Publications

Ohlhausen, J.A.; Tallant, David T.; Kent, Michael S.; Keenan, Michael R.; Hankins, M.G.

Abstract not provided.

Yim, Hyun Y.; Weems, Jessica S.; Tallant, David T.; Garcia, Manuel J.

Abstract not provided.

Yim, Hyun Y.; Tallant, David T.; Garcia, Manuel J.

Abstract not provided.

Friedmann, Thomas A.; Boyce, Brad B.; Czaplewski, David A.; Dyck, Christopher D.; Webster, James R.; Carton, Andrew J.; Carr, Dustin W.; Keeler, Bianca E.; Wendt, J.R.; Tallant, David T.

Nano-electromechanical oscillators (NEMOs), capacitively-coupled radio frequency (RF) MEMS switches incorporating dissipative dielectrics, new processing technologies for tetrahedral amorphous carbon (ta-C) films, and scientific understanding of dissipation mechanisms in small mechanical structures were developed in this project. NEMOs are defined as mechanical oscillators with critical dimensions of 50 nm or less and resonance frequencies approaching 1 GHz. Target applications for these devices include simple, inexpensive clocks in electrical circuits, passive RF electrical filters, or platforms for sensor arrays. Ta-C NEMO arrays were used to demonstrate a novel optomechanical structure that shows remarkable sensitivity to small displacements (better than 160 fm/Hz {sup 1/2}) and suitability as an extremely sensitive accelerometer. The RF MEMS capacitively-coupled switches used ta-C as a dissipative dielectric. The devices showed a unipolar switching response to a unipolar stimulus, indicating the absence of significant dielectric charging, which has historically been the major reliability issue with these switches. This technology is promising for the development of reliable, low-power RF switches. An excimer laser annealing process was developed that permits full in-plane stress relaxation in ta-C films in air under ambient conditions, permitting the application of stress-reduced ta-C films in areas where low thermal budget is required, e.g. MEMS integration with pre-existing CMOS electronics. Studies of mechanical dissipation in micro- and nano-scale ta-C mechanical oscillators at room temperature revealed that mechanical losses are limited by dissipation associated with mechanical relaxation in a broad spectrum of defects with activation energies for mechanical relaxation ranging from 0.35 eV to over 0.55 eV. This work has established a foundation for the creation of devices based on nanomechanical structures, and outstanding critical research areas that need to be addressed for the successful application of these technologies have been identified.

Burns, George B.; Palmer, Jeremy A.; Harris, Marc F.; McDaniel, Karen L.; Guo, Junpeng; Vawter, Gregory A.; Tallant, David T.; Griffith, M.L.; Luk, Ting S.

At Sandia National Laboratories, miniaturization dominates future hardware designs, and technologies that address the manufacture of micro-scale to nano-scale features are in demand. Currently, Sandia is developing technologies such as photolithography/etching (e.g. silicon MEMS), LIGA, micro-electro-discharge machining (micro-EDM), and focused ion beam (FIB) machining to fulfill some of the component design requirements. Some processes are more encompassing than others, but each process has its niche, where all performance characteristics cannot be met by one technology. For example, micro-EDM creates highly accurate micro-scale features but the choice of materials is limited to conductive materials. With silicon-based MEMS technology, highly accurate nano-scale integrated devices are fabricated but the mechanical performance may not meet the requirements. Femtosecond laser processing has the potential to fulfill a broad range of design demands, both in terms of feature resolution and material choices, thereby improving fabrication of micro-components. One of the unique features of femtosecond lasers is the ability to ablate nearly all materials with little heat transfer, and therefore melting or damage, to the surrounding material, resulting in highly accurate micro-scale features. Another unique aspect to femtosecond radiation is the ability to create localized structural changes thought nonlinear absorption processes. By scanning the focal point within transparent material, we can create three-dimensional waveguides for biological sensors and optical components. In this report, we utilized the special characteristics of femtosecond laser processing for microfabrication. Special emphasis was placed on the laser-material interactions to gain a science-based understanding of the process and to determine the process parameter space for laser processing of metals and glasses. Two areas were investigated, including laser ablation of ferrous alloys and direct-write optical waveguides and integrated optics in bulk glass. The effects of laser and environmental parameters on such aspects as removal rate, feature size, feature definition, and ablation angle during the ablation process of metals were studied. In addition, the manufacturing requirements for component fabrication including precision and reproducibility were investigated. The effect of laser processing conditions on the optical properties of direct-written waveguides and an unusual laser-induced birefringence in an optically isotropic glass are reported. Several integrated optical devices, including a Y coupler, directional coupler, and Mach-Zehnder interferometer, were made to demonstrate the simplicity and flexibility of this technique in comparison to the conventional waveguide fabrication processes.

Journal of Materials Research

Kent, Michael S.; Reedy, Earl D.; Yim, Hyun Y.; Matheson, A.; Sorenson, J.; Hall, J.; Schubert, K.; Tallant, David T.; Garcia, Manuel J.; Ohlhausen, T.; Assink, R.

The effect of the density and in-plane distribution of interfacial interactions on crack initiation in an epoxy-silicon joint was studied in nominally pure shear loading. Well-defined combinations of strong (specific) and weak (nonspecific) interactions were created using self-assembling monolayers. The in-plane distribution of strong and weak interactions was varied by employing two deposition methods: depositing mixtures of molecules with different terminal groups resulting in a nominally random distribution, and depositing methyl-terminated molecules in domains defined lithographically with the remaining area interacting through strong acid-base interactions. The two distributions lead to very different fracture behavior. For the case of the methyl-terminated domains (50 μm on a side) fabricated lithographically, the joint shear strength varies almost linearly with the area fraction of strongly interacting sites. From this we infer that cracks nucleate on or near the interface over nearly the entire range of bonded area fraction and do so at nearly the same value of local stress (load/bonded area). We postulate that the imposed heterogeneity in interfacial interactions results in heterogeneous stress and strain fields within the epoxy in close proximity to the interface. Simply, the bonded areas carry load while the methyl terminated domains carry negligible load. Stress is amplified adjacent to the well-bonded regions (and reduced adjacent to the poorly bonded regions), and this leads to crack initiation by plastic deformation and chain scission within the epoxy near the interface. For the case of mixed monolayers, the dependence is entirely different. At low areal density of strongly interacting sites, the joint shear strength is below the detection limit of our transducer for a significant range of mixed monolayer composition. With increasing density of strongly interacting sites, a sharp increase in joint shear strength occurs at a methyl terminated area fraction of roughly 0.90. We postulate that this coincides with the onset of yielding in the epoxy. For methyl-terminated area fractions less than 0.85, the joint shear strength becomes independent of the interfacial interactions. This indicates that fracture no longer initiates on the interface but away from the interface by a competing mechanism, likely plastic deformation and chain scission within the bulk epoxy. The data demonstrate that the in-plane distribution of interaction sites alone can affect the location of crack nucleation and the far-field stress required.

Proposed for publication in Journal of Applied Physics.

Sullivan, John P.; Tallant, David T.; Boyce, Brad B.

Abstract not provided.

Simmons, J.A.; Fischer, Arthur J.; Crawford, Mary H.; Abrams, B.L.; Biefeld, Robert M.; Koleske, Daniel K.; Allerman, A.A.; Figiel, J.J.; Creighton, J.R.; Coltrin, Michael E.; Tsao, Jeffrey Y.; Mitchell, Christine C.; Kerley, Thomas M.; Wang, George T.; Bogart, Katherine B.; Seager, Carleton H.; Campbell, Jonathan C.; Follstaedt, D.M.; Norman, Adam K.; Kurtz, S.R.; Wright, Alan F.; Myers, S.M.; Missert, Nancy A.; Copeland, Robert G.; Provencio, P.N.; Wilcoxon, Jess P.; Hadley, G.R.; Wendt, J.R.; Kaplar, Robert K.; Shul, Randy J.; Rohwer, Lauren E.; Tallant, David T.; Simpson, Regina L.; Moffat, Harry K.; Salinger, Andrew G.; Pawlowski, Roger P.; Emerson, John A.; Thoma, Steven T.; Cole, Phillip J.; Boyack, Kevin W.; Garcia, Marie L.; Allen, Mark S.; Burdick, Brent B.; Rahal, Nabeel R.; Monson, Mary A.; Chow, Weng W.; Waldrip, Karen E.

This SAND report is the final report on Sandia's Grand Challenge LDRD Project 27328, 'A Revolution in Lighting -- Building the Science and Technology Base for Ultra-Efficient Solid-state Lighting.' This project, which for brevity we refer to as the SSL GCLDRD, is considered one of Sandia's most successful GCLDRDs. As a result, this report reviews not only technical highlights, but also the genesis of the idea for Solid-state Lighting (SSL), the initiation of the SSL GCLDRD, and the goals, scope, success metrics, and evolution of the SSL GCLDRD over the course of its life. One way in which the SSL GCLDRD was different from other GCLDRDs was that it coincided with a larger effort by the SSL community - primarily industrial companies investing in SSL, but also universities, trade organizations, and other Department of Energy (DOE) national laboratories - to support a national initiative in SSL R&D. Sandia was a major player in publicizing the tremendous energy savings potential of SSL, and in helping to develop, unify and support community consensus for such an initiative. Hence, our activities in this area, discussed in Chapter 6, were substantial: white papers; SSL technology workshops and roadmaps; support for the Optoelectronics Industry Development Association (OIDA), DOE and Senator Bingaman's office; extensive public relations and media activities; and a worldwide SSL community website. Many science and technology advances and breakthroughs were also enabled under this GCLDRD, resulting in: 55 publications; 124 presentations; 10 book chapters and reports; 5 U.S. patent applications including 1 already issued; and 14 patent disclosures not yet applied for. Twenty-six invited talks were given, at prestigious venues such as the American Physical Society Meeting, the Materials Research Society Meeting, the AVS International Symposium, and the Electrochemical Society Meeting. This report contains a summary of these science and technology advances and breakthroughs, with Chapters 1-5 devoted to the five technical task areas: 1 Fundamental Materials Physics; 2 111-Nitride Growth Chemistry and Substrate Physics; 3 111-Nitride MOCVD Reactor Design and In-Situ Monitoring; 4 Advanced Light-Emitting Devices; and 5 Phosphors and Encapsulants. Chapter 7 (Appendix A) contains a listing of publications, presentations, and patents. Finally, the SSL GCLDRD resulted in numerous actual and pending follow-on programs for Sandia, including multiple grants from DOE and the Defense Advanced Research Projects Agency (DARPA), and Cooperative Research and Development Agreements (CRADAs) with SSL companies. Many of these follow-on programs arose out of contacts developed through our External Advisory Committee (EAC). In h s and other ways, the EAC played a very important role. Chapter 8 (Appendix B) contains the full (unedited) text of the EAC reviews that were held periodically during the course of the project.

Proposed for publication in Nano Letters.

Sounart, Thomas L.; Voigt, James A.; Tallant, David T.

Abstract not provided.

Boyle, Timothy J.; Segall, Judith M.; Cherry, Brian R.; Butler, Paul C.; Alam, Todd M.; Tallant, David T.; Malizia, Louis A.; Rodriguez, Marko A.; Ingersoll, David I.; Clark, Nancy H.; Garcia, Manuel J.; Simpson, Regina L.

Exploration of the fundamental chemical behavior of the AlCl{sub 3}/SO{sub 2}Cl{sub 2} catholyte system for the ARDEC Self-Destruct Fuze Reserve Battery Project under accelerated aging conditions was completed using a variety of analytical tools. Four different molecular species were identified in this solution, three of which are major. The relative concentrations of the molecular species formed were found to depend on aging time, initial concentrations, and storage temperature, with each variable affecting the kinetics and thermodynamics of this complex reaction system. We also evaluated the effect of water on the system, and determined that it does not play a role in dictating the observed molecular species present in solution. The first Al-containing species formed was identified as the dimer [Al({mu}-Cl)Cl{sub 2}]{sub 2}, and was found to be in equilibrium with the monomer, AlCl{sub 3}. The second species formed in the reaction scheme was identified by single crystal X-ray diffraction studies as [Cl{sub 2}Al({mu}-O{sub 2}SCl)]{sub 2} (I), a scrambled AlCl{sub 3}{center_dot}SO{sub 2} adduct. The SO{sub 2}(g) present, as well as CL{sub 2}(g), was formed through decomposition of SO{sub 2}CL{sub 2}. The SO{sub 2}(g) generated was readily consumed by AlCl{sub 3} to form the adduct 1 which was experimentally verified when 1 was also isolated from the reaction of SO{sub 2}(g) and AlCl {sub 3}. The third species found was tentatively identified as a compound having the general formula {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2}]{r_brace}{sub n}. This was based on {sup 27}Al NMR data that revealed a species with tetrahedrally coordinated Al metal centers with increased oxygen coordination and the fact that the precipitate, or gel, that forms over time was shown by Raman spectroscopic studies to possess a component that is consistent with SOCl{sub 2}. The precursor to the precipitate should have similar constituents, thus the assignment of {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2}]{r_brace}{sub n}. The precipitate was further identified by solid state {sup 27}Al MAS NMR data to possess predominantly octahedral A1 metal center which implies {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2}]{r_brace}{sub n} must undergo some internal rearrangements. A reaction sequence has been proposed to account for the various molecular species identified in this complex reaction mixture during the aging process. The metallurgical welds were of high quality. These results were all visually determined there was no mechanical testing performed. However, it is recommended that the end plate geometry and weld be changed. If the present weld strength, based on .003' - .005' penetration, is sufficient for unit performance, the end plate thickness can be reduced to .005' instead of the .020' thickness. This will enable the plug to be stamped so that it can form a cap rather than a plug and solve existing problems and increase the amount of catholyte which may be beneficial to battery performance.

Bell, Nelson S.; Bell, Nelson S.; Tallant, David T.; Rodriguez, Marko A.

The purpose of this program was to investigate methods to characterize the colloidal stability of nanoparticles during the synthesis reaction, and to characterize their organization related to interparticle forces. Studies were attempted using Raman spectroscopy and ultrasonic attenuation to observe the nucleation and growth process with characterization of stability parameters such as the zeta potential. The application of the techniques available showed that the instrumentation requires high sensitivity to the concentration of the system. Optical routes can be complicated by the scattering effects of colloidal suspensions, but dilution can cause a lowering of signal that prevents collection of data. Acoustic methods require a significant particle concentration, preventing the observation of nucleation events. Studies on the dispersion of nanoparticles show that electrostatic routes are unsuccessful with molecular surfactants at high particle concentration due to electrostatic interaction collapse by counterions. The study of molecular surfactants show that steric lengths on the order of 2 nm are successful for dispersion of nanoparticle systems at high particle concentration, similar to dispersion with commercial polyelectrolyte surfactants.

Tallant, David T.; Tallant, David T.; Cich, Michael C.; Garcia, Manuel J.; Hafich, Michael J.; Kent, Michael S.; Simpson, Regina L.

Abstract not provided.

Proposed for publication in Journal of Luminescence.

Seager, Carleton H.; Seager, Carleton H.; Tallant, David T.

Abstract not provided.

Giunta, Rachel K.; Kent, Michael S.; Weems, Jessica S.; Tallant, David T.; Garcia, M.C.; Emerson, John A.

Abstract not provided.

Tallant, David T.; Simpson, Regina L.

Abstract not provided.

Seager, Carleton H.; Tallant, David T.

The design of field emission displays is severely constrained by the universally poor cathodoluminescence (CL) efficiency of most phosphors at low excitation energies. As part of the effort to understand this phenomenon, the authors have measured the time decay of spectrally-resolved, pulsed CL and photoluminescence (PL) in several phosphors activated by rare earth and transition metal impurities, including Y{sub 2}O{sub 3}:Eu, Y{sub 2}SiO{sub 5}:Tb, and Zn{sub 2}SiO{sub 4}:Mn. Activator concentrations ranged from {approximately}0.25 to 10%. The CL decay curves are always non-linear on a log(CL)-linear(time) plot--i.e. they deviate from first order decay kinetics. These deviations are always more pronounced at short times and larger activator concentrations and are largest at low beam energies where the decay rates are noticeably faster. PL decay is always slower than that seen for CL, but these differences disappear after most of the excited species have decayed. They have also measured the dependence of steady state CL efficiency on beam energy. They find that larger activator concentrations accelerate the drop in CL efficiency seen at low beam energies. These effects are largest for the activators which interact more strongly with the host lattice. While activator-activator interactions are known to limit PL and CL efficiency in most phosphors, the present data suggest that a more insidious version of this mechanism is partly responsible for poor CL efficiency at low beam energies. This enhanced concentration quenching is due to the interaction of nearby excited activators. These interactions can lead to non-radiative activator decay, hence lower steady state CL efficiency. Excited state clustering, which may be caused by the large energy loss rate of low energy primary electrons, appears to enhance these interactions. In support of this idea, they find that PL decays obtained at high laser pulse energies resemble the non-linear decays seen in the CL data.

Applied Physics Letters

Siegal, Michael P.; Tallant, David T.; Provencio, P.N.; Overmyer, Donald L.; Simpson, Regina L.; Martinez-Miranda, L.J.

Modest thermal annealing to 600°C of diamondlike amorphous-carbon (a-C) films grown at room temperature results in the formation of carbon nanocomposites with hardness similar to diamond. These nanocomposite films consist of nanometer-sized regions of high density a-C embedded in an a-C matrix with a reduced density of 5%-10%. We report on the evolution of density and bonding topologies as a function of annealing temperature. Despite a decrease in density, film hardness actually increases ∼15% due to the development of the nanocomposite structure. © 2000 American Institute of Physics.

Applied Physics Letters

Siegal, Michael P.; Provencio, P.N.; Tallant, David T.; Simpson, Regina L.; Kleinsorge, B.; Milne, W.I.

The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces; their thicknesses increase with deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies <60 eV and increases for films grown using ion energies >160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of σ-to π-bonded carbon atoms. © 2000 American Institute of Physics.

Alam, Todd M.; Lang, David P.; Tallant, David T.; Garcia, Manuel J.; Simpson, Regina L.; McKenzie, Bonnie B.; Bencoe, Denise N.

Abstract not provided.

Tallant, David T.; Simpson, Regina L.; Grazier, J.M.; Zeuch, David H.; Olson, Walter R.; Tuttle, Bruce T.

The authors used micro-Raman spectroscopy to monitor the ferroelectric (FE) to antiferroelectric (AFE) phase transition in PZT ceramic bars during the application of uniaxial stress. They designed and constructed a simple loading device, which can apply sufficient uniaxial force to transform reasonably large ceramic bars while being small enough to fit on the mechanical stage of the microscope used for Raman analysis. Raman spectra of individual grains in ceramic PZT bars were obtained as the stress on the bar was increased in increments. At the same time gauges attached to the PZT bar recorded axial and lateral strains induced by the applied stress. The Raman spectra were used to calculate an FE coordinate, which is related to the fraction of FE phase present. The authors present data showing changes in the FE coordinates of individual PZT grains and correlate these changes to stress-strain data, which plot the macroscopic evolution of the FE-to-AFE transformation. Their data indicates that the FE-to-AFE transformation does not occur simultaneously for all PZT grains but that grains react individually to local conditions.

Physical Review B

Siegal, Michael P.; Tallant, David T.; Barbour, J.C.; Simpson, Regina L.; Overmyer, Donald L.

Nanostructural characterization of amorphous diamondlike carbon (a-C) films grown on silicon using pulsed-laser deposition (PLD) is correlated to both growth energetic and film thickness. Raman spectroscopy and x-ray reflectivity probe both the topological nature of 3- and 4-fold coordinated carbon atom bonding and the topographical clustering of their distributions within a given film. In general, increasing the energetic of PLD growth results in films becoming more ``diamondlike'', i.e. increasing mass density and decreasing optical absorbance. However, these same properties decrease appreciably with thickness. The topology of carbon atom bonding is different for material near the substrate interface compared to material within the bulk portion of an a-C film. A simple model balancing the energy of residual stress and the free energies of resulting carbon topologies is proposed to provide an explanation of the evolution of topographical bonding clusters in a growing a-C film.

Materials Research Society Symposium - Proceedings

Tallant, David T.; Seager, Carleton H.; Simpson, Regina L.

The relatively poor efficiency of phosphor materials in cathodoluminescence with low accelerating voltages is a major concern in the design of field emission fiat panel displays operated below 5 kv. Our research on rare-earth-activated phosphors indicates that mechanisms involving interactions of excited activators have a significant impact on phosphor efficiency. Persistence measurements in photoluminescence (PL) and cathodoluminescence (CL) show significant deviations from the sequential relaxation model. This model assumes that higher excited manifolds in an activator de-excite primarily by phonon-mediated sequential relaxation to lower energy manifolds in the same activator ion. In addition to sequential relaxation, there appears to be strong coupling between activators, which results in energy transfer interactions. Some of these interactions negatively impact phosphor efficiency by nonradiatively de-exciting activators, increasing activator concentration enhances these interactions. The net effect is a significant degradation in phosphor efficiency at useful activator concentrations, which is exaggerated when low-energy electron beams are used to excite the emission.