopy. The binding of planarized layer and FRP is evaluated using nanoscratch technique and surface energies are studied using contact angle measurements. In addition, adhesion properties of the metal electrodes, which are deposited on planarized FRP are evaluated using nanoscratch technique. Fabrication of OPV requires a top transparent electrode. Simple spin coating technique is used to optimize the top electrode. The property of top electrode is evaluated using UV-visible spectroscopy for transmittance, and sheet resistance of the electrode is characterized. OPV device is fabricated on planarized FRP substrate using optimized top transparent electrode and its PV properties is evaluated. Performance of the device is evaluated for two different bottom electrodes and further performance of device is enhanced using buffer layers. Usually flexible OPVs are fabricated on plastic substrate such as PET, PEN. However they are not structurally stable at high temperatures and have high oxygen and moisture Permeability. In Chapter 6 Organic based photovoltaic devices were fabricated on flexible glass. Flexible glass has high strength and it is also known for low oxygen and moisture permeability. Fabrication of device on flexible glass has never been done before and hence, generation of data is necessary for commercialization of the technology. Device fabrication is optimized by using two different transparent conducting layers (ITO- sputter deposited, PEDOT: PSS-solution processed) and device performance was evaluated for both. Since the substrate is flexible in nature understanding the performance of the device during flexing is important. For this 2-parallel plate flexural apparatus is fabricated for in-situ measurements along with current voltage measurements. These devices are flexed cyclically and performance of device is evaluated. Therefore, work discussed in the thesis show by modifying the interface of the device, and understanding various interfaces of the device is crucial for improving the performance of the device. Also by engineering the interface, devices can be fabricated on various types of substrate.

Recently, efforts have been made for self-powering the batteries and portable electronic devices by piezoelectric nanogenerators. The piezoelectric nanogenerators can work as a power source for nano-systems and also as an active sensor. The piezoelectric nanogenerator is a device that converts random mechanical energy into electrical energy by utilizing the semiconducting and piezoelectric properties. Also, the mechanical energy is always available in and around us for powering these nano devices. The aim of the present thesis work is to explore 1D and 2D ZnO nanostructures (nanorods and nanosheets) on metal alloy substrates for the development of piezoelectric nanogenerators in energy harvesting and sensors applications. Hydrothermal synthesis method was adopted for the growth of ZnO nanostructures. The nanogenerators were fabricated by using the optimized synthesis parameters and subsequently studied their performance for power generation and as an active speed sensor. These 1D and 2D nanostructures based nanogenerators have opened up a new window for the energy harvesting applications and sensors development. The thesis is divided into following six chapters. Chapter 1: This chapter gives a general introduction about energy harvesting devices such as nanogenerators, available energy sources, mechanical energy harvesting, ZnO material and the details on hydrothermal synthesis process. A brief literature survey on different applications of piezoelectric nanogenerators is also included. Chapter 2: A novel flexible metal alloy (Phynox) and its properties along with its applications are discussed in this chapter. Details on the synthesis of 1D ZnO nanorods on Phynox alloy substrate by hydrothermal method are presented. Further, the optimization of parameters such as growth temperature, seed layer annealing and substrate temperature effects on the synthesis of ZnO nanorods are discussed in detail. As-synthesized ZnO nanorods have been characterized using XRD, FE-SEM, TEM and XPS. Chapter 3: It reports on the fabrication of piezoelectric nanogenerator on Phynox alloy substrate as power generating device by harvesting the mechanical energy. Initially, the performance of the nanogenerator for power generation due to finger tip impacts was studied and subsequently its switching polarity test was also carried out. Output voltage measurements were carried out using the in-house developed experimental setup. Stability test was also carried out to see the robustness of the nanogenerator. Finally, the output voltage response of the nanogenerator was studied for its use as an active speed sensor. Chapter 4: Synthesis of Al doped 2D ZnO nanorsheets on Aluminum alloy (AA-6061) substrate by hydrothermal method is reported in this chapter. The optimized parameters such as growth temperature and growth time effects on the synthesis of ZnO nanosheets are discussed. As-synthesized ZnO nanosheets were characterized using XRD, FE-SEM, TEM and XPS. The Al doping in ZnO is confirmed by EDXS and XPS analysis. Chapter 5: Cost effective fabrication of Al doped 2D ZnO nanosheets based nanogenerator for direct current (DC) power generation is reported in this chapter. The performance of the nanogenerator for DC power generation due to finger tip impacts was studied and subsequently its switching polarity test was also carried out. Output voltage measurements were carried out using the in-house developed experimental setup. Stability test was also carried out to see the robustness of the nanogenerator. Finally, the DC output voltage response of the nanogenerator was studied for its use as an active speed sensor. Chapter 6: The first section summarizes the significant features of the work presented in this thesis. In the second section the scope for carrying out the further work is given.

This thesis deals with the research work carried out for the development of novel applications by integrating biomolecules with various nanostructures. The thesis is organized as follows: Chapter 1 reviews the properties of nanomaterials which are important to consider while developing them for various biological and other applications. It discusses the factors which affect the cytotoxicity of nanocrystals towards living cells, photocatalytic mechanisms of nanocrystals that work behind the inactivation of bacterial cells and gas sensing properties of nanocrystals. It also mentions about the integration of biomolecules with nanomaterials which is useful for the development of biosensors, materials that are presently used for fabricating biosensors and the challenges associated with designing successful biosensors. Chapter 2 presents the antibacterial and anticancer properties of ZnO/Ag nanohybids. In this study a simple route to synthesize ZnO/Ag nanohybrids by microwave synthesis has been established where ZnO/Ag nanohybrids have shown synergistic cytotoxicity towards mammalian cells. The observed synergism in the cytotoxicity of ZnO/Ag nanohybrids could lead to the development of low dose therapeutics for cancer treatment. Chapter 3 presents photocatalytic inactivation of bacterial cells by pentavalent bismuthates class of materials. AgBiO3 which was obtained from KBiO3 by ion-exchange method was investigated for its photocatalytic inactivation properties towards E.coli and S.aureus cells under dark and UV illumination conditions. Chapter 4 presents the integration of DNA molecules with ZnO nanorods for the observation of Mott-Gurney characteristics. In this study, ZnO nanorods were synthesized hydrothermally and were characterized by TEM and XRD analysis. DNA molecules were immobilized over ZnO nanorods which were confirmed by UV-Vis spectroscopy and confocal florescence microscopy. Solution processed devices were fabricated by using these DNA immobilized nanostructures and I-V characteristics of these devices were taken in dark and under illumination conditions at different wavelengths of light at fixed intensity. Interestingly, Mott-Gurney law was observed in the I-V characteristics of the devices fabricated using DNA immobilized ZnO nanorods. Chapter 5 presents the chemical synthesis of molecular scale ultrathin Au nanowires. These nanostructures were then used for fabricating electronic biosensors. In this study, the devices were fabricated over Au nanowires by e-beam lithography and a methodology to functionalize Au nanowires and then characterize them by florescence microscopy as well as AFM has been established. The fabricated biosensors were employed for the label free, electrical detection of DNA hybridization process. Chapter 6 presents a simple, cost effective and solution processed route to fabricate devices using ultrathin Au nanowires. The devices were then used for sensing ethanol, H2 and NH3. An important property of these devices is that they can sense these gases at room temperature which reduce their operation cost and makes them desirable to use under explosive conditions.