<p>This dissertation develops a novel application of the resonant-infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) technique toward the end goal of conjugated-polymer-based optoelectronic device fabrication. Conjugated polymers are attractive materials that are being investigated in the development of efficient optoelectronic devices due to their inexpensive material costs. Moreover, they can easily be combined with inorganic nanomaterials, such as colloidal quantum dots (CQDs), so as to realize hybrid nanocomposite-based optoelectronic devices with tunable optoelectronic characteristics and enhanced desirable features. One of the most significant challenges to the realization of optimal conjugated polymer-CQD hybrid nanocomposite-based optoelectronics has been the processes by which these materials are deposited as thin films, that is, conjugated polymer thin film processing techniques lack sufficient control so as to maintain preferred optoelectronic device behavior. More specifically, conjugated-polymer-based optoelectronics device operation and efficiency are a function of several attributes, including surface film morphology, internal polymer chain morphology, and the distribution and type of nanomaterials in the film bulk. Typical conjugated-polymer thin-film fabrication methodologies involve solution-based deposition, and the presence of the solvent has a deleterious impact, resulting in films with poor charge transport properties and subsequently poor device efficiencies. In addition, many next-generation conjugated polymer-based optoelectronics will require multi-layer device architectures, which can be difficult to achieve using traditional solution processing techniques. These issues direct the need for the development of a new polymer thin film processing technique that is less susceptible to solvent-related polymer chain morphology problems and is more capable of achieving better controlled nanocomposite thin films and multi-layer heterostructures comprising a wide range of materials. Therefore, this dissertation describes the development of a new variety of RIR-MAPLE that uses a unique target emulsion technique to address the aforementioned challenges.</p><p>The emulsion-based RIR-MAPLE technique was first developed for the controlled deposition of the conjugated polymers poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and poly[2-methoxy-5-(2'ethylhexyloxy)-1,4-(1-cyanovinylene) phenylene] (MEH-CN-PPV) into homogenous thin films. Therein, it was identified that target composition had the most significant influence on film surface morphology, and by tuning the concentration of hydroxyl bonds in the target bulk, the laser-target absorption depth could be tuned so as to yield more or less evaporative deposition, resulting in films with tunable surface morphologies and optical behaviors.</p><p>Next, the internal morphologies of emulsion-based RIR-MAPLE-deposited MEH-PPV thin films were investigated by measuring their hole drift mobilities using the time-of-flight (TOF) photoconductivity method in the context of amorphous materials disorder models (Bässler's Gaussian Disorder model and the Correlated Disorder model) in order to provide a quantitative measure of polymer chain packing. The polymer chain packing of the RIR-MAPLE-deposited films was demonstrated to be superior and more conducive to charge transport in comparison to spin-cast and drop-cast MEH-PPV films, yielding enhanced hole mobilities.</p><p>The emulsion-based RIR-MAPLE technique was also developed for the deposition of different classes of inorganic nanoparticles, namely un-encapsulated nanoparticles and ligand-encapsulated nanoparticles. These different classes of nanoparticles were identified to have different film growth regimes, such that either rough or smooth films were obtained, respectively. The ligand-encapsulated nanoparticles were then co-deposited with MEH-PPV as conjugated polymer-CQD hybrid nanocomposites, wherein the distributions of the constituent materials in the film bulk were identified to be tunable, from homogeneous to highly clustered. The RIR-MAPLE deposition regime determined the said distributions, that is, if the polymer and CQDs were sequentially deposited from a sectioned target or simultaneously deposited from a single target, respectively. The homogeneous conjugated polymer-CQD nanocomposites were also investigated in terms of their charge transport properties using the TOF photoconductivity technique, where it was identified that despite the enhanced dispersion of CQDs in the film bulk, the presence of a high concentration of CQDs degraded hole drift mobility, which indicates that special considerations must be taken when incorporating CQDs into conjugated-polymer-based nanocomposite optoelectronics.</p><p>Finally, the unique capability of RIR-MAPLE to enable novel conjugated polymer-based optical heterostructures and optoelectronic devices was evaluated by the successful demonstration of a conjugated polymer-based distributed Bragg reflector (DBR), a plasmonic absorption enhancement layer, and a conjugated polymer-based photovoltaic solar cell featuring a novel electron-transporting layer. These optical heterostructures and optoelectronic devices demonstrate that all of the constituent polymer and nanocomposite layers have controllable thicknesses and abrupt interfaces, thereby confirming the capability of RIR-MAPLE to achieve multi-layer, conjugated polymer-based heterostructures and device architectures that are appropriate for enhancing specific desired optical behaviors and optoelectronic device efficiencies.</p> / Dissertation

Luminescent quantum dots (QDs) or rods are semiconductor nano-particles that may be used for a wide array of applications such as in electro-optical devices, spectral bar coding, tagging and light filtering. In the case under investigation, the nano-particles are cadmium-selenide (CdSe), though they can be made from cadmium-sulfide, cadmium-telluride or a number of other II-VI and III-V material combinations. The CdSe quantum dots emit visible light at a repeatable wavelength when excited by an ultraviolet source. The synthesis of colloidal quantum dot nanoparticles is usually an organo-metallic precursor, high temperature, solvent based, airless chemical procedure that begins with the raw materials CdO, a high boiling point ligand, and a Se-trioctylphosphine conjugate. This investigation explores the means to produce quantum dots by this method and to activate the surface or modify the reaction chemistry with such molecules as trioctylphosphine oxide, stearic acid, dodecylamine, phenyl sulfone, aminophenyl sulfone, 4,4'dichlorodiphenyl sulfone, 4,4'difluorodiphenyl sulfone, sulfanilamide and zinc sulfide during the production to allow for further applications of quantum dots involving new chemistries of the outer surface. Overall, the project has been an interesting and successful one, producing a piece of equipment, a lot of ideas, and many dots with varied capping structures that have been purified, characterized, and stored in such a way that they are ready for immediate use in future projects. / Master of Science

Herein, we report the first solution-processed broadband photodetectors to break the past compromise between sensitivity and speed of response. Specifically, we report photodiodes having normalized detectivity (D*) > 1012 Jones and a 3dB bandwidth of > 2.9 MHz. This finding represents a 170,000 fold improvement in response speed over the most sensitive colloidal quantum dot (CQD) photodetector reported1 and a 100,000 fold improvement in sensitivity over the fastest CQD photodetector reported2. At the outset of this study, sensitive, solution-processed IR photodetectors were severely limited by low response speeds1. Much faster response speeds had been demonstrated by solution-processed photodetectors operating in the visible3, but these devices offered no benefits for extending the spectral sensitivity of silicon. No available solution-processed photodetector combined high sensitivity, high operating speed, and response to illumination across the UV, visible and IR. We developed a fast, sensitive, solution-processed photodetector based on a photodiode formed by a Schottky barrier to a CQD film. Previous attempts to form sensitive photodetectors based on CQD photodiodes had demonstrated low quantum efficiencies that limited sensitivity4,5. Efficient, sensitive semiconductor photodiodes are based on two fundamental characteristics: a large built-in potential that separates photogenerated charge carriers and minimizes internal noise generation, and high semiconductor conductivity for efficient collection of photogenerated charge. Schottky barriers to CQD films were developed to provide high, uniform built-in potentials. A multi-step CQD ligand exchange procedure was developed to allow deposition of tightly packed films of CQDs with high mobility and sufficiently well-passivated surfaces to form high-quality metallurgical junctions. The temporal response of the CQD photodiodes showed separate drift and diffusion components. Combined with detailed measurements of the Schottky barrier, these characteristics provided the physical basis for a numerical model of device operation. Based on this understanding, devices that excluded the slow diffusive component were fabricated, exploiting only the sub-microsecond field-driven transient to achieve MHz response bandwidth. These devices are the first to combine megahertz-bandwidth, high sensitivity, and spectral-tunability in photodetectors based on semiconducting CQDs. Record performance is achieved through advances in materials and device architecture based on a detailed understanding the physical mechanisms underlying the operation of CQD photodiodes.

Herein, we report the first solution-processed broadband photodetectors to break the past compromise between sensitivity and speed of response. Specifically, we report photodiodes having normalized detectivity (D*) > 1012 Jones and a 3dB bandwidth of > 2.9 MHz. This finding represents a 170,000 fold improvement in response speed over the most sensitive colloidal quantum dot (CQD) photodetector reported1 and a 100,000 fold improvement in sensitivity over the fastest CQD photodetector reported2. At the outset of this study, sensitive, solution-processed IR photodetectors were severely limited by low response speeds1. Much faster response speeds had been demonstrated by solution-processed photodetectors operating in the visible3, but these devices offered no benefits for extending the spectral sensitivity of silicon. No available solution-processed photodetector combined high sensitivity, high operating speed, and response to illumination across the UV, visible and IR. We developed a fast, sensitive, solution-processed photodetector based on a photodiode formed by a Schottky barrier to a CQD film. Previous attempts to form sensitive photodetectors based on CQD photodiodes had demonstrated low quantum efficiencies that limited sensitivity4,5. Efficient, sensitive semiconductor photodiodes are based on two fundamental characteristics: a large built-in potential that separates photogenerated charge carriers and minimizes internal noise generation, and high semiconductor conductivity for efficient collection of photogenerated charge. Schottky barriers to CQD films were developed to provide high, uniform built-in potentials. A multi-step CQD ligand exchange procedure was developed to allow deposition of tightly packed films of CQDs with high mobility and sufficiently well-passivated surfaces to form high-quality metallurgical junctions. The temporal response of the CQD photodiodes showed separate drift and diffusion components. Combined with detailed measurements of the Schottky barrier, these characteristics provided the physical basis for a numerical model of device operation. Based on this understanding, devices that excluded the slow diffusive component were fabricated, exploiting only the sub-microsecond field-driven transient to achieve MHz response bandwidth. These devices are the first to combine megahertz-bandwidth, high sensitivity, and spectral-tunability in photodetectors based on semiconducting CQDs. Record performance is achieved through advances in materials and device architecture based on a detailed understanding the physical mechanisms underlying the operation of CQD photodiodes.

This dissertation presents results of a project bringing Scanning Tunneling Microscope (STM) into a regime of unlimited operational time at cryogenic conditions. Freedom from liquid helium consumption was achieved and technical characteristics of the instrument are reported, including record low noise for a scanning probe instrument coupled to a close-cycle cryostat, which allows for atomically resolved imaging, and record low thermal drift. Subsequent studies showed that the new STM opened new prospects in nanoscience research by enabling Scanning Tunneling Spectroscopic (STS) spatial mapping to reveal details of the electronic structure in real space for molecules and low-dimensional nanomaterials, for which this depth of investigation was previously prohibitively expensive. Quantum-confined electronic states were studied in single-walled carbon nanotubes (SWCNTs) deposited on the Au(111) surface. Localization on the nanometer-scale was discovered to produce a local vibronic manifold resulting from the localization-enhanced electron-vibrational coupling. STS showed the vibrational overtones, identified as D-band Kekulé vibrational modes and K-point transverse out-of plane phonons. This study experimentally connected the properties of well-defined localized electronic states to the properties of associated vibronic states. Electronic structures of alkyl-substituted oligothiophenes with different backbone lengths were studied and correlated with torsional conformations assumed on the Au(111) surface. The molecules adopted distinct planar conformations with alkyl ligands forming cis- or trans- mutual orientations and at higher coverage self-assembled into ordered structures, binding to each other via interdigitated alkyl ligands. STS maps visualized, in real space, particle-in-a-box-like molecular orbitals. Shorter quaterthiophenes have substantially varying orbital energies because of local variations in surface reactivity. Different conformers of longer oligothiophenes with significant geometrical distortions of the oligothiophene backbones surprisingly exhibited similar electronic structures, indicating insensitivity of interaction with the surface to molecular conformation. Electronic states for annealed ligand-free lead sulfide nanocrystals were investigated, as well as hydrogen-passivated silicon nanocrystals, supported on the Au(111) surface. Delocalized quantum-confined states and localized defect-related states were identified, for the first time, via STS spatial mapping. Physical mechanisms, involving surface reconstruction or single-atom defects, were proposed for surface state formation to explain the observed spatial behavior of the electronic density of states. This dissertation includes previously published co-authored material.

In this thesis, the strength of the LBIC system is enhanced in different aspects that includes its feasibility as a non-destructive characterization tool, the signal analysis and development of analytical solution to have better understanding on the defects and inhomogeneities in the quantum dot based hetero-structures for device applications, finally understanding its limits due to the size of the laser beam and interpretation of artefacts in the signal appearance due to the presence of co-devices. Chapter#1 provides the introduction and literature survey of the LBIC system. It covers the importance and area of application of the LBIC. Chapter#2 various tools and instrumentation are discussed briefly for the systems that are developed in the lab as well as standard tools utilised for the material characterization. A LBIC instrumentation a novel colloidal quantum dots (CQD) thin film deposition system is discussed. In the last part along with the standard characterization systems a software tool (semiconductor device simulator) is discussed, which is used to visualize and understand the LBIC profile that is obtained experimentally. Chapter#3 provides the information of colloidal synthesis of PbS and HgxCd1-xTe quantum dots. Device fabrication process is explained step by step for the following devices. p-n junction silicon diodes, PbS-CQD/Si hetero-structures, ITO/PbS-CQD/Al crossbar structures and HgCdTe-CQD/Si hetero-structures. Chapter#4 deals with the major constraints imposed on the LBIC due to the need of Ohmic contacts. To overcome this major limitation, in this work, the origin of the signal is studied with the remote contact geometry for silicon p-n junction devices. It was observed that the signals can be collected with the capacitively coupled remote contacts, where LBIC was ultimately demonstrated as contactless measurement tool without any compromise on the measurements and thus obtained physical parameters. The effect of finite laser beam size is also described, which was found to have effect on the actual dimensions measured with the LBIC images. LBIC utility is further enhanced with the Si/CQD based hetero-structure devices, which are the potential candidates in the evolving device technology to be utilized in various modular systems such as PDs and LED applications. Chapter#5 discusses the origin and possible mechanisms for lateral photo-voltage which is closely monitored in the PbS-CQD/Si hetero-junction device systems. Interestingly, it is observed that there are two different line profiles for n and p type Si substrates. Different mechanisms that give rise to this kind of profiles were found to be distinct and are related to the band alignment of the CQD/Si hetero-structure. It lead to the revelation of an interesting phenomenon and believed to be universally observed irrespective of the materials involved in the formation of hetero-junction. Simulations and experimental results are quite consistent and in agreement with each other, which confirm the underlying physical mechanism that connects the LBIC anomalies with the band alignment. Chapter#6 deals with the spatial variations in the transverse photocurrent in the PbS-CQD film which is studied as a function of applied bias. Analytical equation is setup for the photocurrent in the CQD film under applied bias with the help of available transport mechanism and equations from the literature. The spatial non-uniformity that exists in the photocurrent proved to be the result of spatial inhomoginities in the physical parameters. By correlating the spatial data to the analytical equation, it is shown that the inhomoginities can be predicted. This approach is important for the devices, where monolithic detectors are fabricated by depositing CQD film on Read-Out-Integrated-Circuit (ROIC), where the manifestation of non-uniformity can be understood and probably fixed. Chapter#7 HgCdTe CQD based devices are studied for the purpose of photo-detector applications in MWIR (3  5 μm) region. HgxCd1-xTe Colloidal quantum dots are technologically important due to their wide absorption range that covers different regions of the atmospheric window. HgxCd1-xTe are successfully synthesised, which covers the absorption edge up to ~6.25 m in the IR region. Absorption and photo-response studies are carried out on HgxCd1-xTe/Si hetero-junctions under incident IR radiation. It is observed that the band gap of the quantum dots can be tuned easily by controlling the growth time as a parameter, thus moulded HgxCd1-xTe CQD/Si hetero-structures were found to have good photo-response. Chapter#8 the summary and the future direction and scope of the work is discussed. This includes the interesting observations during this thesis work which are not reported here in details.