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.
The most energy efficient solid state white light source will likely be a combination of individually efficient red, green, and blue LED. For any multi-color approach to be successful the efficiency of deep green LEDs must be significantly improved. While traditional approaches to improve InGaN materials have yielded incremental success, we proposed a novel approach using group IIIA and IIIB nitride semiconductors to produce efficient green and high wavelength LEDs. To obtain longer wavelength LEDs in the nitrides, we attempted to combine scandium (Sc) and yttrium (Y) with gallium (Ga) to produce ScGaN and YGaN for the quantum well (QW) active regions. Based on linear extrapolation of the proposed bandgaps of ScN (2.15 eV), YN (0.8 eV) and GaN (3.4 eV), we expected that LEDs could be fabricated from the UV (410 nm) to the IR (1600 nm), and therefore cover all visible wavelengths. The growth of these novel alloys potentially provided several advantages over the more traditional InGaN QW regions including: higher growth temperatures more compatible with GaN growth, closer lattice matching to GaN, and reduced phase separation than is commonly observed in InGaN growth. One drawback to using ScGaN and YGaN films as the active regions in LEDs is that little research has been conducted on their growth, specifically, are there metalorganic precursors that are suitable for growth, are the bandgaps direct or indirect, can the materials be grown directly on GaN with a minimal defect formation, as well as other issues related to growth. The major impediment to the growth of ScGaN and YGaN alloys was the low volatility of metalorganic precursors. Despite this impediment some progress was made in incorporation of Sc and Y into GaN which is detailed in this report. Primarily, we were able to incorporate up to 5 x 10{sup 18} cm{sup -3} Y atoms into a GaN film, which are far below the alloy concentrations needed to evaluate the YGaN optical properties. After a no-cost extension was granted on this program, an additional more 'liquid-like' Sc precursor was evaluated and the nitridation of Sc metals on GaN were investigated. Using the Sc precursor, dopant level quantities of Sc were incorporated into GaN, thereby concluding the growth of ScGaN and YGaN films. Our remaining time during the no-cost extension was focused on pulsed laser deposition of Sc metal films on GaN, followed by nitridation in the MOCVD reactor to form ScN. Finally, GaN films were deposited on the ScN thin films in order to study possible GaN dislocation reduction.
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 report growth of InGaN/GaN multi-quantum well (MQW) and LED structures on a novel composite substrate designed to eliminate the coefficient of thermal expansion (CTE) mismatch problems which impact GaN growth on bulk sapphire. To form the composite substrate, a thin sapphire layer is wafer-bonded to a polycrystalline aluminum nitride (P-AlN) support substrate. The sapphire layer provides the epitaxial template for the growth; however, the thermo-mechanical properties of the composite substrate are determined by the P-AlN. Using these substrates, thermal stresses associated with temperature changes during growth should be reduced an order of magnitude compared to films grown on bulk sapphire, based on published CTE data. In order to test the suitability of the substrates for GaN LED growth, test structures were grown by metalorganic chemical vapor deposition (MOCVD) using standard process conditions for GaN growth on sapphire. Bulk sapphire substrates were included as control samples in all growth runs. In situ reflectance monitoring was used to compare the growth dynamics for the different substrates. The material quality of the films as judged by X-ray diffraction (XRD), photoluminescence and transmission electron microscopy (TEM) was similar for the composite substrate and the sapphire control samples. Electroluminescence was obtained from the LED structure grown on a P-AlN composite substrate, with a similar peak wavelength and peak width to the control samples. XRD and Raman spectroscopy results confirm that the residual strain in GaN films grown on the composite substrates is dramatically reduced compared to growth on bulk sapphire substrates.
We present the results of a three year LDRD project which has focused on the development of novel, compact, ultraviolet solid-state sources and fluorescence-based sensing platforms that apply such devices to the sensing of biological and nuclear materials. We describe our development of 270-280 nm AlGaN-based semiconductor UV LEDs with performance suitable for evaluation in biosensor platforms as well as our development efforts towards the realization of a 340 nm AlGaN-based laser diode technology. We further review our sensor development efforts, including evaluation of the efficacy of using modulated LED excitation and phase sensitive detection techniques for fluorescence detection of bio molecules and uranyl-containing compounds.
We present the results of a one year LDRD program that has focused on evaluating the use of newly developed deep ultraviolet LEDs in water purification. We describe our development efforts that have produced an LED-based water exposure set-up and enumerate the advances that have been made in deep UV LED performance throughout the project. The results of E. coli inactivation with 270-295 nm LEDs are presented along with an assessment of the potential for applying deep ultraviolet LED-based water purification to mobile point-of-use applications as well as to rural and international environments where the benefits of photovoltaic-powered systems can be realized.
Transmission electron microscopy and x-ray diffraction were used to assess the microstructure and strain of Al{sub x}Ga{sub 1?x}N(x = 0.61-0.64) layers grown on AlN. The compressively-strained AlGaN is partially relaxed by inclined threading dislocations, similar to observations on Si-doped AlGaN by P. Cantu, F. Wu, P. Waltereit, S. Keller, A. E. Romanov, U. K. Mishra, S. P. DenBaars, and J. S. Speck [Appl. Phys. Lett. 83, 674 (2003) ]; however, in our material, the dislocations bend before the introduction of any Si. The bending may be initiated by the greater lattice mismatch or the lower dislocation density of our material, but the presence of Si is not necessarily required. The relaxation by inclined dislocations is quantitatively accounted for with the model of A. E. Romanov and J. S. Speck [Appl. Phys. Lett. 83, 2569 (2003)], and we demonstrate the predicted linear dependence of relaxation on layer thickness. Notably, such relaxation was not found in tensile strained AlGaN grown on GaN [J. A. Floro, D. M. Follstaedt, P. Provencio, S. J. Hearne, and S. R. Lee, J. Appl. Phys. 96, 7087 (2004)], even though the same mechanism appears applicable.
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.
Forward-to-reverse bias step-recovery measurements were performed on In.07Ga.93N/GaN and Al.36Ga.64N/Al.46Ga.54N quantum-well (QW) light-emitting diodes grown on sapphire. With the QW sampling the minority-carrier hole density at a single position, distinctive two-phase optical decay curves were observed. Using diffusion equation solutions to self-consistently model both the electrical and optical responses, hole transport parameters tp = 758 {+-} 44 ns, Lp = 588 {+-} 45 nm, and up = 0.18 {+-} 0.02 cm2/Vs were obtained for GaN. The mobility was thermally activated with an activation energy of 52 meV, suggesting trap-modulated transport. Optical measurements of sub-bandgap peaks exhibited slow responses approaching the bulk lifetime. For Al.46Ga.54N, a longer lifetime of tp = 3.0 us was observed, and the diffusion length was shorter, Lp = 280 nm. Mobility was an order of magnitude smaller than in GaN, up = 10-2 cm2/Vs, and was insensitive to temperature, suggesting hole transport through a network of defects.
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.
An AlGaN Light-emitting diode (LED) emitting with a peak wavelength at 291 nm and a radiant power of 0.5 mW @ 100 mA was fabricated on a sapphire substrate. A compact gated fluorescence detection system was built using this LED as the excitation light source. We demonstrate that it provides sufficient power using Terbium enhanced fluorescence to detect subnanomolar concentrations of dipicolinic acid (DPA, 2, 6-pyridinedicarboxylic acid), a substance uniquely present in bacterial spores such as that from B. anthracis, providing a basis for convenient early warning detectors. We also describe initial results from a novel approach for biological aerosol detection using long lived fluorescence from a Europium tagged dye that binds to proteins.
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.
The diffusion, uptake, and release of H in p-type GaN are modeled employing state energies from density-function theory and compared with measurements of deuterium uptake and release using nuclear-reaction analysis. Good semiquantitative agreement is found when account is taken of a surface permeation barrier.
Formation energies and vibrational frequencies for H in wurtzite GaN were calculated from density functional theory and used to predict equilibrium state occupancies and solid solubilities for p-type, intrinsic, and n-type material. The solubility of deuterium (D) was measured at 600--800 C as a function of D{sub 2} pressure and doping and compared with theory. Agreement was obtained by reducing the H formation energies 0.2 eV from ab-initio theoretical values. The predicted stretch-mode frequency for H bound to the Mg acceptor lies 5% above an observed infrared absorption attributed to this complex. It is concluded that currently recognized H states and physical processes account for the equilibrium behavior of H examined in this work.
We report the growth and characterization of quaternary AlGaInN. A combination of photoluminescence (PL), high-resolution x-ray diffraction (XRD), and Rutherford backscattering spectrometry (RBS) characterizations enables us to explore the contours of constant PL peak energy and lattice parameter as functions of the quaternary compositions. The observation of room temperature PL emission at 351nm (with 20% Al and 5% In) renders initial evidence that the quaternary could be used to provide confinement for GaInN (and possibly GaN). AlGaInN/GrdnN MQW heterostructures have been grown; both XRD and PL measurements suggest the possibility of incorporating this quaternary into optoelectronic devices.
In this paper, we overview several of the critical materials growth, design and performance issues for nitride-based UV (<400 nm) LEDs. The critical issue of optical efficiency is presented through temperature-dependent photoluminescence studies of various UV active regions. These studies demonstrate enhanced optical efficiencies for active regions with In-containing alloys (InGaN, AlInGaN). We discuss the trade-off between the challenging growth of high Al containing alloys (AlGaN, AlGaInN), and the need for sufficient carrier confinement in UV heterostructures. Carrier leakage for various composition AlGaN barriers is examined through a calculation of the total unconfined carrier density in the quantum well system. We compare the performance of two distinct UV LED structures: GaN/AlGaN quantum well LEDs for λ<360 nm emission, and InGaN/AlGaInN quantum well LEDs for 370 nm<λ<390 nm emission.
The LDRD entitled ``Role of Defects in III-Nitride Based Devices'' is aimed to place Sandia National Laboratory at the forefront of the field of GaN materials and devices by establishing a scientific foundation in areas such as material growth, defect characterization/modeling, and processing (metalization and etching) chemistry. In this SAND report the authors summarize their studies such as (1) the MOCVD growth and doping of GaN and AlGaN, (2) the characterization and modeling of hydrogen in GaN, including its bonding, diffusion, and activation behaviors, (3) the calculation of energetic of various defects including planar stacking faults, threading dislocations, and point defects in GaN, and (4) dry etching (plasma etching) of GaN (n- and p-types) and AlGaN. The result of the first AlGaN/GaN heterojunction bipolar transistor is also presented.