Cavity-enhanced spectroscopies for applications of remote sensing, chemical kinetics and detection of radical species

This thesis describes applications of cavity enhanced spectroscopy towards applications of remote sensing, chemical kinetics and detection of transient radical molecular species. Both direct absorption spectroscopy and cavity ring-down spectroscopy are used in this work. Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was utilized for measurements of spectral lineshapes of O₂ and CO₂ for obtaining laboratory reference data in support of NASA’s OCO-2 mission. FS-CRDS is highly sensitive (> 10 km absorption path length) and precise (> 10000:1 SNR), making it ideal to study subtle non-Voigt lineshape effects. In addition, these advantages of FS-CRDS were further extended for measuring kinetic isotope effects: A dual-wavelength variation of FS-CRDS was used for measuring precise D/H and ¹³C/¹²C methane isotope ratios (sigma>0.026%) for the purpose of measuring the temperature dependent kinetic isotope effects of methane oxidation with O(¹D) and OH radicals. Finally, direct absorption spectroscopic detection of the trans-DOCO radical via a frequency combs spectrometer was conducted in collaboration with professor Jun Ye at JILA/University of Colorado.

Scalable Methods for Deterministic Integration of Quantum Emitters in Photonic Crystal Cavities

We investigated four unique methods for achieving scalable, deterministic integration of quantum emitters into ultra-high Q{V photonic crystal cavities, including selective area heteroepitaxy, engineered photoemission from silicon nanostructures, wafer bonding and dimensional reduction of III-V quantum wells, and cavity-enhanced optical trapping. In these areas, we were able to demonstrate site-selective heteroepitaxy, size-tunable photoluminescence from silicon nanostructures, Purcell modification of QW emission spectra, and limits of cavity-enhanced optical trapping designs which exceed any reports in the literature and suggest the feasibility of capturing- and detecting nanostructures with dimensions below 10 nm. In addition to process scalability and the requirement for achieving accurate spectral- and spatial overlap between the emitter and cavity, these techniques paid specific attention to the ability to separate the cavity and emitter material systems in order to allow optimal selection of these independently, and eventually enable monolithic integration with other photonic and electronic circuitry.

We also developed an analytic photonic crystal design process yielding optimized cavity tapers with minimal computational effort, and reported on a general cavity modification which exhibits improved fabrication tolerance by relying exclusively on positional- rather than dimensional tapering. We compared several experimental coupling techniques for device characterization. Significant efforts were devoted to optimizing cavity fabrication, including the use of atomic layer deposition to improve surface quality, exploration into factors affecting the design fracturing, and automated analysis of SEM images. Using optimized fabrication procedures, we experimentally demonstrated 1D photonic crystal nanobeam cavities exhibiting the highest Q/V reported on substrate. Finally, we analyzed the bistable behavior of the devices to quantify the nonlinear optical response of our cavities.

Metaconcrete: Engineered aggregates for enhanced dynamic performance

This work presents the development and investigation of a new type of concrete for the attenuation of waves induced by dynamic excitation. Recent progress in the field of metamaterials science has led to a range of novel composites which display unusual properties when interacting with electromagnetic, acoustic, and elastic waves. A new structural metamaterial with enhanced properties for dynamic loading applications is presented, which is named metaconcrete. In this new composite material the standard stone and gravel aggregates of regular concrete are replaced with spherical engineered inclusions. Each metaconcrete aggregate has a layered structure, consisting of a heavy core and a thin compliant outer coating. This structure allows for resonance at or near the eigenfrequencies of the inclusions, and the aggregates can be tuned so that resonant oscillations will be activated by particular frequencies of an applied dynamic loading. The activation of resonance within the aggregates causes the overall system to exhibit negative effective mass, which leads to attenuation of the applied wave motion. To investigate the behavior of metaconcrete slabs under a variety of different loading conditions a finite element slab model containing a periodic array of aggregates is utilized. The frequency dependent nature of metaconcrete is investigated by considering the transmission of wave energy through a slab, which indicates the presence of large attenuation bands near the resonant frequencies of the aggregates. Applying a blast wave loading to both an elastic slab and a slab model that incorporates the fracture characteristics of the mortar matrix reveals that a significant portion of the supplied energy can be absorbed by aggregates which are activated by the chosen blast wave profile. The transfer of energy from the mortar matrix to the metaconcrete aggregates leads to a significant reduction in the maximum longitudinal stress, greatly improving the ability of the material to resist damage induced by a propagating shock wave. The various analyses presented in this work provide the theoretical and numerical background necessary for the informed design and development of metaconcrete aggregates for dynamic loading applications, such as blast shielding, impact protection, and seismic mitigation.

Nonlinear optics and wavelength translation via cavity-optomechanics

The field of cavity-optomechanics explores the interaction of light with sound in an ever increasing array of devices. This interaction allows the mechanical system to be both sensed and controlled by the optical system, opening up a wide variety of experiments including the cooling of the mechanical resonator to its quantum mechanical ground state and the squeezing of the optical field upon interaction with the mechanical resonator, to name two.

In this work we explore two very different systems with different types of optomechanical coupling. The first system consists of two microdisk optical resonators stacked on top of each other and separated by a very small slot. The interaction of the disks causes their optical resonance frequencies to be extremely sensitive to the gap between the disks. By careful control of the gap between the disks, the optomechanical coupling can be made to be quadratic to first order which is uncommon in optomechanical systems. With this quadratic coupling the light field is now sensitive to the energy of the mechanical resonator and can directly control the potential energy trapping the mechanical motion. This ability to directly control the spring constant without modifying the energy of the mechanical system, unlike in linear optomechanical coupling, is explored.

Next, the bulk of this thesis deals with a high mechanical frequency optomechanical crystal which is used to coherently convert photons between different frequencies. This is accomplished via the engineered linear optomechanical coupling in these devices. Both classical and quantum systems utilize the interaction of light and matter across a wide range of energies. These systems are often not naturally compatible with one another and require a means of converting photons of dissimilar wavelengths to combine and exploit their different strengths. Here we theoretically propose and experimentally demonstrate coherent wavelength conversion of optical photons using photon-phonon translation in a cavity-optomechanical system. For an engineered silicon optomechanical crystal nanocavity supporting a 4 GHz localized phonon mode, optical signals in a 1.5 MHz bandwidth are coherently converted over a 11.2 THz frequency span between one cavity mode at wavelength 1460 nm and a second cavity mode at 1545 nm with a 93% internal (2% external) peak efficiency. The thermal and quantum limiting noise involved in the conversion process is also analyzed and, in terms of an equivalent photon number signal level, are found to correspond to an internal noise level of only 6 and 4 times 10x^-3 quanta, respectively.

We begin by developing the requisite theoretical background to describe the system. A significant amount of time is then spent describing the fabrication of these silicon nanobeams, with an emphasis on understanding the specifics and motivation. The experimental demonstration of wavelength conversion is then described and analyzed. It is determined that the method of getting photons into the cavity and collected from the cavity is a fundamental limiting factor in the overall efficiency. Finally, a new coupling scheme is designed, fabricated, and tested that provides a means of coupling greater than 90% of photons into and out of the cavity, addressing one of the largest obstacles with the initial wavelength conversion experiment.

Dynamics of rotationally resolved multiphoton ionization processes in molecules

This dissertation presents the results of studies of several rotationally- resolved resonance enhanced multiphoton ionization (REMPI) processes in some simple molecular systems. The objective of these studies is to quantitatively identify the underlying dynamics of this highly state-specific process which utilizes the narrow bandwidth radiation of a laser to ionize a molecule by first preparing an excited state via multiphoton absorption and subsequently ionizing that state before it can decay. Coupled with high-resolution photoelectron spectroscopy, REMPI is clearly an important probe of molecular excited states and their photoioniza tion dynamics.

A key feature of our studies is that they are carried out using accurate Hartree-Fock orbitals to describe the photoelectron orbitals of the molecular ions. The use of such photoelectron orbitals is important in rotationally-resolved studies where the angular momentum coupling in the photoelectron orbital plays a significant role in the photoionization dynamics. In these studies the Hartree-Fock molecular molecular photoelectron orbitals are obtained by numerical solution of a Lippmann-Schwinger integral equation.

Studies reported here include investigations of (i) ionic rotational branching ratios and their energy dependence for REMPI via the A^2Σ^+(3sσ) and D^2Σ^+(3pσ)states of NO, (ii) the influence of angular momentum constraints on branching ratios at low photoelectron energies for REMPI via low-J levels of the resonant intermediate state, (iii) the strong dependence of photoelectron angular distributions on final ionic rotational state and on the alignment in REMPI of the A^2Σ^+ state of NO, (iv) vibrational state dependence of ionic rotational branching ratios arising from rapid orbital evolution in resonant states (E'^2Σ^+(3pσ) of CH), (v) the influence of rovibronic interactions on the rotational branching ratios seen in REMPI via the D^2Σ^+(3pσ) state of NO, and (vi) effects of laser intensity on the photoionization dynamics of REMPI.

Phase conjugation via four-wave mixing in a resonant medium

This thesis describes the theoretical solution and experimental verification of phase conjugation via nondegenerate four-wave mixing in resonant media. The theoretical work models the resonant medium as a two-level atomic system with the lower state of the system being the ground state of the atom. Working initially with an ensemble of stationary atoms, the density matrix equations are solved by third-order perturbation theory in the presence of the four applied electro-magnetic fields which are assumed to be nearly resonant with the atomic transition. Two of the applied fields are assumed to be non-depleted counterpropagating pump waves while the third wave is an incident signal wave. The fourth wave is the phase conjugate wave which is generated by the interaction of the three previous waves with the nonlinear medium. The solution of the density matrix equations gives the local polarization of the atom. The polarization is used in Maxwell's equations as a source term to solve for the propagation and generation of the signal wave and phase conjugate wave through the nonlinear medium. Studying the dependence of the phase conjugate signal on the various parameters such as frequency, we show how an ultrahigh-Q isotropically sensitive optical filter can be constructed using the phase conjugation process.

In many cases the pump waves may saturate the resonant medium so we also present another solution to the density matrix equations which is correct to all orders in the amplitude of the pump waves since the third-order solution is correct only to first-order in each of the field amplitudes. In the saturated regime, we predict several new phenomena associated with degenerate four-wave mixing and also describe the ac Stark effect and how it modifies the frequency response of the filtering process. We also show how a narrow bandwidth optical filter with an efficiency greater than unity can be constructed.

In many atomic systems the atoms are moving at significant velocities such that the Doppler linewidth of the system is larger than the homogeneous linewidth. The latter linewidth dominates the response of the ensemble of stationary atoms. To better understand this case the density matrix equations are solved to third-order by perturbation theory for an atom of velocity v. The solution for the polarization is then integrated over the velocity distribution of the macroscopic system which is assumed to be a gaussian distribution of velocities since that is an excellent model of many real systems. Using the Doppler broadened system, we explain how a tunable optical filter can be constructed whose bandwidth is limited by the homogeneous linewidth of the atom while the tuning range of the filter extends over the entire Doppler profile.

Since it is a resonant system, sodium vapor is used as the nonlinear medium in our experiments. The relevant properties of sodium are discussed in great detail. In particular, the wavefunctions of the 3S and 3P states are analyzed and a discussion of how the 3S-3P transition models a two-level system is given.

Using sodium as the nonlinear medium we demonstrate an ultrahigh-Q optical filter using phase conjugation via nondegenerate four-wave mixing as the filtering process. The filter has a FWHM bandwidth of 41 MHz and a maximum efficiency of 4 x 10^-3. However, our theoretical work and other experimental work with sodium suggest that an efficient filter with both gain and a narrower bandwidth should be quite feasible.

Upper hybrid resonance absorption and scattering from a plasma column

The electromagnetic scattering and absorption properties of small (kr~1/2) inhomogeneous magnetoplasma columns are calculated via the full set of Maxwell's equations with tensor dielectric constitutive relation. The cold plasma model with collisional damping is used to describe the column. The equations are solved numerically, subject to boundary conditions appropriate to an infinite parallel strip line and to an incident plane wave. The results are similar for several density profiles and exhibit semiquantitative agreement with measurements in waveguide. The absorption is spatially limited, especially for small collision frequency, to a narrow hybrid resonant layer and is essentially zero when there is no hybrid layer in the column. The reflection is also enhanced when the hybrid layer is present, but the value of the reflection coefficient is strongly modified by the presence of the glass tube. The nature of the solutions and an extensive discussion of the conditions under which the cold collisional model should yield valid results is presented.

Enhanced Thermoelectric Performance at the Superionic Phase Transitions of Mixed Ion-Electron Conducting Materials

The quality of a thermoelectric material is judged by the size of its temperature de- pendent thermoeletric-figure-of-merit (zT ). Superionic materials, particularly Zn₄Sb₃ and Cu₂Se, are of current interest for the high zT and low thermal conductivity of their disordered, superionic phase. In this work it is reported that the super-ionic materials Ag₂Se, Cu₂Se and Cu_1.97Ag_0.03Se show enhanced zT in their ordered, normal ion-conducting phases. The zT of Ag₂Se is increased by 30% in its ordered phase as compared to its disordered phase, as measured just below and above its first order phase transition. The zT ’s of Cu₂Se and Cu_1.97Ag_0.03Se both increase by more than 100% over a 30 K temperatures range just below their super-ionic phase transitions. The peak zT of Cu₂Se is 0.7 at 406 K and of Cu_1.97Ag_0.03Se is 1.0 at 400 K. In all three materials these enhancements are due to anomalous increases in their Seebeck coefficients, beyond that predicted by carrier concentration measurements and band structure modeling. As the Seebeck coefficient is the entropy transported per carrier, this suggests that there is an additional quantity of entropy co-transported with charge carriers. Such co-transport has been previously observed via co-transport of vibrational entropy in bipolaron conductors and spin-state entropy in Na_xCo₂O₄. The correlation of the temperature profile of the increases in each material with the nature of their phase transitions indicates that the entropy is associated with the thermodynamcis of ion-ordering. This suggests a new mechanism by which high thermoelectric performance may be understood and engineered.

Nanofabrication for On-Chip Optical Levitation, Atom-Trapping, and Superconducting Quantum Circuits

Researchers have spent decades refining and improving their methods for fabricating smaller, finer-tuned, higher-quality nanoscale optical elements with the goal of making more sensitive and accurate measurements of the world around them using optics. Quantum optics has been a well-established tool of choice in making these increasingly sensitive measurements which have repeatedly pushed the limits on the accuracy of measurement set forth by quantum mechanics. A recent development in quantum optics has been a creative integration of robust, high-quality, and well-established macroscopic experimental systems with highly-engineerable on-chip nanoscale oscillators fabricated in cleanrooms. However, merging large systems with nanoscale oscillators often require them to have extremely high aspect-ratios, which make them extremely delicate and difficult to fabricate with an "experimentally reasonable" repeatability, yield and high quality. In this work we give an overview of our research, which focused on microscopic oscillators which are coupled with macroscopic optical cavities towards the goal of cooling them to their motional ground state in room temperature environments. The quality factor of a mechanical resonator is an important figure of merit for various sensing applications and observing quantum behavior. We demonstrated a technique for pushing the quality factor of a micromechanical resonator beyond conventional material and fabrication limits by using an optical field to stiffen and trap a particular motional mode of a nanoscale oscillator. Optical forces increase the oscillation frequency by storing most of the mechanical energy in a nearly loss-less optical potential, thereby strongly diluting the effects of material dissipation. By placing a 130 nm thick SiO₂ pendulum in an optical standing wave, we achieve an increase in the pendulum center-of-mass frequency from 6.2 to 145 kHz. The corresponding quality factor increases 50-fold from its intrinsic value to a final value of Q_m = 5.8(1.1) x 10⁵, representing more than an order of magnitude improvement over the conventional limits of SiO₂ for a pendulum geometry. Our technique may enable new opportunities for mechanical sensing and facilitate observations of quantum behavior in this class of mechanical systems. We then give a detailed overview of the techniques used to produce high-aspect-ratio nanostructures with applications in a wide range of quantum optics experiments. The ability to fabricate such nanodevices with high precision opens the door to a vast array of experiments which integrate macroscopic optical setups with lithographically engineered nanodevices. Coupled with atom-trapping experiments in the Kimble Lab, we use these techniques to realize a new waveguide chip designed to address ultra-cold atoms along lithographically patterned nanobeams which have large atom-photon coupling and near 4π Steradian optical access for cooling and trapping atoms. We describe a fully integrated and scalable design where cold atoms are spatially overlapped with the nanostring cavities in order to observe a resonant optical depth of d₀ ≈ 0.15. The nanodevice illuminates new possibilities for integrating atoms into photonic circuits and engineering quantum states of atoms and light on a microscopic scale. We then describe our work with superconducting microwave resonators coupled to a phononic cavity towards the goal of building an integrated device for quantum-limited microwave-to-optical wavelength conversion. We give an overview of our characterizations of several types of substrates for fabricating a low-loss high-frequency electromechanical system. We describe our electromechanical system fabricated on a Si₃N₄ membrane which consists of a 12 GHz superconducting LC resonator coupled capacitively to the high frequency localized modes of a phononic nanobeam. Using our suspended membrane geometry we isolate our system from substrates with significant loss tangents, drastically reducing the parasitic capacitance of our superconducting circuit to ≈ 2.5$ fF. This opens up a number of possibilities in making a new class of low-loss high-frequency electromechanics with relatively large electromechanical coupling. We present our substrate studies, fabrication methods, and device characterization.

Acceleration Sensing, Feedback Cooling, and Nonlinear Dynamics with Nanoscale Cavity-Optomechanical Devices

Light has long been used for the precise measurement of moving bodies, but the burgeoning field of optomechanics is concerned with the interaction of light and matter in a regime where the typically weak radiation pressure force of light is able to push back on the moving object. This field began with the realization in the late 1960's that the momentum imparted by a recoiling photon on a mirror would place fundamental limits on the smallest measurable displacement of that mirror. This coupling between the frequency of light and the motion of a mechanical object does much more than simply add noise, however. It has been used to cool objects to their quantum ground state, demonstrate electromagnetically-induced-transparency, and modify the damping and spring constant of the resonator. Amazingly, these radiation pressure effects have now been demonstrated in systems ranging 18 orders of magnitude in mass (kg to fg).

In this work we will focus on three diverse experiments in three different optomechanical devices which span the fields of inertial sensors, closed-loop feedback, and nonlinear dynamics. The mechanical elements presented cover 6 orders of magnitude in mass (ng to fg), but they all employ nano-scale photonic crystals to trap light and resonantly enhance the light-matter interaction. In the first experiment we take advantage of the sub-femtometer displacement resolution of our photonic crystals to demonstrate a sensitive chip-scale optical accelerometer with a kHz-frequency mechanical resonator. This sensor has a noise density of approximately 10 micro-g/rt-Hz over a useable bandwidth of approximately 20 kHz and we demonstrate at least 50 dB of linear dynamic sensor range. We also discuss methods to further improve performance of this device by a factor of 10.

In the second experiment, we used a closed-loop measurement and feedback system to damp and cool a room-temperature MHz-frequency mechanical oscillator from a phonon occupation of 6.5 million down to just 66. At the time of the experiment, this represented a world-record result for the laser cooling of a macroscopic mechanical element without the aid of cryogenic pre-cooling. Furthermore, this closed-loop damping yields a high-resolution force sensor with a practical bandwidth of 200 kHZ and the method has applications to other optomechanical sensors.

The final experiment contains results from a GHz-frequency mechanical resonator in a regime where the nonlinearity of the radiation-pressure interaction dominates the system dynamics. In this device we show self-oscillations of the mechanical element that are driven by multi-photon-phonon scattering. Control of the system allows us to initialize the mechanical oscillator into a stable high-amplitude attractor which would otherwise be inaccessible. To provide context, we begin this work by first presenting an intuitive overview of optomechanical systems and then providing an extended discussion of the principles underlying the design and fabrication of our optomechanical devices.

Cavity Optomechanics at Millikelvin Temperatures

The field of cavity optomechanics, which concerns the coupling of a mechanical object's motion to the electromagnetic field of a high finesse cavity, allows for exquisitely sensitive measurements of mechanical motion, from large-scale gravitational wave detection to microscale accelerometers. Moreover, it provides a potential means to control and engineer the state of a macroscopic mechanical object at the quantum level, provided one can realize sufficiently strong interaction strengths relative to the ambient thermal noise. Recent experiments utilizing the optomechanical interaction to cool mechanical resonators to their motional quantum ground state allow for a variety of quantum engineering applications, including preparation of non-classical mechanical states and coherent optical to microwave conversion. Optomechanical crystals (OMCs), in which bandgaps for both optical and mechanical waves can be introduced through patterning of a material, provide one particularly attractive means for realizing strong interactions between high-frequency mechanical resonators and near-infrared light. Beyond the usual paradigm of cavity optomechanics involving isolated single mechanical elements, OMCs can also be fashioned into planar circuits for photons and phonons, and arrays of optomechanical elements can be interconnected via optical and acoustic waveguides. Such coupled OMC arrays have been proposed as a way to realize quantum optomechanical memories, nanomechanical circuits for continuous variable quantum information processing and phononic quantum networks, and as a platform for engineering and studying quantum many-body physics of optomechanical meta-materials.

However, while ground state occupancies (that is, average phonon occupancies less than one) have been achieved in OMC cavities utilizing laser cooling techniques, parasitic absorption and the concomitant degradation of the mechanical quality factor fundamentally limit this approach. On the other hand, the high mechanical frequency of these systems allows for the possibility of using a dilution refrigerator to simultaneously achieve low thermal occupancy and long mechanical coherence time by passively cooling the device to the millikelvin regime. This thesis describes efforts to realize the measurement of OMC cavities inside a dilution refrigerator, including the development of fridge-compatible optical coupling schemes and the characterization of the heating dynamics of the mechanical resonator at sub-kelvin temperatures.

We will begin by summarizing the theoretical framework used to describe cavity optomechanical systems, as well as a handful of the quantum applications envisioned for such devices. Then, we will present background on the design of the nanobeam OMC cavities used for this work, along with details of the design and characterization of tapered fiber couplers for optical coupling inside the fridge. Finally, we will present measurements of the devices at fridge base temperatures of T_f = 10 mK, using both heterodyne spectroscopy and time-resolved sideband photon counting, as well as detailed analysis of the prospects for future quantum applications based on the observed optically-induced heating.

Part I - The radiation of elastic waves from a spherical cavity in a half space. Part II - Precision determination of focal depths and epicenters of earthquakes.

Part I: The dynamic response of an elastic half space to an explosion in a buried spherical cavity is investigated by two methods. The first is implicit, and the final expressions for the displacements at the free surface are given as a series of spherical wave functions whose coefficients are solutions of an infinite set of linear equations. The second method is based on Schwarz's technique to solve boundary value problems, and leads to an iterative solution, starting with the known expression for the point source in a half space as first term. The iterative series is transformed into a system of two integral equations, and into an equivalent set of linear equations. In this way, a dual interpretation of the physical phenomena is achieved. The systems are treated numerically and the Rayleigh wave part of the displacements is given in the frequency domain. Several comparisons with simpler cases are analyzed to show the effect of the cavity radius-depth ratio on the spectra of the displacements.

Part II: A high speed, large capacity, hypocenter location program has been written for an IBM 7094 computer. Important modifications to the standard method of least squares have been incorporated in it. Among them are a new way to obtain the depth of shocks from the normal equations, and the computation of variable travel times for the local shocks in order to account automatically for crustal variations. The multiregional travel times, largely based upon the investigations of the United States Geological Survey, are confronted with actual traverses to test their validity.

It is shown that several crustal phases provide control enough to obtain good solutions in depth for nuclear explosions, though not all the recording stations are in the region where crustal corrections are considered. The use of the European travel times, to locate the French nuclear explosion of May 1962 in the Sahara, proved to be more adequate than previous work.

A simpler program, with manual crustal corrections, is used to process the Kern County series of aftershocks, and a clearer picture of tectonic mechanism of the White Wolf fault is obtained.

Shocks in the California region are processed automatically and statistical frequency-depth and energy depth curves are discussed in relation to the tectonics of the area.

Polaron hopping in olivine phosphates studied by nuclear resonant scattering

Valence fluctuations of Fe²⁺ and Fe³⁺ were studied in a solid solution of Li_xFePO₄ by nuclear resonant forward scattering of synchrotron x rays while the sample was heated in a diamond-anvil pressure cell. The spectra acquired at different temperatures and pressures were analyzed for the frequencies of valence changes using the Blume-Tjon model of a system with a fluctuating Hamil- tonian. These frequencies were analyzed to obtain activation energies and an activation volume for polaron hopping. There was a large suppression of hopping frequency with pressure, giving an anomalously large activation volume. This large, positive value is typical of ion diffusion, which indicates correlated motions of polarons, and Li⁺ ions that alter the dynamics of both.

In a parallel study of Na_xFePO₄, the interplay between sodium ordering and electron mobility was investigated using a combination of synchrotron x-ray diffraction and nuclear resonant scattering. Conventional Mossbauer spectra were collected while the sample was heated in a resistive furnace. An analysis of the temperature evolution of the spectral shapes was used to identify the onset of fast electron hopping and determine the polaron hopping rate. Synchrotron x-ray diffraction measurements were carried out in the same temperature range. Reitveld analysis of the diffraction patterns was used to determine the temperature of sodium redistribution on the lattice. The diffraction analysis also provides new information about the phase stability of the system. The temperature evolution of the iron site occupancies from the Mossbauer measurements, combined with the synchrotron diffraction results give strong evidence for a relationship between the onset of fast electron dynamics and the redistribution of sodium in the lattice.

Measurements of activation barriers for polaron hopping gave fundamental insights about the correlation between electronic carriers and mobile ions. This work established that polaron-ion interactions can alter the local dynamics of electron and ion transport. These types of coupled processes may be common in many materials used for battery electrodes, and new details concerning the influence of polaron-ion interactions on the charge dynamics are relevant to optimizing their electrochemical performance.

Depth-sensitive analysis of fluorine on lunar sample surfaces and in carbonaceous chondrites by a nuclear resonant reaction technique

The nuclear resonant reaction ¹⁹F(ρ,αγ)¹⁶O has been used to perform depth-sensitive analyses of fluorine in lunar samples and carbonaceous chondrites. The resonance at 0.83 MeV (center-of-mass) in this reaction is utilized to study fluorine surface films, with particular interest paid to the outer micron of Apollo 15 green glass, Apollo 17 orange glass, and lunar vesicular basalts. These results are distinguished from terrestrial contamination, and are discussed in terms of a volcanic origin for the samples of interest. Measurements of fluorine in carbonaceous chondrites are used to better define the solar system fluorine abundance. A technique for measurement of carbon on solid surfaces with applications to direct quantitative analysis of implanted solar wind carbon in lunar samples is described.

High energy heavy ion induced enhanced adhesion

The work described in this thesis represents an attempt to summarize to date the information collected on the process of high energy heavy ion induced enhanced adhesion. Briefly, the process involves the irradiation of materials covered by thin (≾3μm) films with high energy (E > 200 keV I nucleon) heavy ion beams (such as Fluorine or Chlorine). Enhanced adhesion has been observed on all material combinations tested, including metal on metal, metal on semiconductor, metal on dielectric and dielectric on dielectric systems. In some cases, the enhancement can be quite large, so that a film that could be wiped off a substrate quite easily before irradiation can withstand determined scrubbing afterwards.

Very little is understood yet about this adhesion mechanism, so what is presented are primarily observations about systems studied, and descriptions of the actual preparation and irradiation of samples used. Some discussion is presented about mechanisms that have been considered but rejected.