Our ability to field useful, nano-enabled microsystems that capitalize on recent advances in sensor technology is severely limited by the energy density of available power sources. The catalytic nanodiode (reported by Somorjai's group at Berkeley in 2005) was potentially an alternative revolutionary source of micropower. Their first reports claimed that a sizable fraction of the chemical energy may be harvested via hot electrons (a 'chemicurrent') that are created by the catalytic chemical reaction. We fabricated and tested Pt/GaN nanodiodes, which eventually produced currents up to several microamps. Our best reaction yields (electrons/CO{sub 2}) were on the order of 10{sup -3}; well below the 75% values first reported by Somorjai (we note they have also been unable to reproduce their early results). Over the course of this Project we have determined that the whole concept of 'chemicurrent', in fact, may be an illusion. Our results conclusively demonstrate that the current measured from our nanodiodes is derived from a thermoelectric voltage; we have found no credible evidence for true chemicurrent. Unfortunately this means that the catalytic nanodiode has no future as a micropower source.
We present the results of a three year LDRD project that focused on understanding the impact of defects on the electrical, optical and thermal properties of GaN-based nanowires (NWs). We describe the development and application of a host of experimental techniques to quantify and understand the physics of defects and thermal transport in GaN NWs. We also present the development of analytical models and computational studies of thermal conductivity in GaN NWs. Finally, we present an atomistic model for GaN NW electrical breakdown supported with experimental evidence. GaN-based nanowires are attractive for applications requiring compact, high-current density devices such as ultraviolet laser arrays. Understanding GaN nanowire failure at high-current density is crucial to developing nanowire (NW) devices. Nanowire device failure is likely more complex than thin film due to the prominence of surface effects and enhanced interaction among point defects. Understanding the impact of surfaces and point defects on nanowire thermal and electrical transport is the first step toward rational control and mitigation of device failure mechanisms. However, investigating defects in GaN NWs is extremely challenging because conventional defect spectroscopy techniques are unsuitable for wide-bandgap nanostructures. To understand NW breakdown, the influence of pre-existing and emergent defects during high current stress on NW properties will be investigated. Acute sensitivity of NW thermal conductivity to point-defect density is expected due to the lack of threading dislocation (TD) gettering sites, and enhanced phonon-surface scattering further inhibits thermal transport. Excess defect creation during Joule heating could further degrade thermal conductivity, producing a viscous cycle culminating in catastrophic breakdown. To investigate these issues, a unique combination of electron microscopy, scanning luminescence and photoconductivity implemented at the nanoscale will be used in concert with sophisticated molecular-dynamics calculations of surface and defect-mediated NW thermal transport. This proposal seeks to elucidate long standing material science questions for GaN while addressing issues critical to realizing reliable GaN NW devices.
Lack of robust manufacturing capabilities have limited our ability to make tailored materials with useful optical and thermal properties. For example, traditional methods such as spontaneous self-assembly of spheres cannot generate the complex structures required to produce a full bandgap photonic crystals. The goal of this work was to develop and demonstrate novel methods of directed self-assembly of nanomaterials using optical and electric fields. To achieve this aim, our work employed laser tweezers, a technology that enables non-invasive optical manipulation of particles, from glass microspheres to gold nanoparticles. Laser tweezers were used to create ordered materials with either complex crystal structures or using aspherical building blocks.
Using a two-step method of plasma and wet chemical etching, we demonstrate smooth, vertical facets for use in Al{sub x} Ga{sub 1-x} N-based deep-ultraviolet laser-diode heterostructures where x = 0 to 0.5. Optimization of plasma-etching conditions included increasing both temperature and radiofrequency (RF) power to achieve a facet angle of 5 deg from vertical. Subsequent etching in AZ400K developer was investigated to reduce the facet surface roughness and improve facet verticality. The resulting combined processes produced improved facet sidewalls with an average angle of 0.7 deg from vertical and less than 2-nm root-mean-square (RMS) roughness, yielding an estimated reflectivity greater than 95% of that of a perfectly smooth and vertical facet.
We describe the fabrication of silicon three dimensional photonic crystals using polymer templates defined by a single step, two-photon exposure through a layer of photopolymer with relief molded on its surface. The resulting crystals exhibit high structural quality over large areas, displaying geometries consistent with calculation. Spectroscopic measurements of transmission and reflection through the silicon and polymer structures reveal excellent optical properties, approaching properties predicted by simulations that assume ideal layouts.
This report describes the investigations and milestones of the Nano-Scale Optical and Electrical Probes of Materials and Processes Junior/Senior LDRD. The goal of this LDRD was to improve our understanding of radiative and non-radiative mechanisms at the nanometer scale with the aim of increasing LED and solar cell efficiencies. These non-radiative mechanisms were investigated using a unique combination of optical and scanning-probe microscopy methods for surface, materials, and device evaluation. For this research we utilized our new near-field scanning optical microscope (NSOM) system to aid in understanding of defect-related emission issues for GaN-based materials. We observed micrometer-scale variations in photoluminescence (PL) intensity for GaN films grown on Cantilever Epitaxy pattern substrates, with lower PL intensity observed in regions with higher dislocation densities. By adding electrical probes to the NSOM system, the photocurrent and surface morphology could be measured concurrently. Using this capability we observed reduced emission in InGaN MQW LEDs near hillock-shaped material defects. In spatially- and spectrally-resolved PL studies, the emission intensity and measured wavelength varied across the wafer, suggesting the possibility of indium segregation within the InGaN quantum wells. Blue-shifting of the InGaN MQW wavelength due to thinning of quantum wells was also observed on top of large-scale ({micro}m) defect structures in GaN. As a direct result of this program, we have expanded the awareness of our new NSOM/multifunctional SPM capability at Sandia and formed several collaborations within Sandia and with NINE Universities. Possible future investigations with these new collaborators might include GaN-based compound semiconductors for green LEDs, nanoscale materials science, and nanostructures, novel application of polymers for OLEDs, and phase imprint lithography for large area 3D nanostructures.
Calculations of specific contact resistance as a function of doping and barrier height were performed for p-type GaN. These calculations took into account two valence bands, each with different effective masses, and show that at low doping, the heavy hole band accounts for most of the conduction, whereas at heavier doping, the light hole band dominates conduction. These calculations also indicate the barrier height for typical contacts to p-GaN is between 0.75 eV and 1 eV. Specific contact resistance measurements were made for oxidized Ni/Au, Pd, and oxidized Ni/Pd ohmic contact metal schemes to p-GaN. The Ni/Pd contact had the lowest specific contact resistance, 6 x 10{sup -4} {Omega} cm{sup 2}. Auger sputter depth profile analysis showed some Ni diffused away from the GaN surface to the contact surface with the bulk of the Pd located in between two areas of Ni. Both Ni and Pd interdiffused with the GaN at the semiconductor surface. The majority of the oxygen observed was with the Ni as NiO. Angle-resolved-x-ray photoelectron spectroscopy (AR-XPS) analyses showed the formation of predominantly NiO and PdO species, with higher Ni and Pd oxides at the contact surface.
Dipicolinic acid (DPA, 2,6-pyridinedicarboxylic acid) is a substance uniquely present in bacterial spores such as that from anthrax (B. anthracis). It is known that DPA can be detected by the long-lived fluorescence of its terbium chelate; the best limit of detection (LOD) reported thus far using a large benchtop gated fluorescence instrument using a pulsed Xe lamp is 2 nM. We use a novel AlGaN light-emitting diode (LED) fabricated on a sapphire substrate that has peak emission at 291 nm. Although the overlap of the emission band of this LED with the absorption band of Tb-DPA ({lambda}{sub max} doublet: 273, 279 nm) is not ideal, we demonstrate that a compact detector based on this LED and an off-the-shelf gated photodetection module can provide an LOD of 0.4 nM, thus providing a basis for convenient early warning detectors.
The goal of this one year LDRD was to improve the overall efficiency of InGaN LEDs by improving the extraction of light from the semiconductor chip. InGaN LEDs are currently the most promising technology for producing high efficiency blue and green semiconductor light emitters. Improving the efficiency of InGaN LEDs will enable a more rapid adoption of semiconductor based lighting. In this LDRD, we proposed to develop photonic structures to improve light extraction from nitride-based light emitting diodes (LEDs). While many advanced device geometries were considered for this work, we focused on the use of a photonic crystal for improved light extraction. Although resonant cavity LEDs and other advanced structures certainly have the potential to improve light extraction, the photonic crystal approach showed the most promise in the early stages of this short program. The photonic crystal (PX)-LED developed here incorporates a two dimensional photonic crystal, or photonic lattice, into a nitride-based LED. The dimensions of the photonic crystal are selected such that there are very few or no optical modes in the plane of the LED ('lateral' modes). This will reduce or eliminate any radiation in the lateral direction so that the majority of the LED radiation will be in vertical modes that escape the semiconductor, which will improve the light-extraction efficiency. PX-LEDs were fabricated using a range of hole diameters and lattice constants and compared to control LEDs without a photonic crystal. The far field patterns from the PX-LEDs were dramatically modified by the presence of the photonic crystal. An increase in LED brightness of 1.75X was observed for light measured into a 40 degree emission cone with a total increase in power of 1.5X for an unencapsulated LED.
Materials studies of high Al-content (> 30%) AlGaN epilayers and the performance of AlGaN-based LEDs with emission wavelengths shorter than 300 nm are reported. N-type AlGaN films with Al compositions greater than 30% reveal a reduction in conductivity with increasing Al composition. The reduction of threading dislocation density from the 1-5 x10{sup 10} cm{sup -2} range to the 6-9 x 10{sup 9}cm{sup -2} range results in an improvement of electrical conductivity and Al{sub 0.90}Ga{sub 0.10}N films with n= 1.6e17 cm-3 and f{acute Y}=20 cm2/Vs have been achieved. The design, fabrication and packaging of flip-chip bonded deep UV LEDs is described. Large area (1 mm x 1 mm) LED structures with interdigitated contacts demonstrate output powers of 2.25 mW at 297 nm and 1.3 mW at 276 nm when operated under DC current. 300 f{acute Y}m x 300 f{acute Y}m LEDs emitting at 295 nm and operated at 20 mA DC have demonstrated less than 50% drop in output power after more than 2400 hours of operation. Optimization of the electron block layer in 274 nm LED structures has enabled a significant reduction in deep level emission bands, and a peak quantum well to deep level ratio of 700:1 has been achieved for 300 f{acute Y}m x 300 f{acute Y}m LEDs operated at 100 mA DC. Shorter wavelength LED designs are described, and LEDs emitting at 260 nm, 254nm and 237 nm are reported.
Ohmic contacts on p-type GaN utilizing Pd/Ir/Au metallization were fabricated and characterized. Metallized samples that were rapid thermally annealed at 400 C for 1 min exhibited linear current-voltage characteristics. Specific ohmic contact resistivities as low as 2 x 10{sup -5} {Omega} cm{sup 2} were achieved. Auger electron spectroscopy and x-ray photoelectron spectroscopy depth profiles of annealed Pd/Ir/Au contact revealed the formation of Pd- and Ir-related alloys at the metal-semiconductor junction with the creation of Ga vacancies below the contact. The excellent contact resistance obtained is attributed to the formation of these Ga vacancies which resulted in the reduction of the depletion region width at the junction.
The junction temperature of AlGaN/GaN ultraviolet (UV) Light-Emitting Diodes (LEDs) emitting at 295 nm is measured by using the temperature coefficients of the diode forward volt-age and emission peak energy. The high-energy slope of the spectrum is explored to measure the carrier temperature. A linear relation between junction temperature and current is found. Analysis of the experimental methods reveals that the diode-forward voltage is the most accurate method (,,b 3 ,,aC). A theoretical model for the dependence of the diode junction voltage (Vj) on junction temperature (T) is developed that takes into account the temperature dependence of the energy gap. A thermal resistance of 87.6 K/W is obtained with the AlGaN/GaN LED sample mounted with thermal paste on a heat sink.
The junction temperature of AlGaN ultraviolet light-emitting diodes emitting at 295 nm is measured by using the temperature coefficients of the diode forward voltage and emission peak energy. The high-energy slope of the spectrum is explored to measure the carrier temperature. A linear relation between junction temperature and current is found. Analysis of the experimental methods reveals that the diode-forward voltage is the most accurate ({+-}3 C). A theoretical model for the dependence of the diode forward voltage (V{sub f}) on junction temperature (T{sub j}) is developed that takes into account the temperature dependence of the energy gap. A thermal resistance of 87.6 K/W is obtained with the device mounted with thermal paste on a heat sink.
Solid-state light sources emitting at wavelengths less than 300 nm would enable technological advances in many areas such as fluorescence-based biological agent detection, non-line-of-sight communications, water purification, and industrial processing including ink drying and epoxy curing. In this paper, we present our recent progress in the development of LEDs with emission between 237 and 297 nm. We will discuss growth and design issues of deep-UV LEDs, including transport in Si-doped AlGaN layers. The LEDs are designed for bottom emission so that improved heat sinking and light extraction can be achieved by flip chipping. To date, we have demonstrated 2.25 mW of output power at 295 nm from 1 mm x 1 mm LEDs operated at 500 mA. Shorter wavelength LEDs emitting at 276 nm have achieved an output power of 1.3 mW at 400 mA. The heterostructure designs that we have employed have suppressed deep level emission to intensities that are up to 330 x lower than the primary quantum well emission.
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.