The goal of this thesis was the advanced design, fabrication, and application of combined atomic force microscopy - scanning electrochemical microscopy (AFMSECM) probes for high-resolution topographical and electrochemical imaging. The first part of the thesis describes innovative approaches for the optimization of AFM-SECM probe fabrication with recessed frame electrodes. For this purpose, commercial silicon nitride AFM cantilevers were modified using optimized critical fabrication processes including improved metallization for the deposition of the electrode layer, and novel insulation strategies for ensuring localized electrochemical signals. As a novel approach for the insulation of AFM-SECM probes, sandwiched layers of PECVD SixNy and SiO2, and plasma-deposited PFE films were applied and tested. Using sandwiched PECVD SixNy and SiO2 layers, AFM-SECM probes providing straight (unbent) cantilevers along with excellent insulation characteristics facilitating the functionality of the integrated electrode were reproducibly obtained. Alternatively, PFE thin films were tested according to their utility for serving as a mechanically flexible insulating layer for AFM-SECM probes. The electrochemical characterization of PFEinsulated AFM-SECM probes revealed excellent insulating properties at an insulation thickness of only approx. 400 nm. Finally, AFM-SECM cantilevers prepared via both insulation strategies were successfully tested during AFM-SECM imaging experiments. In the second part of this thesis, disk-shaped nanoelectrodes were for the first time integrated into AFM probes for enabling high-resolution AFM-SECM measurements. Disk electrodes with an electrode radius < 100 nm were realized, which provides a significantly improved lateral resolution for SECM experiments performed in synchronicity with AFM imaging. Furthermore, the developed fabrication scheme enables producing AFM-SECM probes with integrated disk nanoelectrodes at significantly reduced time and cost based on a highly reproducible semi-batch fabrication process providing bifunctional probes at a wafer scale. The development of a detailed processing strategy was accompanied by extensive simulation results for developing a fundamental understanding on the electrochemical properties of AFM-SECM probes with nanoscale electrodes, and for optimizing the associated processing parameters. Thus fabricated probes were electrochemically characterized, and their performance was demonstrated via bifunctional imaging at model samples. The third part of this thesis describes the development and characterization of the first AFM tip-integrated potentiometric sensors based on solid-state electrodes with submicrometer dimensions enabling laterally resolved pH imaging. Antimony and iridium oxides were applied as the pH sensitive electrode material, and have been integrated into the AFM probes via conventional microfabrication strategies. The pH response of such AFM tip-integrated integrated pH microsensors was tested for both material systems, and first studies were performed demonstrating localized pH measurements at a model system.

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.

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

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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.

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No description available.