Electrical and optical studies on carbon nanotube arrays

Single-walled carbon nanotubes (SWNTs) have been studied as a prominent class of high performance electronic materials for next generation electronics. Their geometry dependent electronic structure, ballistic transport and low power dissipation due to quasi one dimensional transport, and their capability of carrying high current densities are some of the main reasons for the optimistic expectations on SWNTs. However, device applications of individual SWNTs have been hindered by uncontrolled variations in characteristics and lack of scalable methods to integrate SWNTs into electronic devices. One relatively new direction in SWNT electronics, which avoids these issues, is using arrays of SWNTs, where the ensemble average may provide uniformity from device to device, and this new breed of electronic material can be integrated into electronic devices in a scalable fashion. This dissertation describes (1) methods for characterization of SWNT arrays, (2) how the electrical transport in these two-dimensional arrays depend on length scales and spatial anisotropy, (3) the interaction of aligned SWNTs with the underlying substrate, and (4) methods for scalable integration of SWNT arrays into electronic devices. The electrical characterization of SWNT arrays have been realized by polymer electrolyte-gated SWNT thin film transistors (TFTs). Polymer electrolyte-gating addresses many technical difficulties inherent to electrical characterization by gating through oxide-dielectrics. Having shown polymer electrolyte-gating can be successfully applied on SWNT arrays, we have studied the length scaling dependence of electrical transport in SWNT arrays. Ultrathin films formed by sub-monolayer surface coverage of SWNT arrays are very interesting systems in terms of the physics of two-dimensional electronic transport. We have observed that they behave qualitatively different than the classical conducting films, which obey the Ohm’s law. The resistance of an ultrathin film of SWNT arrays is indeed non-linear with the length of the film, across which the transport occurs. More interestingly, a transition between conducting and insulating states is observed at a critical surface coverage, which is called percolation limit. The surface coverage of conducting SWNTs can be manipulated by turning on and off the semiconductors in the SWNT array, leading to the operation principle of SWNT TFTs. The percolation limit depends also on the length and the spatial orientation of SWNTs. We have also observed that the percolation limit increases abruptly for aligned arrays of SWNTs, which are grown on single crystal quartz substrates. In this dissertation, we also compare our experimental results with a two-dimensional stick network model, which gives a good qualitative picture of the electrical transport in SWNT arrays in terms of surface coverage, length scaling, and spatial orientation, and briefly discuss the validity of this model. However, the electronic properties of SWNT arrays are not only determined by geometrical arguments. The contact resistances at the nanotube-nanotube and nanotube-electrode (bulk metal) interfaces, and interactions with the local chemical groups and the underlying substrates are among other issues related to the electronic transport in SWNT arrays. Different aspects of these factors have been studied in detail by many groups. In fact, I have also included a brief discussion about electron injection onto semiconducting SWNTs by polymer dopants. On the other hand, we have compared the substrate-SWNT interactions for isotropic (in two dimensions) arrays of SWNTs grown on Si/SiO2 substrates and horizontally (on substrate) aligned arrays of SWNTs grown on single crystal quartz substrates. The anisotropic interactions associated with the quartz lattice between quartz and SWNTs that allow near perfect horizontal alignment on substrate along a particular crystallographic direction is examined by Raman spectroscopy, and shown to lead to uniaxial compressive strain in as-grown SWNTs on single crystal quartz. This is the first experimental demonstration of the hard-to-achieve uniaxial compression of SWNTs. Temperature dependence of Raman G-band spectra along the length of individual nanotubes reveals that the compressive strain is non-uniform and can be larger than 1% locally at room temperature. Effects of device fabrication steps on the non-uniform strain are also examined and implications on electrical performance are discussed. Based on our findings, there are discussions about device performances and designs included in this dissertation. The channel length dependences of device mobilities and on/off ratios are included for SWNT TFTs. Time response of polymer-electrolyte gated SWNT TFTs has been measured to be ~300 Hz, and a proof-of-concept logic inverter has been fabricated by using polymer electrolyte gated SWNT TFTs for macroelectronic applications. Finally, I dedicated a chapter on scalable device designs based on aligned arrays of SWNTs, including a design for SWNT memory devices.

Digital nonlinear equalization for optical transmission systems

This thesis focuses on digital equalization of nonlinear fiber impairments for coherent optical transmission systems. Building from well-known physical models of signal propagation in single-mode optical fibers, novel nonlinear equalization techniques are proposed, numerically assessed and experimentally demonstrated. The structure of the proposed algorithms is strongly driven by the optimization of the performance versus complexity tradeoff, envisioning the near-future practical application in commercial real-time transceivers. The work is initially focused on the mitigation of intra-channel nonlinear impairments relying on the concept of digital backpropagation (DBP) associated with Volterra-based filtering. After a comprehensive analysis of the third-order Volterra kernel, a set of critical simplifications are identified, culminating in the development of reduced complexity nonlinear equalization algorithms formulated both in time and frequency domains. The implementation complexity of the proposed techniques is analytically described in terms of computational effort and processing latency, by determining the number of real multiplications per processed sample and the number of serial multiplications, respectively. The equalization performance is numerically and experimentally assessed through bit error rate (BER) measurements. Finally, the problem of inter-channel nonlinear compensation is addressed within the context of 400 Gb/s (400G) superchannels for long-haul and ultra-long-haul transmission. Different superchannel configurations and nonlinear equalization strategies are experimentally assessed, demonstrating that inter-subcarrier nonlinear equalization can provide an enhanced signal reach while requiring only marginal added complexity.

Intraplate versus ridge volcanism on the Pacific-Antarctic Ridge near 37°S -111°W

Exploration of the Foundation Volcanic Chain (33 degrees S-131 degrees W; 37 degrees S-111 degrees W) revealed the existence of different magmatic provinces with relation to their geological settings. (1) The Pacific-Antarctic Ridge (PAR) is made up of several en echelon segments where both glassy midocean ridge basalts (MORBs) with low incompatible elements (K2O<200 ppm, Zr<120 ppm and Ce <20 ppm) as well as andesites and dacites have erupted, (2) Oblique Ridges located up to 300 lan from the PAR axis are topped with seamounts made up essentially of transitional (T) and enriched (E) MORBs with intermediate incompatible elements (K2O=0.11-0.40 %, Zr=70-140 ppm and Ce=15-30 ppm), (3) the Foundation Seamounts (FS) consisting essentially of isolated volcanoes which have erupted alkalic lavas (alkali basalt, trachybasalt and trachyandesite) with high incompatible elements (K2O (0.50-1.1 %, Zr (>150 ppm) and Ce (>48 ppm)) at about 306-1300 km from the PAR axis, (4) The Old Pacific Seamounts built on a crust older than 23 m. y. located west of longitude 124 degrees W (> 1300 km from the PAR axis) consist of T and EMORB. On the PAR axis, extensive crystal fractionation (>65%) produced the silicic lavas. On the basis of Pacific plate reconstruction using a half spreading rate of about 50 mm/yr and integrating the observed compositional changes with respect to the structural settings, it is inferred that the last volcanic events giving rise to the FS took place at about 110 km from the PAR axis about 5 m. y. ago. The Oblique Ridges built between 5 m. y. and <1 m. y. are believed to represent ancient leaky transforms and/or large discontinuities between accreting ridge segments filled by volcanic cones during the interaction (mixing) of the enriched plume components of the FS with PAR depleted (MORB type) magmatism. The Old Pacific Seamounts built on ancient crust (>23 m. y.) with MORB volcanics comparable to those of the the Oblique Ridge-PAR provinces, could also have been formed by an interaction between the Foundation Seamount (dredge site 28) hotspot magmatism and that of an ancient accreting ridge magmatism precursor of the PAR.

Ontogeny and nutritional programming of the hepatic growth hormone-insulin-like growth factor-prolactin axis in the sheep

The liver is an important metabolic and endocrine organ in the fetus but the extent to which its hormone receptor (R) sensitivity is developmentally regulated in early life is not fully established. We, therefore, examined developmental changes in mRNA abundance for the growth hormone (GH) and prolactin (PRL) receptors (R) plus insulin-like growth factor (IGF)-I and –II and their receptors. Fetal and postnatal sheep were sampled at either 80, or 140 days gestation, 1, 30 days or six months of age. The effect of maternal nutrient restriction between early to mid (i.e. 28 to 80 days gestation, the time of early liver growth) gestation on gene expression was also examined in the fetus and juvenile offspring. Gene expression for the GHR, PRLR and IGF-IR increased through gestation peaking at birth, whereas IGF-I was maximal near to term. In contrast, IGF-II mRNA decreased between mid and late gestation to increase after birth whereas IGF-IIR remained unchanged. A substantial decline in mRNA abundance for GHR, PRLR and IGF-IR then occurred up to six months. Maternal nutrient restriction reduced GHR and IGF-IIR mRNA abundance in the fetus, but caused a precocious increase in the PRLR. Gene expression for IGF-I and –II were increased in juvenile offspring born to nutrient restricted mothers. In conclusion, there are marked differences in the developmental ontogeny and nutritional programming of specific hormones and their receptors involved in hepatic growth and development in the fetus. These could contribute to changes in liver function during adult life.

Near-infrared Instrumentation For Rapid-response Astronomy

Ɣ-ray bursts (GRBs) are the Universe's most luminous transient events. Since the discovery of GRBs was announced in 1973, efforts have been ongoing to obtain data over a broader range of the electromagnetic spectrum at the earliest possible times following the initial detection. The discovery of the theorized ``afterglow'' emission in radio through X-ray bands in the late 1990s confirmed the cosmological nature of these events. At present, GRB afterglows are among the best probes of the early Universe (z ≳ 9). In addition to informing theories about GRBs themselves, observations of afterglows probe the circum-burst medium (CBM), properties of the host galaxies and the progress of cosmic reionization. To explore the early-time variability of afterglows, I have developed a generalized analysis framework which models near-infrared (NIR), optical, ultra-violet (UV) and X-ray light curves without assuming an underlying model. These fits are then used to construct the spectral energy distribution (SED) of afterglows at arbitrary times within the observed window. Physical models are then used to explore the evolution of the SED parameter space with time. I demonstrate that this framework produces evidence of the photodestruction of dust in the CBM of GRB 120119A, similar to the findings from a previous study of this afterglow. The framework is additionally applied to the afterglows of GRB 140419A and GRB 080607. In these cases the evolution of the SEDs appears consistent with the standard fireball model. Having introduced the scientific motivations for early-time observations, I introduce the Rapid Infrared Imager-Spectrometer (RIMAS). Once commissioned on the 4.3 meter Discovery Channel Telescope (DCT), RIMAS will be used to study the afterglows of GRBs through photometric and spectroscopic observations beginning within minutes of the initial burst. The instrument will operate in the NIR, from 0.97 μm to 2.37 μm, permitting the detection of very high redshift (z ≳ 7) afterglows which are attenuated at shorter wavelengths by Lyman-ɑ absorption in the intergalactic medium (IGM). A majority of my graduate work has been spent designing and aligning RIMAS's cryogenic (~80 K) optical systems. Design efforts have included an original camera used to image the field surrounding spectroscopic slits, tolerancing and optimizing all of the instrument's optics, thermal modeling of optomechanical systems, and modeling the diffraction efficiencies for some of the dispersive elements. To align the cryogenic optics, I developed a procedure that was successfully used for a majority of the instrument's sub-assemblies. My work on this cryogenic instrument has necessitated experimental and computational projects to design and validate designs of several subsystems. Two of these projects describe simple and effective measurements of optomechanical components in vacuum and at cryogenic temperatures using an 8-bit CCD camera. Models of heat transfer via electrical harnesses used to provide current to motors located within the cryostat are also presented.

In Situ Characterization of Optical Absorption by Carbonaceous Aerosols: Calibration and Measurement

Light absorption by aerosols has a great impact on climate change. A Photoacoustic spectrometer (PA) coupled with aerosol-based classification techniques represents an in situ method that can quantify the light absorption by aerosols in a real time, yet significant differences have been reported using this method versus filter based methods or the so-called difference method based upon light extinction and light scattering measurements. This dissertation focuses on developing calibration techniques for instruments used in measuring the light absorption cross section, including both particle diameter measurements by the differential mobility analyzer (DMA) and light absorption measurements by PA. Appropriate reference materials were explored for the calibration/validation of both measurements. The light absorption of carbonaceous aerosols was also investigated to provide fundamental understanding to the absorption mechanism. The first topic of interest in this dissertation is the development of calibration nanoparticles. In this study, bionanoparticles were confirmed to be a promising reference material for particle diameter as well as ion-mobility. Experimentally, bionanoparticles demonstrated outstanding homogeneity in mobility compared to currently used calibration particles. A numerical method was developed to calculate the true distribution and to explain the broadening of measured distribution. The high stability of bionanoparticles was also confirmed. For PA measurement, three aerosol with spherical or near spherical shapes were investigated as possible candidates for a reference standard: C60, copper and silver. Comparisons were made between experimental photoacoustic absorption data with Mie theory calculations. This resulted in the identification of C60 particles with a mobility diameter of 150 nm to 400 nm as an absorbing standard at wavelengths of 405 nm and 660 nm. Copper particles with a mobility diameter of 80 nm to 300 nm are also shown to be a promising reference candidate at wavelength of 405 nm. The second topic of this dissertation focuses on the investigation of light absorption by carbonaceous particles using PA. Optical absorption spectra of size and mass selected laboratory generated aerosols consisting of black carbon (BC), BC with non-absorbing coating (ammonium sulfate and sodium chloride) and BC with a weakly absorbing coating (brown carbon derived from humic acid) were measured across the visible to near-IR (500 nm to 840 nm). The manner in which BC mixed with each coating material was investigated. The absorption enhancement of BC was determined to be wavelength dependent. Optical absorption spectra were also taken for size and mass selected smoldering smoke produced from six types of commonly seen wood in a laboratory scale apparatus.

Nested Sampling and its Applications in Stable Compressive Covariance Estimation and Phase Retrieval with Near-Minimal Measurements

Compressed covariance sensing using quadratic samplers is gaining increasing interest in recent literature. Covariance matrix often plays the role of a sufficient statistic in many signal and information processing tasks. However, owing to the large dimension of the data, it may become necessary to obtain a compressed sketch of the high dimensional covariance matrix to reduce the associated storage and communication costs. Nested sampling has been proposed in the past as an efficient sub-Nyquist sampling strategy that enables perfect reconstruction of the autocorrelation sequence of Wide-Sense Stationary (WSS) signals, as though it was sampled at the Nyquist rate. The key idea behind nested sampling is to exploit properties of the difference set that naturally arises in quadratic measurement model associated with covariance compression. In this thesis, we will focus on developing novel versions of nested sampling for low rank Toeplitz covariance estimation, and phase retrieval, where the latter problem finds many applications in high resolution optical imaging, X-ray crystallography and molecular imaging. The problem of low rank compressive Toeplitz covariance estimation is first shown to be fundamentally related to that of line spectrum recovery. In absence if noise, this connection can be exploited to develop a particular kind of sampler called the Generalized Nested Sampler (GNS), that can achieve optimal compression rates. In presence of bounded noise, we develop a regularization-free algorithm that provably leads to stable recovery of the high dimensional Toeplitz matrix from its order-wise minimal sketch acquired using a GNS. Contrary to existing TV-norm and nuclear norm based reconstruction algorithms, our technique does not use any tuning parameters, which can be of great practical value. The idea of nested sampling idea also finds a surprising use in the problem of phase retrieval, which has been of great interest in recent times for its convex formulation via PhaseLift, By using another modified version of nested sampling, namely the Partial Nested Fourier Sampler (PNFS), we show that with probability one, it is possible to achieve a certain conjectured lower bound on the necessary measurement size. Moreover, for sparse data, an l1 minimization based algorithm is proposed that can lead to stable phase retrieval using order-wise minimal number of measurements.

Accelerating wide-angle converging waves in the near field

We show that a wide-angle converging wave may be transformed into a shape-preserving accelerating beam having a beam-width near the diffraction limit. For that purpose, we followed a strategy that is particularly conceived for the acceleration of nonparaxial laser beams, in contrast to the well-known method by Siviloglou et al (2007 Phys. Rev. Lett. 99 213901). The concept of optical near-field shaping is applied to the design of non-flat ultra-narrow diffractive optical elements. The engineered curvilinear caustic can be set up by the beam emerging from a dynamic assembly of elementary gratings, the latter enabling to modify the effective refractive index of the metamaterial as it is arranged in controlled orientations. This light shaping process, besides being of theoretical interest, is expected to open up a wide range of broadband application possibilities.

Funtional Near Infrared Spectroscopy Study of Language, Joint Attention and Motor Skills

Near infrared spectroscopy (NIRS) is an emerging non-invasive optical neuro imaging technique that monitors the hemodynamic response to brain activation with ms-scale temporal resolution and sub-cm spatial resolution. The overall goal of my dissertation was to develop and apply NIRS towards investigation of neurological response to language, joint attention and planning and execution of motor skills in healthy adults. Language studies were performed to investigate the hemodynamic response, synchrony and dominance feature of the frontal and fronto-temporal cortex of healthy adults in response to language reception and expression. The mathematical model developed based on granger causality explicated the directional flow of information during the processing of language stimuli by the fronto-temporal cortex. Joint attention and planning/ execution of motor skill studies were performed to investigate the hemodynamic response, synchrony and dominance feature of the frontal cortex of healthy adults and in children (5-8 years old) with autism (for joint attention studies) and individuals with cerebral palsy (for planning/execution of motor skills studies). The joint attention studies on healthy adults showed differences in activation as well as intensity and phase dependent connectivity in the frontal cortex during joint attention in comparison to rest. The joint attention studies on typically developing children showed differences in frontal cortical activation in comparison to that in children with autism. The planning and execution of motor skills studies on healthy adults and individuals with cerebral palsy (CP) showed difference in the frontal cortical dominance, that is, bilateral and ipsilateral dominance, respectively. The planning and execution of motor skills studies also demonstrated the plastic and learning behavior of brain wherein correlation was found between the relative change in total hemoglobin in the frontal cortex and the kinematics of the activity performed by the participants. Thus, during my dissertation the NIRS neuroimaging technique was successfully implemented to investigate the neurological response of language, joint attention and planning and execution of motor skills in healthy adults as well as preliminarily on children with autism and individuals with cerebral palsy. These NIRS studies have long-term potential for the design of early stage interventions in children with autism and customized rehabilitation in individuals with cerebral palsy.

The spectral albedo of sea ice and salt crusts on the tropical ocean of Snowball Earth: II. Optical modeling

During the Snowball Earth events of the Neoproterozoic, tropical regions of the ocean could have developed a precipitated salt lag deposit left behind by sublimating sea ice. The major salt would have been hydrohalite, NaCl•2H2O. The crystals in such a deposit can be small and highly scattering, resulting in an allwave albedo similar to that of snow. The snow-free sea ice from which such a crust could develop has a lower albedo, around 0.5, so the development of a crust would substantially increase the albedo of tropical regions on Snowball Earth. Hydrohalite crystals are much less absorptive than ice in the near- infrared part of the solar spectrum, so their presence at the surface would increase the overall albedo as well as altering its spectral distribution. In this paper, we use laboratory measurements of the spectral albedo of a hydrohalite lag deposit, in combination with a radiative transfer model, to infer the inherent optical properties of hydrohalite as functions of wavelength. Using this result, we model mixtures of hydrohalite and ice representing both artificially created surfaces in the laboratory and surfaces relevant to Snowball Earth. The model is tested against sequences of laboratory measurements taken during the formation and the dissolution of a lag deposit of hydrohalite. We present a parameterization for the broadband albedo of cold, sublimating sea ice as it forms and evolves a hydrohalite crust, for use in climate models of Snowball Earth.

The optical properties of metamaterials

This thesis studies the parametric investigation, polarisation dependence and characterization of fishnet structure at near infrared wavelengths. Detailed simulations are performed to understand the behaviour of the structure at near infrared and optical wavelengths. Simulations are performed to obtain negative refractive index of the fishnet structure formed from nanoimprint lithography (NIL) by taking into account the effect of substrate and polymethyl methacrylate (PMMA) beneath it. Two different structures have been designed and fabricated of varying dimensions using NIL and their resonant wavelength measured in the near infrared at 1.45 µm and 1.88 µm. Simulations suggest that a negative refractive index real part with the magnitude -0.24 is found at 1.53 µm and this decrease to a maximum magnitude of -0.57 at 1.9 µm. The PMMA and suppressed pillars are here responsible for the increasing material losses and limiting the value of negative refractive index. An analytical approach has been suggested to characterise fishnet structures at oblique incidence. The expressions for an absorbing medium are rewritten for an alternative definition of refractive index. The expressions are initially validated for a dielectric slab and a metal film. These results provide the possibility that this proposal may yield a general algorithm for obtaining the complex reflection and transmission coefficients for artificial structures. FDTD simulations have been extensively used in this thesis to understand the optical metamaterials and their characterization.

Near-infrared spectroscopic study of basic aluminum sulfate and nitrate

The tridecameric Al-polymer [AlO4Al12(OH)24(H2O)12]7+ was prepared by forced hydrolysis of Al3+ up to an OH/Al molar ratio of 2.2. Under slow evaporation crystals were formed of Al13-nitrate. Upon addition of sulfate the tridecamer crystallised as the monoclinic Al13-sulfate. These crystals have been studied using near-infrared spectroscopy and compared to Al2(SO4)3.16H2O. Although the near-infrared spectra of the Al13-sulfate and nitrate are very similar indicating similar crystal structures, there are minor differences related to the strength with which the crystal water molecules are bonded to the salt groups. The interaction between crystal water and nitrate is stronger than with the sulfate as reflected by the shift of the crystal water band positions from 6213, 4874 and 4553 cm–1 for the Al13 sulfate towards 5925, 4848 and 4532 cm–1 for the nitrate. A reversed shift from 5079 and 5037 cm–1 for the sulfate towards 5238 and 5040 cm–1 for the nitrate for the water molecules in the Al13 indicate that the nitrate-Al13 bond is weakened due to the influence of the crystal water on the nitrate. The Al-OH bond in the Al13 complex is not influenced by changing the salt group due to the shielding by the water molecules of the Al13 complex.