Different optical and calorimetric techniques were utilized to gain a better understanding of aggregated macromolecules. This research looked at two different macromolecules: poly(9,9'-dioctylfluorene), a conjugated polymer that forms aggregates in organic solvents; and bovine insulin, which forms amyloid fibrils. Conjugated polymers are of increasing interest due to their thermal stability and ease of solution processing for use in devices. A member of the polyfluorene family, poly(9,9'-dioctylfluorene) (PFO), has been studied due to its blue-emitting spectral properties. However, PFO has been found to form aggregates in solution, which is detected by the presence of a red-shifted absorption peak. This peak is caused when a section of the backbone planarizes forming the [beta]-phase. The [beta]-phase can be removed from the solution upon heating and will not return until the solution is cooled, making it a non-equilibrium process. The dissolution and reformation of the -phase were monitored using absorption spectroscopy and differential scanning calorimetry. Atomic force microscopy (AFM) and near-field scanning optical microscopy (NSOM) were able to probe the aggregates in films. It is important to understand polymer properties in solution in order to understand film morphology. Amyloid fibrils contribute to over 20 different neurodegenerative diseases, in which cures have yet to be found. The fibrils form when a soluble protein misfolds and self-assembles to form insoluble protein aggregates, and the cause of the fibril formation in vivo has still yet to be determined. Spectroscopy studies have been made possible with the use of fluorescent dyes: thioflavin T (ThT), BTA-2, and Congo red (CR). These dyes bind to amyloid fibrils and exhibit changes in their spectral properties. However, the exact mechanism for the binding of these dyes has only recently been studied. Through the use of calorimetry, the forces involved with binding of ThT and CR to amyloid fibrils can be determined. Absorption and fluorescence spectroscopy techniques were employed to study the spectral properties of these dyes. Polarized NSOM was used to determine the ThT or BTA-2's orientation with an individual fibril. Understanding how these dyes bind to fibrils will enable researchers to use spectroscopy to study the early stages of fibril formation. / text

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

This dissertation provides a brief introduction into scanning tunneling microscopy, and then Chapter III reports on the design and operation of a cryogenic ultra-high vacuum scanning tunneling microscope (STM) coupled to a closed-cycle cryostat (CCC). The STM is thermally linked to the CCC through helium exchange gas confined inside a volume enclosed by highly flexible rubber bellows. The STM is thus mechanically decoupled from the CCC, which results in a significant reduction of the mechanical noise transferred from the CCC to the STM. Noise analysis of the tunneling current shows current fluctuations up to 4% of the total current, which translates into tip-sample distance variations of up to 1.5 picometers. This noise level is sufficiently low for atomic-resolution imaging of a wide variety of surfaces. To demonstrate this, atomic-resolution images of Au(111) and NaCl(100)/Au(111) surfaces, as well as of carbon nanotubes deposited on Au(111), were obtained. Other performance characteristics such as thermal drift analysis and a cool-down analysis are reported. Scanning tunneling spectroscopy (STS) measurements based on the lock-in technique were also carried out and showed no detectable presence of noise from the CCC. These results demonstrate that the constructed CCC-coupled STM is a highly stable instrument capable of highly detailed spectroscopic investigations of materials and surfaces at the atomic-scale. A study of electron transport in single-walled carbon nanotubes (SWCNTs) was also conducted. In Chapter IV, STS is used to study the quantum-confined electronic states in SWCNTs deposited on the Au(111) surface. The STS spectra show the vibrational overtones which suggest rippling distortion and dimerization of carbon atoms on the SWCNT surface. This study experimentally connects the properties of well-defined localized electronic states to the properties of their associated vibronic states. In Chapter V, a study of PbS nanocrystals was conducted to study the effect of localized sub-bandgap states associated with surface imperfections. A correlation between their properties and the atomic-scale structure of chemical imperfections responsible for their appearance was established to understand the nature of such surface states. This dissertation includes both previously published/unpublished and co-authored material.

This study produced and analyzed shaped tungsten wire tips formed through electrochemical etching. Specifically, the cone length and the radius of curvature of the tip were analyzed. Having the tips move dynamically through an electrolytic solution, such as potassium hydroxide, and tuning the initial starting depth of the tungsten wire along with the dynamic speed of the tungsten wire as it passed throughout the solution allowed various types of tip profiles to be produced. The tip's radius of curvature was able to be reproduced with an accuracy between 88 - 92 %. The method provided would be applicable for the production of various styles of liquid-metal ion source (LMIS) probes and scanning probe microscope (SPM) tips.

High performance natural materials typically employ highly tuned structures spanning the nanoscopic to macroscopic length scales. Synthetically recapitulating this degree of complexity has become a unifying goal connecting the fields of chemistry, nanoscience, biology, and materials science. One common strategy is to direct the bottom up assembly of nanoparticle building blocks into hierarchical structures using stimuli such as electric fields. Despite the promise and great versatility of electric fields, there are many knowledge gaps surrounding their use to assemble highly complex structures. In this thesis, we explore the assembly of nanoparticles into hierarchical structures through dielectrophoresis (DEP), or the motion of polarizable objects in non-uniform electric fields. Critically, through a systematic approach, we study the fundamental polarizability of individual particles, the assembly of particle dimers, and finally the emergence of macroscopic structure from nanoscopic particles. Interweaving these explorations are instrumentation advances that broaden our ability to measure fundamental particle properties and explore hierarchical structures. Initially, we measure the polarizability of nanoparticles in solution using fluorescence microscopy. Specifically, we quantify the polarizability of solution-phase semiconductor quantum dots (QDs) for the first time. Through analyzing the thermodynamic distribution of particles in a microfluidic device with a non-uniform electric field profile, we identify a striking 30-fold increase in polarizability in the presence of low salt conditions due to the Debye screening length being commensurate with the particle size. This increase in polarizability indicates that nanoparticles assemble far more rapidly and easily than previously predicted. Next, we study the assembly of nanoparticles in the vicinity of anisotropic template particles as a path to realizing hierarchical structures. Specifically, we explore eight particle geometries using finite element analysis and find a >10-fold local field enhancement near some shapes, potentially promoting hierarchical assembly. We subsequently introduce a framework for predicting the assembly outcome of particles with multiple distinct sizes and shapes that includes thermodynamic and kinetic considerations. Then, we perform experiments demonstrating the hierarchical assembly of QDs into macroscopic structures. Despite theory predicting the formation of chains, we observe a macroscopic foam-like cellular phase when the QDs experience a combination of alternating current (AC) and direct current (DC) voltages. The resulting materials are both highly hierarchical in that they are 200 µm thick materials comprised of 20 nm particles, but they also represent extremely low-density materials. Finally, we report the invention of a novel instrument for imaging hierarchical materials. Specifically, we describe a massively parallel atomic force microscope with >1000 probes that is made possible through the combination of a new cantilever-free probe architecture and a scalable optical method for detecting probe-sample contact that provides sub-10 nm vertical precision. / 2022-09-28T00:00:00Z

There is a need to discover advanced materials to address the pressing challenges facing humanity, however there are far too many combinations of material composition and processing conditions to explore using conventional experimentation. One powerful approach for accelerating the rate at which materials are explored is by miniaturizing the scale at which experiments take place. Reducing the size of samples has been tremendously productive in biomedicine and drug discovery through standardized formats such as microwell plates, and while these formats may not be the most appropriate for studying polymeric materials, they do highlight the advantages of studying materials in ultra-miniaturized volumes. However, precise and controlled methods for handling diverse samples at the sub-femtoliter-scale have not been demonstrated. In this thesis, we establish that scanning probes can be used as a technique for realizing and interrogating sub-femtoliter scale polymer samples. To do this, we develop and apply methods for patterning materials with control over their size and composition and then use these methods to study material systems of interest. First, we develop a closed-loop method for patterning liquid samples using scanning probes by utilizing tipless cantilevers capable of holding a discrete liquid drop together with an inertial mass sensing scheme to measure the amount of liquid loaded on the probe. Using these innovations, we perform patterning with better than 1% mass accuracy on the pL-scale. While dispensing fluid with tipless cantilevers is successful for patterning pL-scale features and can be considered a candidate for robust nanoscale manipulation of liquids for high-throughput sample preparation, the minimum amount of liquid that can be transferred using this method is limited by number of factors. Thus, in the second section of this thesis, we explore ultrafast cantilevers that feature spherical tips and find them capable of patterning aL-scale features with in situ feedback. The development of methods of interrogating polymers at the pL-scale led us to explore how the mechanical properties of photocurable polymers depend on processing conditions. Specifically, we investigate the degree to which oxygen inhibits photocrosslinking during vat polymerization and how this effect influences the mechanical properties of the final material. We explore this through a series of macroscopic compression studies and AFM-based indentation studies of the cured polymers. Ultimately, the mechanical properties of these systems are compared to pL-scale features patterned using scanning probe lithography and we find that not only does oxygen prevent full crosslinking when it is present during the post-print curing, but the presence of oxygen during printing itself irreversibly softens the material. In addition to developing new methods for realizing ultra-miniaturized samples for study, the novel scanning probe methods in this work have led to new paradigms for rapidly evaluating complex interactions between material systems. In particular, we present a novel method to quantitatively investigate the interaction between the metal-organic frameworks (MOFs) and polymers by attaching a single MOF particle to a cantilever and studying the interaction force between this MOF and model polymer surfaces. Using this approach, we find direct evidence supporting the intercalation of polymer chains into the pores of MOFs. This work lays the foundation for directly characterizing the facet-specific interactions between MOFs and polymers in a high-throughput manner sufficient to fuel a data-driven accelerated material discovery pipeline. Collectively, the focus of this thesis is the development and utilization of novel scanning probe methods to collect data on extremely small systems and advance our understanding of important classes of materials. We expect this thesis to provide the foundation needed to transform scanning probe systems into instruments for performing reliable nanochemistry by combining controlled and quantitative sample preparation at the nanoscale and high-throughput characterization of materials. To conclude, we present an outlook about the necessary technological advancements and promising directions for materials innovations that stem from this work.

No description available.

Since the discovery of carbon nanotubes (CNT) in 1999, they have attracted much attention due to their unique mechanical and electrical properties and potential applications. Yet their nanosize makes the study of individual CNTs easier said than done. In our laboratory, carbon fibers with nanotube cores have been synthesized with conventional chemical vapor deposition (CVD) method. The single multiwall carbon nanotube (MWNT) sticks out as a tip of the carbon fiber. In order to pick up the individual CNT tips, focused ion beam (FIB) technique is applied to cut and adhere the samples. The carbon fiber with nanotube tip was first adhered on a micro-manipulator with the FIB welding function. Afterwards, by applying the FIB milling function, the fiber was cut from the base. This enables us to handle the individual CNT tips conveniently. By the same method, we can attach the nanotube tip on any geometry of solid samples such as conventional atomic force microscopy (AFM) silicon tips. The procedures developed for the FIB assisted individual CNT tip fabrication will be described in detail. Because of their excellent electrical and stable chemical properties, individual CNTs are potential candidates as electron guns for electron based microscopes to produce highly coherent electron beams. Due to the flexibility of the FIB fabrication, the individual CNT tips can be easily fabricated on a sharpened clean tungsten wire for field emission (FE) experimentation. Another promising application for individual CNT tips is as AFM probes. The high aspect ratio and mechanical resilience make individual CNTs ideal for scanning probe microscopy (SPM) tips. Atomic force microscopy with nanotube tips allows us to image relatively deep features of the sample surface at near nanometer resolution. Characterization of AFM with individual CNT tips and field emission properties of single CNT emitters will be studied and presented.

The focus of this dissertation is the study of measuring light not by energy transfer as is done with a standard photodetector such as a photographic film or charged coupled device, but rather by the forces which the light exerts on matter. In this manner we are able to replace or complement standard photodetector-based light detection techniques. One key attribute of force detection is that it permits the measurement of light over a very large range of frequencies including those which are difficult to access with standard photodetectors, such as the far IR and THz. The dissertation addresses the specific phenomena associated with optically induced force (OIF) detection in the near-field where light can be detected with high spatial resolution close to material interfaces. This is accomplished using a scanning probe microscope (SPM), which has the advantage of already having a sensitive force detector integrated into the system. The two microscopies we focus on here are atomic force microscopy (AFM) and nearfield scanning optical microscopy (NSOM). By detecting surface-induced forces or force gradients applied to a very small size probe (~ 20 nm diameter), AFM measures the force acting on the probe as a function of the tip-sample separation or extracts topography information. Typical NSOM utilizes either a small aperture (~ 50 150  nm diameter) to collect and/or radiate light in a small volume or a small scatterer (~ 20 nm diameter) in order to scatter light in a very small volume. This light is then measured with an avalanche photodiode or a photomultiplier tube. These two modalities may be combined in order to simultaneously map the local intensity distribution and topography of a sample of interest. A critical assumption made when performing iv such a measurement is that the distance regulation, which is based on surface induced forces, and the intensity distribution are independent. In other words, it is assumed that the presence of optical fields does not influence the AFM operation. However, it is well known that light exerts forces on the matter with which it interacts. This light-induced force may affect the atomic force microscope tip-sample distance regulation mechanism or, by modifying the tip, it may also indirectly influence the distance between the probe and the surface. This dissertation will present evidence that the effect of optically induced forces is strong enough to be observed when performing typical NSOM measurements. This effect is first studied on common experimental situations to show where and how these forces manifest themselves. Afterward, several new measurement approaches are demonstrated, which take advantage of this additional information to either complement or replace standard NSOM detection. For example, the force acting on the probe can be detected while simultaneously extracting the tip-sample separation, a measurement characteristic which is typically difficult to obtain. Moreover, the standard field collection with an aperture NSOM and the measurement of optically induced forces can be operated simultaneously. Thus, complementary information about the field intensity and its gradient can be, for the first time, collected with a single probe. Finally, a new scanning probe modality, multi-frequency NSOM (MF-NSOM), will be demonstrated. In this approach, the tuning fork is driven electrically at one frequency to perform a standard tip-sample distance regulation to follow the sample topography and optically driven at another frequency to measure the optically induced force. This novel technique provides a viable alternative to standard NSOM scanning and should be of particular interest in the long wavelength regime, e.g. far IR and THz.

No description available.