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Reversible computing with fast, fully static, fully adiabatic CMOS

Proceedings - 2020 International Conference on Rebooting Computing, ICRC 2020

Frank, Michael P.; Brocato, Robert W.; Tierney, Brian D.; Missert, Nancy A.; Hsia, Alexander H.

To advance the energy efficiency of general digital computing far beyond the thermodynamic limits that apply to conventional digital circuits will require utilizing the principles of reversible computing. It has been known since the early 1990s that reversible computing based on adiabatic switching is possible in CMOS, although almost all the “adiabatic” CMOS logic families in the literature are not actually fully adiabatic, which limits their achievable energy savings. The first CMOS logic style achieving truly, fully adiabatic operation if leakage was negligible (CRL) was not fully static, which led to practical engineering difficulties in the presence of certain nonidealities. Later, “static” adiabatic logic families were described, but they were not actually fully adiabatic, or fully static, and were much slower. In this paper, we describe a new logic family, Static 2-Level Adiabatic Logic (S2LAL), which is, to our knowledge, the first CMOS logic family that is both fully static, and truly, fully adiabatic (modulo leakage). In addition, S2LAL is, we think, the fastest possible such family (among fully pipelined sequential circuits), having a latency per logic stage of one tick (transition time), and a minimum clock period (initiation interval) of 8 ticks. S2LAL requires 8 phases of a trapezoidal power-clock waveform (plus constant power and ground references) to be supplied. We argue that, if implemented in a suitable fabrication process designed to aggressively minimize leakage, S2LAL should be capable of demonstrating a greater level of energy efficiency than any other semiconductor-based digital logic family known today.

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Characterization of Amplification Properties of the Superconducting-Ferromagnetic Transistor

IEEE Transactions on Applied Superconductivity

Nevirkovets, Ivan P.; Kojima, Takafumi; Uzawa, Yoshinori; Kotula, Paul G.; Missert, Nancy A.; Mukhanov, Oleg A.

We report on the measurement results of the superconducting-ferromagnetic transistors (SFTs). The devices were made at Northwestern University and Hypres (SeeQC), Inc. (Nevirkovets et al., 2014; 2015). SFT is a multiterminal device with the SISFIFS (or SFIFSIS) structure (where S, I, and F denote a superconductor, an insulator, and a ferromagnetic material, respectively) exploiting intense quasiparticle injection in order to modify the nonlinear I-V curve of a superconducting tunnel junction. SFT is capable of providing voltage, current, and power amplification while having good input/output isolation. We characterized the devices using different measurement techniques. We measured S parameters of the single- and double-acceptor devices at frequencies up to 5 MHz. Importantly, we confirmed that the isolation between the input and output of the device is quite good. However, the techniques typically employed to characterize semiconductor devices do not allow for revealing the full potential of our low-resistive SFT devices, especially those having two acceptors. In the latter case, we also tested the devices using the battery-powered current sources with floating grounds. Analyzing double-acceptor I-V curves recorded at different levels of injection currents, for an optimal load, we deduced a small-signal voltage gain of 33 and a power gain of 2.4. We suggest that further improvement of the SFT device parameters is possible in optimized devices, so that the device potentially may serve as a preamplifier for readout of output signals of cryogenic detectors and be useful as an element of other superconductor-based circuits. In addition, we used scanning transmission electron microscopy to identify some problems in the fabrication of the devices without any planarization.

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Spin transport in an insulating ferrimagnetic-antiferromagnetic-ferrimagnetic trilayer as a function of temperature

AIP Advances

Chen, Yizhang; Cogulu, Egecan; Roy, Debangsu; Ding, Jinjun; Mohammadi, Jamileh B.; Kotula, Paul G.; Missert, Nancy A.; Wu, Mingzhong; Kent, Andrew D.

We present a study of the transport properties of thermally generated spin currents in an insulating ferrimagnetic-antiferromagnetic-ferrimagnetic trilayer over a wide range of temperature. Spin currents generated by the spin Seebeck effect (SSE) in a yttrium iron garnet (YIG) YIG/NiO/YIG trilayer on a gadolinium gallium garnet (GGG) substrate were detected using the inverse spin Hall effect (ISHE) in Pt. By studying samples with different NiO thicknesses, the spin diffusion length of NiO was determined to be ∼3.8 nm at room temperature. Surprisingly, a large increase of the SSE signal was observed below 30 K, and the field dependence of the signal closely follows a Brillouin function for an S=7/2 spin. The increase of the SSE signal at low temperatures could thus be associated with the paramagnetic SSE from the GGG substrate. Besides, a broad peak in the SSE response was observed around 100 K. These observations are important in understanding the generation and transport properties of spin currents through magnetic insulators and the role of a paramagnetic substrate in spin current generation.

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Asynchronous Ballistic Reversible Fluxon Logic

IEEE Transactions on Applied Superconductivity

Frank, Michael P.; Lewis, Rupert; Missert, Nancy A.; Wolak, Matthaeus W.; Henry, Michael D.

In a previous paper, we described a new abstract circuit model for reversible computation called asynchronous ballistic reversible computing (ABRC), in which localized information-bearing pulses propagate ballistically along signal paths between stateful abstract devices and elastically scatter off those devices serially, while updating the device state in a logically-reversible and deterministic fashion. The ABRC model has been shown to be capable of universal computation. In the research reported here, we begin exploring how the ABRC model might be realized in practice using single flux quantum solitons (fluxons) in superconducting Josephson junction (JJ) circuits. One natural family of realizations could utilize fluxon polarity to represent binary data in individual pulses propagating near-ballistically, along discrete or continuous long Josephson junctions or microstrip passive transmission lines, and utilize the flux charge (-1, 0, +1) of a JJ-containing superconducting loop with Φ0 < IcL < 2Φ0 to encode a ternary state variable internal to a device. A natural question then arises as to which of the definable abstract ABRC device functionalities using this data representation might be implementable using a JJ circuit that dissipates only a small fraction of the input fluxon energy. We discuss conservation rules and symmetries considered as constraints to be obeyed in these circuits, and begin the process of classifying the possible ABRC devices in this family having up to three bidirectional I/O terminals, and up to three internal states.

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SNS Josephson Junctions with Tunable Ta-N Barriers

IEEE Transactions on Applied Superconductivity

Wolak, Matthaeus W.; Missert, Nancy A.; Henry, Michael D.; Lewis, Rupert; Wolfley, Steven L.; Brunke, Lyle B.; Sierra Suarez, Jonatan A.

We report on the fabrication and characterization of Nb/Ta-N/Nb Josephson junctions grown by room temperature magnetron sputtering on 150-mm diameter Si wafers. Junction characteristics depend upon the Ta-N barrier composition, which was varied by adjusting the N2 flow during film deposition. Higher N2 flow rates raise the barrier resistance and increase the junction critical current. This work demonstrates the viability of Ta-N as an alternative barrier to aluminum oxide, with the potential for large scale integration.

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Diagnosis of Factors Impacting Yield in Multilayer Devices for Superconducting Electronics

IEEE Transactions on Applied Superconductivity

Missert, Nancy A.; Jenkins, Mark W.; Tangyunyong, Paiboon T.; Mook, William; Vernik, Igor V.; Kirichenko, Alex F.; Mukhanov, Oleg A.; Wynn, Alex; Day, Alexandra L.; Bolkhovsky, Vladimir; Johnson, Leonard M.

The ability to localize defects in order to understand failure mechanisms in complex superconducting electronics circuits, while operating at low temperature, does not yet exist. This work applies thermally-induced voltage alteration (TIVA), to a biased superconducting electronics (SCE) circuit at ambient temperature. TIVA is a commonly used, laser-based failure analysis technique developed for silicon-based microelectronics. The non-operational circuit consisted of an arithmetic logic unit (ALU) in a high-frequency test bed designed at HYPRES and fabricated by MIT Lincoln Laboratory using their SFQ5ee process. Localized TIVA signals were correlated with reflected light images at the surface, and these sites were further investigated by scanning electron microscopy imaging of focused ion-beam cross-sections. The areas investigated, where prominent TIVA signals were observed, showed seams in the Nb wiring layers at contacts to Josephson junctions or inductors and/or disrupted junction morphologies. These results suggest that the TIVA technique can be used at ambient temperature to diagnose fabrication defects that may cause low temperature circuit failure.

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Measuring Changes in Inductance with Microstrip Resonators

IEEE Transactions on Applied Superconductivity

Lewis, Rupert; Henry, Michael D.; Young, Travis R.; Frank, Michael P.; Wolak, Matthaeus W.; Missert, Nancy A.

We measure the frequency dependence of a niobium microstrip resonator as a function of temperature from 1.4 to 8.4 K. In a 2-micrometer-wide half-wave resonator, we find the frequency of resonance changes by a factor of 7 over this temperature range. From the resonant frequencies, we extract inductance per unit length, characteristic impedance, and propagation velocity (group velocity). We discuss how these results relate to superconducting electronics. Over the 2 K to 6 K temperature range where superconducting electronic circuits operate, inductance shows a 19% change and both impedance and propagation velocity show an 11% change.

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Semi-Automated Design of Functional Elements for a New Approach to Digital Superconducting Electronics: Methodology and Preliminary Results

ISEC 2019 - International Superconductive Electronics Conference

Frank, Michael P.; Lewis, Rupert; Missert, Nancy A.; Henry, M.D.; Wolak, Matthaeus W.; Debenedictis, Erik P.

In an ongoing project at Sandia National Laboratories, we are attempting to develop a novel style of superconducting digital processing, based on a new model of reversible computation called Asynchronous Ballistic Reversible Computing (ABRC). We envision an approach in which polarized flux-ons scatter elastically from near-lossless functional components, reversibly updating the local digital state of the circuit, while dissipating only a small fraction of the input fluxon energy. This approach to superconducting digital computation is sufficiently unconventional that an appropriate methodology for hand-design of such circuits is not immediately obvious. To gain insight into the design principles that are applicable in this new domain, we are creating a software tool to automatically enumerate possible topologies of reactive, undamped Josephson junction circuits, and sweep the parameter space of each circuit searching for designs exhibiting desired dynamical behaviors. But first, we identified by hand a circuit implementing the simplest possible nontrivial ABRC functional behavior with bits encoded as conserved polarized fluxons, namely, a one-bit reversible memory cell with one bidirectional I/O port. We expect the tool to be useful for designing more complex circuits.

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Spin-triplet supercurrent in Josephson junctions containing a synthetic antiferromagnet with perpendicular magnetic anisotropy

Physical Review B

Click, J.A.; Edwards, S.E.; Korucu, D.K.; Aguilar, V.A.; Niedzielski, B.M.; Loloee, R.L.; Pratt, W.P.; Birge, N.O.; Kotula, Paul G.; Missert, Nancy A.

In this paper, we present measurements of Josephson junctions containing three magnetic layers with noncollinear magnetizations. The junctions are of the form

S/F'/N/F/N/F"/S

, where

S

is superconducting Nb,

F'

is either a thin Ni or Permalloy layer with in-plane magnetization,

N

is the normal metal Cu,

F

is a synthetic antiferromagnet with magnetization perpendicular to the plane, composed of Pd/Co multilayers on either side of a thin Ru spacer, and

F"

is a thin Ni layer with in-plane magnetization. The supercurrent in these junctions decays more slowly as a function of the

F

-layer thickness than for similar spin-singlet junctions not containing the

F'

and

F"

layers. The slower decay is the prime signature that the supercurrent in the central part of these junctions is carried by spin-triplet pairs. Finally, the junctions containing

F'=

Permalloy are suitable for future experiments where either the amplitude of the critical current or the ground-state phase difference across the junction is controlled by changing the relative orientations of the magnetizations of the

F'

and

F"

layers.

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Tunable Nitride Josephson Junctions

Missert, Nancy A.; Henry, Michael D.; Lewis, Rupert; Howell, Stephen W.; Wolfley, Steven L.; Brunke, Lyle B.; Wolak, Matthaeus W.

We have developed an ambient temperature, SiO2/Si wafer - scale process for Josephson junctions based on Nb electrodes and Ta x N barriers with tunable electronic properties. The films are fabricated by magnetron sputtering. The electronic properties of the TaxN barriers are controlled by adjusting the nitrogen flow during sputtering. This technology offers a scalable alternative to the more traditional junctions based on AlOx barriers for low - power, high - performance computing.

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Critical current oscillations of elliptical Josephson junctions with single-domain ferromagnetic layers

Journal of Applied Physics

Glick, Joseph A.; Khasawneh, Mazin A.; Niedzielski, Bethany M.; Loloee, Reza; Pratt, W.P.; Birge, Norman O.; Gingrich, E.C.; Kotula, Paul G.; Missert, Nancy A.

Josephson junctions containing ferromagnetic layers are of considerable interest for the development of practical cryogenic memory and superconducting qubits. Such junctions exhibit a ground-state phase shift of π for certain ranges of ferromagnetic layer thicknesses. We present studies of Nb based micron-scale elliptically shaped Josephson junctions containing ferromagnetic barriers of Ni81Fe19 or Ni65Fe15Co20. By applying an external magnetic field, the critical current of the junctions is found to follow characteristic Fraunhofer patterns and display sharp switching behavior suggestive of single-domain magnets. The high quality of the Fraunhofer patterns enables us to extract the maximum value of the critical current even when the peak is shifted significantly outside the range of the data due to the magnetic moment of the ferromagnetic layer. The maximum value of the critical current oscillates as a function of the ferromagnetic barrier thickness, indicating transitions in the phase difference across the junction between values of zero and π. We compare the data to previous work and to models of the 0-π transitions based on existing theories.

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Materials Study of NbN and TaxN Thin Films for SNS Josephson Junctions

IEEE Transactions on Applied Superconductivity

Missert, Nancy A.; Brunke, Lyle B.; Henry, Michael D.; Wolfley, Steven L.; Howell, Stephen W.; Mudrick, John M.; Lewis, Rupert

Properties of NbN and TaxN thin films grown at ambient temperatures on SiO2/Si substrates by reactive-pulsed laser deposition and reactive magnetron sputtering (MS) as a function of N2 gas flow were investigated. Both techniques produced films with smooth surfaces, where the surface roughness did not depend on the N2 gas flow during growth. High crystalline quality, (111) oriented NbN films with Tc up to 11 K were produced by both techniques for N contents near 50%. The low temperature transport properties of the TaxN films depended upon both the N2 partial pressure used during growth and the film thickness. The root mean square surface roughness of TaxN films grown by MS increased as the film thickness decreased down to 10 nm.

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Analysis of multilayer devices for superconducting electronics by high-resolution scanning transmission electron microscopy and energy dispersive spectroscopy

IEEE Transactions on Applied Superconductivity

Missert, Nancy A.; Kotula, Paul G.; Rye, Michael J.; Rehm, Laura; Sluka, Volker; Kent, Andrew D.; Yohannes, Daniel; Kirichenko, Alex F.; Vernik, Igor V.; Mukhanov, Oleg A.; Bolkhovsky, Vladimir; Wynn, Alex; Johnson, Leonard; Gouker, Mark

A focused ion beam was used to obtain cross-sectional specimens from both magnetic multilayer and Nb/Al-AlOx/Nb Josephson junction devices for characterization by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX). Automated multivariate statistical analysis of the EDX spectral images produced chemically unique component images of individual layers within the multilayer structures. STEM imaging elucidated distinct variations in film morphology, interface quality, and/or etch artifacts that could be correlated to magnetic and/or electrical properties measured on the same devices.

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Corrosion Monitors for Embedded Evaluation

Robinson, Alex L.; Pfeifer, Kent B.; Casias, Adrian L.; Howell, Stephen W.; Sorensen, Neil R.; Missert, Nancy A.

We have developed and characterized novel in-situ corrosion sensors to monitor and quantify the corrosive potential and history of localized environments. Embedded corrosion sensors can provide information to aid health assessments of internal electrical components including connectors, microelectronics, wires, and other susceptible parts. When combined with other data (e.g. temperature and humidity), theory, and computational simulation, the reliability of monitored systems can be predicted with higher fidelity.

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Degradation of superconducting Nb/NbN films by atmospheric oxidation

IEEE Transactions on Applied Superconductivity

Henry, Michael D.; Wolfley, Steven L.; Young, Travis R.; Monson, Todd M.; Pearce, Charles J.; Lewis, Rupert; Clark, Blythe C.; Brunke, Lyle B.; Missert, Nancy A.

Niobium and niobium nitride thin films are transitioning from fundamental research toward wafer scale manufacturing with technology drivers that include superconducting circuits and electronics, optical single photon detectors, logic, and memory. Successful microfabrication requires precise control over the properties of sputtered superconducting films, including oxidation. Previous work has demonstrated the mechanism in oxidation of Nb and how film structure could have deleterious effects upon the superconducting properties. This study provides an examination of atmospheric oxidation of NbN films. By examination of the room temperature sheet resistance of NbN bulk oxidation was identified and confirmed by secondary ion mass spectrometry. As a result, Meissner magnetic measurements confirmed the bulk oxidation not observed with simple cryogenic resistivity measurements.

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Thermal battery degradation mechanisms

Missert, Nancy A.; Brunke, Lyle B.

Diffuse reflectance IR spectroscopy (DRIFTS) was used to investigate the effect of accelerated aging on LiSi based anodes in simulated MC3816 batteries. DRIFTS spectra showed that the oxygen, carbonate, hydroxide and sulfur content of the anodes changes with aging times and temperatures, but not in a monotonic fashion that could be correlated to phase evolution. Bands associated with sulfur species were only observed in anodes taken from batteries aged in wet environments, providing further evidence for a reaction pathway facilitated by H2S transport from the cathode, through the separator, to the anode. Loss of battery capacity with accelerated aging in wet environments was correlated to loss of FeS2 in the catholyte pellets, suggesting that the major contribution to battery performance degradation results from loss of active cathode material.

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Hierarchical electrode architectures for electrical energy storage & conversion

Zavadil, Kevin R.; Missert, Nancy A.; Van Swol, Frank

The integration and stability of electrocatalytic nanostructures, which represent one level of porosity in a hierarchical structural scheme when combined with a three-dimensional support scaffold, has been studied using a combination of synthetic processes, characterization techniques, and computational methods. Dendritic platinum nanostructures have been covalently linked to common electrode surfaces using a newly developed chemical route; a chemical route equally applicable to a range of metals, oxides, and semiconductive materials. Characterization of the resulting bound nanostructure system confirms successful binding, while electrochemistry and microscopy demonstrate the viability of these electroactive particles. Scanning tunneling microscopy has been used to image and validate the short-term stability of several electrode-bound platinum dendritic sheet structures toward Oswald ripening. Kinetic Monte Carlo methods have been applied to develop an understanding of the stability of the basic nano-scale porous platinum sheets as they transform from an initial dendrite to hole containing sheets. Alternate synthetic strategies were pursued to grow dendritic platinum structures directly onto subunits (graphitic particles) of the electrode scaffold. A two-step photocatalytic seeding process proved successful at generating desirable nano-scale porous structures. Growth in-place is an alternate strategy to the covalent linking of the electrocatalytic nanostructures.

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Nanoengineering for solid-state lighting

Crawford, Mary H.; Fischer, Arthur J.; Koleske, Daniel K.; Missert, Nancy A.

This report summarizes results from a 3-year Laboratory Directed Research and Development project performed in collaboration with researchers at Rensselaer Polytechnic Institute. Our collaborative effort was supported by Sandia's National Institute for Nanoengineering and focused on the study and application of nanoscience and nanoengineering concepts to improve the efficiency of semiconductor light-emitting diodes for solid-state lighting applications. The project explored LED efficiency advances with two primary thrusts: (1) the study of nanoscale InGaN materials properties, particularly nanoscale crystalline defects, and their impact on internal quantum efficiency, and (2) nanoscale engineering of dielectric and metal materials and integration with LED heterostructures for enhanced light extraction efficiency.

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Luminescent properties of solution-grown ZnO nanorods

Applied Physics Letters

Hsu, Julia W.; Tallant, David T.; Simpson, Regina L.; Missert, Nancy A.; Copeland, Robert G.

The optical properties of solution-grown ZnO nanorods were investigated using photolumincscence and cathodoluminescence. The as-grown nanorods displayed a broad yellow-orange sub-band-gap luminescence and a small near-band-gap emission peak. The sub-band-gap luminescence can only be observed when exciting above band gap. Scanning cathodoluminescence experiments showed that the width of the sub-band-gap luminescence is not due to an ensemble effect. Upon reduction, the sub-band-gap luminescence disappeared and the near-band-gap emission increased. Compared to ZnO powders that are stoichiometric and oxygen deficient, we conclude that the yellow-orange sub-band-gap luminescence most likely arises from bulk defects that, are associated with excess oxygen. © 2006 American Institute of Physics.

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Materials physics and device development for improved efficiency of GaN HEMT high power amplifiers

Koleske, Daniel K.; Shul, Randy J.; Follstaedt, D.M.; Provencio, P.N.; Allerman, A.A.; Wright, Alan F.; Missert, Nancy A.; Baca, A.G.; Briggs, R.D.; Marsh, Philbert F.; Tigges, Chris P.

GaN-based microwave power amplifiers have been identified as critical components in Sandia's next generation micro-Synthetic-Aperture-Radar (SAR) operating at X-band and Ku-band (10-18 GHz). To miniaturize SAR, GaN-based amplifiers are necessary to replace bulky traveling wave tubes. Specifically, for micro-SAR development, highly reliable GaN high electron mobility transistors (HEMTs), which have delivered a factor of 10 times improvement in power performance compared to GaAs, need to be developed. Despite the great promise of GaN HEMTs, problems associated with nitride materials growth currently limit gain, linearity, power-added-efficiency, reproducibility, and reliability. These material quality issues are primarily due to heteroepitaxial growth of GaN on lattice mismatched substrates. Because SiC provides the best lattice match and thermal conductivity, SiC is currently the substrate of choice for GaN-based microwave amplifiers. Obviously for GaN-based HEMTs to fully realize their tremendous promise, several challenges related to GaN heteroepitaxy on SiC must be solved. For this LDRD, we conducted a concerted effort to resolve materials issues through in-depth research on GaN/AlGaN growth on SiC. Repeatable growth processes were developed which enabled basic studies of these device layers as well as full fabrication of microwave amplifiers. Detailed studies of the GaN and AlGaN growth of SiC were conducted and techniques to measure the structural and electrical properties of the layers were developed. Problems that limit device performance were investigated, including electron traps, dislocations, the quality of semi-insulating GaN, the GaN/AlGaN interface roughness, and surface pinning of the AlGaN gate. Surface charge was reduced by developing silicon nitride passivation. Constant feedback between material properties, physical understanding, and device performance enabled rapid progress which eventually led to the successful fabrication of state of the art HEMT transistors and amplifiers.

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Scanning probe studies of water nucleation on aluminum oxide and gold surfaces

Proposed for publication in Applied Surface Science.

Missert, Nancy A.; Copeland, Robert G.

The nucleation of nanoscale water at surfaces in humid environments is sensitive to several factors, including the details of the surface morphology, ability of the surface to hydrate and the presence of contaminants. Tapping mode atomic force microscopy was used to investigate the nucleation process as a function of relative humidity (RH) on passive aluminum and gold thin films. Films exposed to the ambient environment prior to RH exposure showed discrete structures with lateral sizes ranging from 10 to 100 nm only at RH > 70%. These structures formed preferentially at grain boundaries, triple points and regions with significant topography such as protruding grains. The morphology of the passive aluminum surface is permanently altered at the sites where discrete structures were observed; nodules with heights ranging from 0.5 to 2 nm persist even after reducing the RH to <2%. The gold surface does not show such a permanent change in morphology after reducing the RH. Passive aluminum films exposed to high RH immediately after growth (e.g. no ambient exposure) do not show discrete structures even at the highest RH exposures of 90%, suggesting a hydrophilic surface and the importance of surface hydrocarbon contaminants in affecting the distribution of the water layer.

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Final report on grand challenge LDRD project : a revolution in lighting : building the science and technology base for ultra-efficient solid-state lighting

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.

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The effects of varying humidity on copper sulfide film formation

Sullivan, John P.; Sullivan, John P.; Barbour, J.C.; Missert, Nancy A.; Copeland, Robert G.; Mayer, T.M.

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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Plan-view image contrast of dislocations in GaN

Proposed for publication in Applied Physics Letters.

Follstaedt, D.M.; Follstaedt, D.M.; Missert, Nancy A.; Koleske, Daniel K.; Mitchell, Christine C.; Cross, Karen C.

We demonstrate that when vertical threading dislocations in (0001) GaN are imaged in plan-view by transmission electron microscopy, a surface-relaxation contrast operates in addition to that due to the strain fields of dislocations passing through the specimen. We show that all three dislocation types (edge, screw, and mixed) can be detected in the same image using g = (11{bar 2}0) and 18{sup o} specimen tilt from [0001], allowing total densities to be assessed properly. The type of an individual dislocation can also be readily identified.

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Mechanisms of Atmospheric Copper Sulfidation and Evaluation of Parallel Experimentation Techniques

Barbour, J.C.; Breiland, William G.; Moffat, Harry K.; Sullivan, John P.; Campin, Michael J.; Wright, Alan F.; Missert, Nancy A.; Braithwaite, J.W.; Zavadil, Kevin R.; Sorensen, Neil R.; Lucero, Samuel J.

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.

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Low-Dislocation-Density GaN from a Single Growth on a Textured Substrate

Applied Physics Letters

Ashby, Carol I.; Mitchell, Christine C.; Han, J.; Missert, Nancy A.; Provencio, P.N.; Follstaedt, D.M.; Peake, Gregory M.; Griego, Leonardo G.

The density of threading dislocations (TD) in GaN grown directly on flat sapphire substrates is typically greater than 10{sup 9}/cm{sup 2}. Such high dislocation densities degrade both the electronic and photonic properties of the material. The density of dislocations can be decreased by orders of magnitude using cantilever epitaxy (CE), which employs prepatterned sapphire substrates to provide reduced-dimension mesa regions for nucleation and etched trenches between them for suspended lateral growth of GaN or AlGaN. The substrate is prepatterned with narrow lines and etched to a depth that permits coalescence of laterally growing III-N nucleated on the mesa surfaces before vertical growth fills the etched trench. Low dislocation densities typical of epitaxial lateral overgrowth (ELO) are obtained in the cantilever regions and the TD density is also reduced up to 1 micrometer from the edge of the support regions.

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Electronic defects and interface potentials for Al oxide films on Al and their relationship to electrochemical properties

Sullivan, John P.; Dunn, Roberto G.; Barbour, J.C.; Wall, Frederick D.; Missert, Nancy A.

The relative electronic defect densities and oxide interface potentials were determined for naturally-occurring and synthetic Al oxides on Al. In addition, the effect of electrochemical treatment on the oxide electrical properties was assessed. The measurements revealed (1) that the open circuit potential of Al in aqueous solution is inversely correlated with the oxide electronic defect density (viz., lower oxide conductivities are correlated with higher open circuit potentials), and (2) the electronic defect density within the Al oxide is increased upon exposure to an aqueous electrolyte at open circuit or applied cathodic potentials, while the electronic defect density is reduced upon exposure to slight anodic potentials in solution. This last result, combined with recent theoretical predictions, suggests that hydrogen may be associated with electronic defects within the Al oxide, and that this H may be a mobile species, diffusing as H{sup +}. The potential drop across the oxide layer when immersed in solution at open circuit conditions was also estimated and found to be 0.3 V, with the field direction attracting positive charge towards the Al/oxide interface.

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Growth and Oxidation of Thin Film Al(2)Cu

Journal of the Electrochemical Society

Missert, Nancy A.; Barbour, J.C.; Copeland, Robert G.; Minor, Kenneth G.

Al{sub 2}Cu thin films ({approx} 382 nm) are fabricated by melting and resolidifying Al/Cu bilayers in the presence of a {micro} 3 nm Al{sub 2}O{sub 3} passivating layer. X-ray Photoelectron Spectroscopy (XPS) measures a 1.0 eV shift of the Cu2p{sub 3/2} peak and a 1.6 eV shift of the valence band relative to metallic Cu upon Al{sub 2}Cu formation. Scanning Electron microscopy (SEM) and Electron Back-Scattered Diffraction (EBSD) show that the Al{sub 2}Cu film is composed of 30-70 {micro}m wide and 10-25 mm long cellular grains with (110) orientation. The atomic composition of the film as estimated by Energy Dispersive Spectroscopy (EDS) is 67 {+-} 2% Al and 33 {+-} 2% Cu. XPS scans of Al{sub 2}O{sub 3}/Al{sub 2}Cu taken before and after air exposure indicate that the upper Al{sub 2}Cu layers undergo further oxidation to Al{sub 2}O{sub 3} even in the presence of {approx} 5 nm Al{sub 2}O{sub 3}. The majority of Cu produced from oxidation is believed to migrate below the Al{sub 2}O{sub 3} layers, based upon the lack of evidence for metallic Cu in the XPS scans. In contrast to Al/Cu passivated with Al{sub 2}O{sub 3}, melting/resolidifying the Al/Cu bilayer without Al{sub 2}O{sub 3} results in phase-segregated dendritic film growth.

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87 Results
87 Results