Single Nanowire Structural Electrical and Electrochemical Characterization During Lithium Insertion
Nano Letters
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Nano Letters
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Science
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The use of nanowires for thermoelectric energy generation has gained momentum in recent years as an approach to improve the figure of merit (ZT) due in part to larger phonon scattering at the boundary resulting in reduced thermal conductivity while electrical conductivity is not significantly affected. Silicon-germanium (SiGe) alloy nanowires are promising candidates to further reduce thermal conductivity by phonon scattering because bulk SiGe alloys already have thermal conductivity comparable to reported Si nanowires. In this work, we show that thermal and electrical conductivity can be measured for the same single nanowire eliminating the uncertainties in ZT estimation due to measuring the thermal conduction on one set of wires and the electrical conduction on another set. In order to do so, we use nanomanipulation to place vapor-liquid-solid boron-doped SiGe alloy nanowires on predefined surface structures. Furthermore, we developed a contact-annealing technique to achieve negligible electrical contact resistance for the placed nanowires that allows us, for the first time, to measure electrical and thermal properties on the same device. We observe that thermal conductivity for SiGe nanowires is dominated by alloy scattering for nanowires down to 100 nm in diameter between the temperature range 40-300 K. The estimated electronic contribution of the thermal conductivity as given by the Wiedemann-Franz relationship is about 1 order of magnitude smaller than the measured thermal conductivity which indicates that phonons carry a large portion of the heat even at such small dimensions.
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Understanding the physics of phonon transport at small length scales is increasingly important for basic research in nanoelectronics, optoelectronics, nanomechanics, and thermoelectrics. We conducted several studies to develop an understanding of phonon behavior in very small structures. This report describes the modeling, experimental, and fabrication activities used to explore phonon transport across and along material interfaces and through nanopatterned structures. Toward the understanding of phonon transport across interfaces, we computed the Kapitza conductance for {Sigma}29(001) and {Sigma}3(111) interfaces in silicon, fabricated the interfaces in single-crystal silicon substrates, and used picosecond laser pulses to image the thermal waves crossing the interfaces. Toward the understanding of phonon transport along interfaces, we designed and fabricated a unique differential test structure that can measure the proportion of specular to diffuse thermal phonon scattering from silicon surfaces. Phonon-scale simulation of the test ligaments, as well as continuum scale modeling of the complete experiment, confirmed its sensitivity to surface scattering. To further our understanding of phonon transport through nanostructures, we fabricated microscale-patterned structures in diamond thin films.
Proposed for publication in Thin Solid Films.
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Applied Physics Letters
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Proposed for publication in Diamond and Related Materials
Due to material limitations of poly-Si resonators, polycrystalline diamond (poly-C) has been explored as a new MEMS resonator material. The poly-C resonators are designed, fabricated and tested using electrostatic (Michigan State University) and piezoelectric (Sandia National Laboratories) actuation methods, and the results are compared. For comparable resonator structures, although the resonance frequencies are similar, the measured Q values in the ranges of 1000-2000 and 10,000-15,000 are obtained for electrostatic and piezoelectric actuation methods, respectively. The difference in Q for the two methods is related to different pressures used during the measurement and not to the method of measurement. For the poly-C cantilever beam resonators, the highest value of their quality factor (Q) is reported for the first time (15,263).
Proposed for publication in Diamond and Related Materials
We have measured the temperature dependence of mechanical dissipation in tetrahedral amorphous carbon flexural and torsional resonators over the temperature range from 300 to 1023 K. The mechanical dissipation was found to be controlled by defects within the material, and the magnitude and temperature dependence of the dissipation were found to depend on whether flexural or torsional vibrational modes were excited. The defects that were active under flexural stresses have a relatively flat concentration from 0.4 to 0.7 eV with an ever increasing defect concentration up to 1.9 eV. Under shear stresses (torsion), the defect activation energies increase immediately beginning at 0.4 eV, with increasing defect concentration at higher energies.
We have studied the feasibility of an innovative device to sample 1ns low-power single current transients with a time resolution better than 10 ps. The new concept explored here is to close photoconductive semiconductor switches (PCSS) with a Laser for a period of 10 ps. The PCSSs are in a series along a Transmission Line (TL). The transient propagates along the TL allowing one to carry out a spatially resolved sampling of charge at a fixed time instead of the usual timesampling of the current. The fabrication of such a digitizer was proven to be feasible but very difficult.
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Proposed for publication in Journal of Applied Physics.
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Detailed experiments involving extensive high resolution transmission electron microscopy (TEM) revealed significant microstructural differences between Cu sulfides formed at low and high relative humidity (RH). It was known from prior experiments that the sulfide grows linearly with time at low RH up to a sulfide thickness approaching or exceeding one micron, while the sulfide initially grows linearly with time at high RH then becomes sub-linear at a sulfide thickness less than about 0.2 microns, with the sulfidation rate eventually approaching zero. TEM measurements of the Cu2S morphology revealed that the Cu2S formed at low RH has large sized grains (75 to greater than 150 nm) that are columnar in structure with sharp, abrupt grain boundaries. In contrast, the Cu2S formed at high RH has small equiaxed grains of 20 to 50 nm in size. Importantly, the small grains formed at high RH have highly disordered grain boundaries with a high concentration of nano-voids. Two-dimensional diffusion modeling was performed to determine whether the existence of localized source terms at the Cu/Cu2S interface could be responsible for the suppression of Cu sulfidation at long times at high RH. The models indicated that the existence of static localized source terms would not predict the complete suppression of growth that was observed. Instead, the models suggest that the diffusion of Cu through Cu2S becomes restricted during Cu2S formation at high RH. The leading speculation is that the extensive voiding that exists at grain boundaries in this material greatly reduces the flux of Cu between grains, leading to a reduction in the rate of sulfide film formation. These experiments provide an approach for adding microstructural information to Cu sulfidation rate computer models. In addition to the microstructural studies, new micro-patterned test structures were developed in this LDRD to offer insight into the point defect structure of Cu2S and to permit measurement of surface reaction rates during Cu sulfidation. The surface reaction rate was measured by creating micropatterned Cu lines of widths ranging from 5 microns to 100 microns. When sulfidized, the edges of the Cu lines show greater sulfidation than the center, an effect known as microloading. Measurement of the sulfidation profile enables an estimate of the ratio of the diffusivity of H2S in the gas phase to the surface reaction rate constant, k. Our measurements indicated that the gas phase diffusivity exceeds k by more than 10, but less than 100. This is consistent with computer simulations of the sulfidation process. Other electrical test structures were developed to measure the electrical conductivity of Cu2S that forms on Cu. This information can be used to determine relative vacancy concentrations in the Cu2S layer as a function of RH. The test structures involved micropatterned Cu disks and thin films, and the initial measurements showed that the electrical approach is feasible for point defect studies in Cu2S.
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Proposed for publication in Physical Review B - Rapid Communications, May 2003.
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Proposed for publication in Optics Letters.
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This report describes a new microsystems technology for the creation of microsensors and microelectromechanical systems (MEMS) using stress-free amorphous diamond (aD) films. Stress-free aD is a new material that has mechanical properties close to that of crystalline diamond, and the material is particularly promising for the development of high sensitivity microsensors and rugged and reliable MEMS. Some of the unique properties of aD include the ability to easily tailor film stress from compressive to slightly tensile, hardness and stiffness 80-90% that of crystalline diamond, very high wear resistance, a hydrophobic surface, extreme chemical inertness, chemical compatibility with silicon, controllable electrical conductivity from insulating to conducting, and biocompatibility. A variety of MEMS structures were fabricated from this material and evaluated. These structures included electrostatically-actuated comb drives, micro-tensile test structures, singly- and doubly-clamped beams, and friction and wear test structures. It was found that surface micromachined MEMS could be fabricated in this material easily and that the hydrophobic surface of the film enabled the release of structures without the need for special drying procedures or the use of applied hydrophobic coatings. Measurements using these structures revealed that aD has a Young's modulus of {approx}650 GPa, a tensile fracture strength of 8 GPa, and a fracture toughness of 8 MPa{center_dot}m {sup 1/2}. These results suggest that this material may be suitable in applications where stiction or wear is an issue. Flexural plate wave (FPW) microsensors were also fabricated from aD. These devices use membranes of aD as thin as {approx}100 nm. The performance of the aD FPW sensors was evaluated for the detection of volatile organic compounds using ethyl cellulose as the sensor coating. For comparable membrane thicknesses, the aD sensors showed better performance than silicon nitride based sensors. Greater than one order of magnitude increase in chemical sensitivity is expected through the use of ultra-thin aD membranes in the FPW sensor. The discoveries and development of the aD microsystems technology that were made in this project have led to new research projects in the areas of aD bioMEMS and aD radio frequency MEMS.
A physics-based understanding of material aging mechanisms helps to increase reliability when predicting the lifetime of mechanical and electrical components. This report examines in detail the mechanisms of atmospheric copper sulfidation and evaluates new methods of parallel experimentation for high-throughput corrosion analysis. Often our knowledge of aging mechanisms is limited because coupled chemical reactions and physical processes are involved that depend on complex interactions with the environment and component functionality. Atmospheric corrosion is one of the most complex aging phenomena and it has profound consequences for the nation's economy and safety. Therefore, copper sulfidation was used as a test-case to examine the utility of parallel experimentation. Through the use of parallel and conventional experimentation, we measured: (1) the sulfidation rate as a function of humidity, light, temperature and O{sub 2} concentration; (2) the primary moving species in solid state transport; (3) the diffusivity of Cu vacancies through Cu{sub 2}S; (4) the sulfidation activation energies as a function of relative humidity (RH); (5) the sulfidation induction times at low humidities; and (6) the effect of light on the sulfidation rate. Also, the importance of various sulfidation mechanisms was determined as a function of RH and sulfide thickness. Different models for sulfidation-reactor geometries and the sulfidation reaction process are presented.
Abstract not provided.