Writing self-assembled monolayers with Cs: Optimization of atomic nanolithography imaging using self-assembled monolayers on gold substrates

We report the results of a study into the factors controlling the quality of nanolithographic imaging. Self-assembled monolayer (SAM) coverage, subsequent postetch pattern definition, and minimum feature size all depend on the quality of the Au substrate used in material mask atomic nanolithographic experiments. We find that sputtered Au substrates yield much smoother surfaces and a higher density of {111}-oriented grains than evaporated Au surfaces. Phase imaging with an atomic force microscope shows that the quality and percentage coverage of SAM adsorption are much greater for sputtered Au surfaces. Exposure of the self-assembled monolayer to an optically cooled atomic Cs beam traversing a two-dimensional array of submicron material masks mounted a few microns above the self-assembled monolayer surface allowed determination of the minimum average Cs dose (2 Cs atoms per self-assembled monolayer molecule) to write the monolayer. Suitable wet etching, with etch rates of 2.2 nm min-1, results in optimized pattern definition. Utilizing these optimizations, material mask features as small as 230 nm in diameter with a fractional depth gradient of 0.820 nm were realized.

Multimode Atomic Pattern Formation via Enhanced Light-atom Interactions

The nonlinear interaction between light and atoms is an extensive field of study with a broad range of applications in quantum information science and condensed matter physics. Nonlinear optical phenomena occurring in cold atoms are particularly interesting because such slowly moving atoms can spatially organize into density gratings, which allows for studies involving optical interactions with structured materials. In this thesis, I describe a novel nonlinear optical effect that arises when cold atoms spatially bunch in an optical lattice. I show that employing this spatial atomic bunching provides access to a unique physical regime with reduced thresholds for nonlinear optical processes and enhanced material properties. Using this method, I observe the nonlinear optical phenomenon of transverse optical pattern formation at record-low powers. These transverse optical patterns are generated by a wave- mixing process that is mediated by the cold atomic vapor. The optical patterns are highly multimode and induce rich non-equilibrium atomic dynamics. In particular, I find that there exists a synergistic interplay between the generated optical pat- terns and the atoms, wherein the scattered fields help the atoms to self-organize into new, multimode structures that are not externally imposed on the atomic sample. These self-organized structures in turn enhance the power in the optical patterns. I provide the first detailed investigation of the motional dynamics of atoms that have self-organized in a multimode geometry. I also show that the transverse optical patterns induce Sisyphus cooling in all three spatial dimensions, which is the first observation of spontaneous three-dimensional cooling. My experiment represents a unique means by which to study nonlinear optics and non-equilibrium dynamics at ultra-low required powers.

Atomic vapor deposition of bismuth titanate thin films

c-axis oriented ferroelectric bismuth titanate (Bi4Ti 3O12) thin films were grown on (001) strontium titanate (SrTiO3) substrates by an atomic vapor deposition technique. The ferroelectric properties of the thin films are greatly affected by the presence of various kinds of defects. Detailed x-ray diffraction data and transmission electron microscopy analysis demonstrated the presence of out-of-phase boundaries (OPBs). It is found that the OPB density changes appreciably with the amount of titanium injected during growth of the thin films. Piezo-responses of the thin films were measured by piezo-force microscopy. It is found that the in-plane piezoresponse is stronger than the out-of-plane response, due to the strong c-axis orientation of the films.

The structural and piezoresponse properties of c-axis-oriented Aurivillius phase Bi5Ti3FeO15 thin films deposited by atomic vapor deposition

The deposition by atomic vapor deposition of highly c-axis-oriented Aurivillius phase Bi 5Ti 3FeO 15 (BTFO) thin films on (100) Si substrates is reported. Partially crystallized BTFO films with c-axis perpendicular to the substrate surface were first deposited at 610°C (8 excess Bi), and subsequently annealed at 820°C to get stoichiometric composition. After annealing, the films were highly c-axis-oriented, showing only (00l) peaks in x-ray diffraction (XRD), up to (0024). Transmission electron microscopy (TEM) confirms the BTFO film has a clear layered structure, and the bismuth oxide layer interleaves the four-block pseudoperovskite layer, indicating the n 4 Aurivillius phase structure. Piezoresponse force microscopy measurements indicate strong in-plane piezoelectric response, consistent with the c-axis layered structure, shown by XRD and TEM.

Effect of reaction mechanism on precursor exposure time in atomic layer deposition of silicon oxide and silicon nitride

Atomic layer deposition (ALD) of highly conformal, silicon-based dielectric thin films has become necessary because of the continuing decrease in feature size in microelectronic devices. The ALD of oxides and nitrides is usually thought to be mechanistically similar, but plasma-enhanced ALD of silicon nitride is found to be problematic, while that of silicon oxide is straightforward. To find why, the ALD of silicon nitride and silicon oxide dielectric films was studied by applying ab initio methods to theoretical models for proposed surface reaction mechanisms. The thermodynamic energies for the elimination of functional groups from different silicon precursors reacting with simple model molecules were calculated using density functional theory (DFT), explaining the lower reactivity of precursors toward the deposition of silicon nitride relative to silicon oxide seen in experiments, but not explaining the trends between precursors. Using more realistic cluster models of amine and hydroxyl covered surfaces, the structures and energies were calculated of reaction pathways for chemisorption of different silicon precursors via functional group elimination, with more success. DFT calculations identified the initial physisorption step as crucial toward deposition and this step was thus used to predict the ALD reactivity of a range of amino-silane precursors, yielding good agreement with experiment. The retention of hydrogen within silicon nitride films but not in silicon oxide observed in FTIR spectra was accounted for by the theoretical calculations and helped verify the application of the model.

Bomb-tritium input function calculated from the details of the nuclear atmospheric bomb tests released by the UNSCEAR [2000]

Improving the representation of the hydrological cycle in Atmospheric General Circulation Models (AGCMs) is one of the main challenges in modeling the Earth's climate system. One way to evaluate model performance is to simulate the transport of water isotopes. Among those available, tritium (HTO) is an extremely valuable tracer, because its content in the different reservoirs involved in the water cycle (stratosphere, troposphere, ocean) varies by order of magnitude. Previous work incorporated natural tritium into LMDZ-iso, a version of the LMDZ general circulation model enhanced by water isotope diagnostics. Here for the first time, the anthropogenic tritium injected by each of the atmospheric nuclear-bomb tests between 1945 and 1980 has been first estimated and further implemented in the model; it creates an opportunity to evaluate certain aspects of LDMZ over several decades by following the bomb-tritium transient signal through the hydrological cycle. Simulations of tritium in water vapor and precipitation for the period 1950-2008, with both natural and anthropogenic components, are presented in this study. LMDZ-iso satisfactorily reproduces the general shape of the temporal evolution of tritium. However, LMDZ-iso simulates too high a bomb-tritium peak followed by too strong a decrease of tritium in precipitation. The too diffusive vertical advection in AGCMs crucially affects the residence time of tritium in the stratosphere. This insight into model performance demonstrates that the implementation of tritium in an AGCM provides a new and valuable test of the modeled atmospheric transport, complementing water stable isotope modeling.

Approach to chaos in ultracold atomic and molecular physics: Statistics of near-threshold bound states for Li+CaH and Li+CaF

We calculate near-threshold bound states and Feshbach resonance positions for atom–rigid-rotor models of the highly anisotropic systems Li+CaH and Li+CaF. We perform statistical analysis on the resonance positions to compare with the predictions of random matrix theory. For Li+CaH with total angular momentum J=0 we find fully chaotic behavior in both the nearest-neighbor spacing distribution and the level number variance. However, for J>0 we find different behavior due to the presence of a nearly conserved quantum number. Li+CaF (J=0) also shows apparently reduced levels of chaotic behavior despite its stronger effective coupling. This may indicate the development of another good quantum number relating to a bending motion of the complex. However, continuously varying the rotational constant over a wide range shows unexpected structure in the degree of chaotic behavior, including a dramatic reduction around the rotational constant of CaF. This demonstrates the complexity of the relationship between coupling and chaotic behavior.

Reactions of atomic and molecular ions with acetone, 1,1,1- trifluoroacetone, and hexafluoroacetone: An investigation of the effects of molecular structure on the dynamics and kinetics of ion-molecule reactions

A selected ion flow tube study of the reactions of a series of gas-phase atomic cations (S⁺, Xe⁺, O⁺, Kr⁺, N⁺, Ar⁺ and Ne⁺) and molecular ions (SF _n⁺ (n = 1-5), CF_n⁺ (n = 1-3), CF₂Cl⁺, H₃O⁺, NO⁺, N ₂O⁺, CO₂⁺, CO⁺, and N₂⁺) spanning a large range of recombination energies (6.3-21.6 eV), with acetone, 1,1,1-trifluoroacetone, and hexafluoroacetone has been undertaken with the objective of exploring the nature of the reaction ion chemistry as the methyl groups in acetone are substituted for CF₃. The reaction rate coefficients and product ion branching ratios for all 66 reactions, measured at 298 K, are reported. The experimental reaction rate coefficients are compared to theoretically calculated collisional values. Several distinct reaction processes were observed among the large number of reactions studied, including charge transfer (non-dissociative and dissociative), abstraction, ion-molecule associations and, in the case of the reactions involving the reagent ion H₃O⁺, proton transfer. 

Benchmarking a modified version of the civ3 nonrelativistic atomic-structure code within Na-like-tungsten R -matrix calculations

In this work we explore the validity of employing a modified version of the nonrelativistic structure code civ3 for heavy, highly charged systems, using Na-like tungsten as a simple benchmark. Consequently, we present radiative and subsequent collisional atomic data compared with corresponding results from a fully relativistic structure and collisional model. Our motivation for this line of study is to benchmark civ3 against the relativistic grasp0 structure code. This is an important study as civ3 wave functions in nonrelativistic R-matrix calculations are computationally less expensive than their Dirac counterparts. There are very few existing data for the W LXIV ion in the literature with which we can compare except for an incomplete set of energy levels available from the NIST database. The overall accuracy of the present results is thus determined by the comparison between the civ3 and grasp0 structure codes alongside collisional atomic data computed by the R-matrix Breit-Pauli and Dirac codes. It is found that the electron-impact collision strengths and effective collision strengths computed by these differing methods are in good general agreement for the majority of the transitions considered, across a broad range of electron temperatures.

Direct observation of a long-lived single-atom catalyst chiseling atomic structures in graphene

Fabricating stable functional devices at the atomic scale is an ultimate goal of nanotechnology. In biological processes, such high-precision operations are accomplished by enzymes. A counterpart molecular catalyst that binds to a solid-state substrate would be highly desirable. Here, we report the direct observation of single Si adatoms catalyzing the dissociation of carbon atoms from graphene in an aberration-corrected high-resolution transmission electron microscope (HRTEM). The single Si atom provides a catalytic wedge for energetic electrons to chisel off the graphene lattice, atom by atom, while the Si atom itself is not consumed. The products of the chiseling process are atomic-scale features including graphene pores and clean edges. Our experimental observations and first-principles calculations demonstrated the dynamics, stability, and selectivity of such a single-atom chisel, which opens up the possibility of fabricating certain stable molecular devices by precise modification of materials at the atomic scale.