We present the results of a three year LDRD project that has focused on overcoming major materials roadblocks to achieving AlGaN-based deep-UV laser diodes. We describe our growth approach to achieving AlGaN templates with greater than ten times reduction of threading dislocations which resulted in greater than seven times enhancement of AlGaN quantum well photoluminescence and 15 times increase in electroluminescence from LED test structures. We describe the application of deep-level optical spectroscopy to AlGaN epilayers to quantify deep level energies and densities and further correlate defect properties with AlGaN luminescence efficiency. We further review our development of p-type short period superlattice structures as an approach to mitigate the high acceptor activation energies in AlGaN alloys. Finally, we describe our laser diode fabrication process, highlighting the development of highly vertical and smooth etched laser facets, as well as characterization of resulting laser heterostructures.
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 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.
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.
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.
Experimental studies have been performed on the velocity-field characteristics of AlGaN/GaN heterostructures. A pulsed voltage input in combination with a four-point measurement was used in a 50 {Omega} environment to determinethe drift velocity of electrons in the two-dimensional electron gas as a function of the applied electric field. These measurements show an apparent saturation velocity near 3.1 x 10{sub 7} cm/s, at a field of 140 kV/cm. A comparison of these studies shows that the experimental velocities are close to previously published simulations based upon Monte Carlo techniques.
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.
The AlGaInN material system is used for virtually all advanced solid state lighting and short wavelength optoelectronic devices. Although metal-organic chemical vapor deposition (MOCVD) has proven to be the workhorse deposition technique, several outstanding scientific and technical challenges remain, which hinder progress and keep RD&A costs high. The three most significant MOCVD challenges are: (1) Accurate temperature measurement; (2) Reliable and reproducible p-doping (Mg); and (3) Low dislocation density GaN material. To address challenge (1) we designed and tested (on reactor mockup) a multiwafer, dual wavelength, emissivity-correcting pyrometer (ECP) for AlGaInN MOCVD. This system simultaneously measures the reflectance (at 405 and 550 nm) and emissivity-corrected temperature for each individual wafer, with the platen signal entirely rejected. To address challenge (2) we measured the MgCp{sub 2} + NH{sub 3} adduct condensation phase diagram from 65-115 C, at typical MOCVD concentrations. Results indicate that it requires temperatures of 80-100 C in order to prevent MgCp{sub 2} + NH{sub 3} adduct condensation. Modification and testing of our research reactor will not be complete until FY2005. A new commercial Veeco reactor was installed in early FY2004, and after qualification growth experiments were conducted to improve the GaN quality using a delayed recovery technique, which addresses challenge (3). Using a delayed recovery technique, the dislocation densities determined from x-ray diffraction were reduced from 2 x 10{sup 9} cm{sup -2} to 4 x 10{sup 8} cm{sup -2}. We have also developed a model to simulate reflectance waveforms for GaN growth on sapphire.
We develop a reciprocal-space model that describes the (hkl) dependence of the broadened Bragg peakwidths produced by x-ray diffraction from a dislocated epilayer. We compare the model to experiments and find that it accurately describes the peakwidths of 16 different Bragg reflections in the [010] zone of both GaN and AlN heterolayers. Using lattice-distortion parameters determined by fitting the model to selected reflections, we estimate threading-dislocation densities for seven different GaN and AlGaN samples and find improved agreement with transmission electron microscopy measurements.
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.
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.
We report micro-Raman studies of self-heating in an AlGaN/GaN heterostructure field-effect transistor using below (visible 488.0 nm) and near (UV 363.8 nm) GaN band-gap excitation. The shallow penetration depth of the UV light allows us to measure temperature rise ({Delta}T) in the two-dimensional electron gas (2DEG) region of the device between drain and source. Visible light gives the average {Delta}T in the GaN layer, and that of the SiC substrate, at the same lateral position. Combined, we depth profile the self-heating. Measured {Delta}T in the 2DEG is consistently over twice the average GaN-layer value. Electrical and thermal transport properties are simulated. We identify a hotspot, located at the gate edge in the 2DEG, as the prevailing factor in the self-heating.
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.
AlGaN/GaN test structures were fabricated with an etched constriction. A nitrogen plasma treatment was used to remove the disordered layer, including natural oxides on the AlGaN surface, before the growth of the silicon nitride passivation film on several of the test structures. A pulsed voltage input, with a 200 ns pulse width, and a four-point measurement were used in a 50 {Omega} environment to determine the room temperature velocity-field characteristic of the structures. The samples performed similarly over low fields, giving a low-field mobility of 545 cm{sup 2} V{sup -1} s{sup -1}. The surface treated sample performed slightly better at higher fields than the untreated sample. The highest velocity measured was 1.25 x 10{sup 7} cm s{sup -1} at a field of 26 kV cm{sup -1}.
The goal of this LDRD was to investigate III-antimonide/nitride based materials for unique semiconductor properties and applications. Previous to this study, lack of basic information concerning these alloys restricted their use in semiconductor devices. Long wavelength emission on GaAs substrates is of critical importance to telecommunication applications for cost reduction and integration into microsystems. Currently InGaAsN, on a GaAs substrate, is being commercially pursued for the important 1.3 micrometer dispersion minima of silica-glass optical fiber; due, in large part, to previous research at Sandia National Laboratories. However, InGaAsN has not shown great promise for 1.55 micrometer emission which is the low-loss window of single mode optical fiber used in transatlantic fiber. Other important applications for the antimonide/nitride based materials include the base junction of an HBT to reduce the operating voltage which is important for wireless communication links, and for improving the efficiency of a multijunction solar cell. We have undertaken the first comprehensive theoretical, experimental and device study of this material with promising results. Theoretical modeling has identified GaAsSbN to be a similar or potentially superior candidate to InGaAsN for long wavelength emission on GaAs. We have confirmed these predictions by producing emission out to 1.66 micrometers and have achieved edge emitting and VCSEL electroluminescence at 1.3 micrometers. We have also done the first study of the transport properties of this material including mobility, electron/hole mass, and exciton reduced mass. This study has increased the understanding of the III-antimonide/nitride materials enough to warrant consideration for all of the target device applications.
The wavelength splitting between the LP01 and LP11 modes of selectively oxidized, ion implanted, and hybrid ion implanted/selectively oxidized vertical-cavity surface-emitting lasers is studied by experiment and theory. Measured splittings at threshold show marked differences between the different laser structures due to the effects of index guiding and thermal lensing. Theoretical results were obtained using a vector optical mode solver and show good agreement with experimental results. The hybrid lasers exhibited behavior intermediate between the ion implanted and selectively oxidized lasers and could be optimized for high power single transverse mode emission.
This report describes the research accomplishments achieved under the LDRD Project ''High-Bandwidth Optical Data Interconnects for Satellite Applications.'' The goal of this LDRD has been to address the future needs of focal-plane-array (FPA) sensors by exploring the use of high-bandwidth fiber-optic interconnects to transmit FPA signals within a satellite. We have focused primarily on vertical-cavity surface-emitting laser (VCSEL) based transmitters, due to the previously demonstrated immunity of VCSELs to total radiation doses up to 1 Mrad. In addition, VCSELs offer high modulation bandwidth (roughly 10 GHz), low power consumption (roughly 5 mW), and high coupling efficiency (greater than -3dB) to optical fibers. In the first year of this LDRD, we concentrated on the task of transmitting analog signals from a cryogenic FPA to a remote analog-to-digital converter. In the second year, we considered the transmission of digital signals produced by the analog-to-digital converter to a remote computer on the satellite. Specifically, we considered the situation in which the FPA, analog-to-digital converter, and VCSEL-based transmitter were all cooled to cryogenic temperatures. This situation requires VCSELs that operate at cryogenic temperature, dissipate minimal heat, and meet the electrical drive requirements in terms of voltage, current, and bandwidth.
We have used selective AlGaAs oxidation, dry-etching, and high-gain semiconductor laser simulation to create new in-plane lasers with interconnecting passive waveguides for use in high-density photonic circuits and future integration of photonics with electronics. Selective oxidation and doping of semiconductor heterostructures have made vertical cavity surface emitting lasers (VCSELs) into the world's most efficient low-power lasers. We apply oxidation technology to improve edge-emitting lasers and photonic-crystal waveguides, making them suitable for monolithic integrated microsystems. Two types of lasers are investigated: (1) a ridge laser with resonant coupling to an output waveguide; (2) a selectively-oxidized laser with a low active volume and potentially sub-milliAmp threshold current. Emphasis is on development of high-performance lasers suited for monolithic integration with photonic circuit elements.
InxGa1-xAs1-yNy quaternary alloys offer the promise of longer wavelength, ≥ 1.3 μm optical transceivers grown on GaAs substrates. To achieve acceptable radiative efficiencies at 1.3 μm, highly-strained InGaAsN quantum wells (x ≈ 0.4, y ≈ 0.005) are being developed as laser active regions. By introducing GaAsP layers into the active region for strain-compensation, gain can be increased using multiple InGaAsN quantum wells. In this work, we report the first strain-compensated, 1.3 μm InGaAsN MQW lasers. Our devices were grown by metal-organic chemical vapor deposition. Lasers with InGaAsN quantum well active regions are proving superior to lasers constructed with competing active region materials. Under pulsed operation, our 1.3 μm InGaAsN lasers displayed negligible blue-shift from the low-injection LED emission, and state-of-the-art characteristic temperature (159 K) was obtained for a 1.3 μm laser.
Selectively oxidized vertical cavity surface emitting lasers (VCSEL) typically operate in multiple transverse optical modes. High power VCSEL operation is desirable for many applications such as optical storage and printing, modulation spectroscopy, bar code scanning, and data communication over single mode optical fiber. The modal discrimination can be augmented by creating a central region of gain surrounded by a region of optical loss. A VCSEL fabricated via hybrid ion implantation and selective oxidation device structure is designed to demonstrate a single mode output of more than 5 mW for 850 nm.