Publications

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We demonstrate a new route toward the integration and deterministic placement of quantum dots (QDs) within prepatterned nanostructures. Using standard electron-beam lithography (EBL) and inductively coupled plasma reactive-ion etching (ICP-RIE), we fabricate arrays of nanowires on a III-nitride platform. Next, we integrate QDs of controlled size within the prepatterned nanowires using a bandgap-selective, wet-etching technique: quantum-size-controlled photoelectrochemical (QSC-PEC) etching. Low-Temperature microphotoluminescence (μ-PL) measurements of individual nanowires reveal sharp spectral signatures, indicative of QD formation. Further, internal quantum efficiency (IQE) measurements reveal a near order of magnitude improvement in emitter efficiency following QSC-PEC etching. Finally, second-order cross-correlation (g(2)(0)) measurements of individual QDs directly confirm nonclassical, antibunching behavior. Our results illustrate an exciting approach toward the top-down integration of nonclassical light sources within nanophotonic platforms.

The goal of this LDRD is to develop a quantum nanophotonics capability that will allow practical control over electron (hole) and photon confinement in more than one dimension. We plan to use quantum dots (QDs) to control electrons, and photonic crystals to control photons. InGaN QDs will be fabricated using quantum size control processes, and methods will be developed to add epitaxial layers for hole injection and surface passivation. We will also explore photonic crystal nanofabrication techniques using both additive and subtractive fabrication processes, which can tailor photonic crystal properties. These two efforts will be combined by incorporating the QDs into photonic crystal surface emitting lasers (PCSELs). Modeling will be performed using finite-different time-domain and gain analysis to optimize QD-PCSEL designs that balance laser performance with the ability to nano-fabricate structures. Finally, we will develop design rules for QD-PCSEL architectures, to understand their performance possibilities and limits.

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Due to the ultra-wide bandgap of Al-rich AlGaN, up to 5.8 eV for the structures in this study, obtaining low resistance ohmic contacts is inherently difficult to achieve. A comparative study of three different fabrication schemes is presented for obtaining ohmic contacts to an Al-rich AlGaN channel. Schottky-like behavior was observed for several different planar metallization stacks (and anneal temperatures), in addition to a dry-etch recess metallization contact scheme on Al0.85Ga0.15N/Al0.66Ga0.34N. However, a dry etch recess followed by n+-GaN regrowth fabrication process is reported as a means to obtain lower contact resistivity ohmic contacts on a Al0.85Ga0.15N/Al0.66Ga0.34N heterostructure. Specific contact resistivity of 5 × 10−3 Ω cm2 was achieved after annealing Ti/Al/Ni/Au metallization.

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Using metalorganic vapor phase epitaxy, a comprehensive study of BxGa1−xN growth on GaN and AlN templates is described. BGaN growth at high-temperature and high-pressure results in rough surfaces and poor boron incorporation efficiency, while growth at low-temperature and low-pressure (750–900 °C and 20 Torr) using nitrogen carrier gas results in improved surface morphology and boron incorporation up to ~7.4% as determined by nuclear reaction analysis. However, further structural analysis by transmission electron microscopy and x-ray pole figures points to severe degradation of the high boron composition films, into a twinned cubic structure with a high density of stacking faults and little or no room temperature photoluminescence emission. Films with <1% triethylboron (TEB) flow show more intense, narrower x-ray diffraction peaks, near-band-edge photoluminescence emission at ~362 nm, and primarily wurtzite-phase structure in the x-ray pole figures. For films with >1% TEB flow, the crystal structure becomes dominated by the cubic phase. Only when the TEB flow is zero (pure GaN), does the cubic phase entirely disappear from the x-ray pole figure, suggesting that under these growth conditions even very low boron compositions lead to mixed crystalline phases.

We report lasing from nonpolar p-i-n InGaN/GaN multi-quantum well core-shell single-nanowire lasers by optical pumping at room temperature. The nanowire lasers were fabricated using a hybrid approach consisting of a top-down two-step etch process followed by a bottom-up regrowth process, enabling precise geometrical control and high material gain and optical confinement. The modal gain spectra and the gain curves of the core-shell nanowire lasers were measured using micro-photoluminescence and analyzed using the Hakki-Paoli method. Significantly lower lasing thresholds due to high optical gain were measured compared to previously reported semipolar InGaN/GaN core-shell nanowires, despite significantly shorter cavity lengths and reduced active region volume. Mode simulations show that due to the core-shell architecture, annular-shaped modes have higher optical confinement than solid transverse modes. The results show the viability of this p-i-n nonpolar core-shell nanowire architecture, previously investigated for next-generation light-emitting diodes, as low-threshold, coherent UV-visible nanoscale light emitters, and open a route toward monolithic, integrable, electrically injected single-nanowire lasers operating at room temperature.

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We experimentally investigate a new class of quasi-aperiodic structures for improving the emission pattern in nanowire arrays. Efficient normal emission, as well as lasing, can be obtained from III-nitride photonic crystal (PhC) nanowire arrays that utilize slow group velocity modes near the G-point in reciprocal space. However, due to symmetry considerations, the emitted far-field pattern of such modes are often 'donut'-like. Many applications, including lighting for displays or lasers, require a more uniform beam profile in the far-field. Previous work has improved far-field beam uniformity of uncoupled modes by changing the shape of the emitting structure. However, in nanowire systems, the shape of nanowires cannot always be arbitrarily changed due to growth or etch considerations. Here, we investigate breaking symmetry by instead changing the position of emitters. Using a quasi-aperiodic geometry, which changes the emitter position within a photonic crystal supercell (2x2), we are able to linearize the photonic bandstructure near the G-point and greatly improve emitted far-field uniformity. We realize the III-nitride nanowires structures using a top-down fabrication procedure that produces nanowires with smooth, vertical sidewalls. Comparison of room-temperature micro-photoluminescence (μ-PL) measurements between periodic and quasi-aperiodic nanowire arrays reveal resonances in each structure, with the simple periodic structure producing a donut beam in the emitted far-field and the quasi-aperiodic structure producing a uniform Gaussian-like beam. We investigate the input pump power vs. output intensity in both systems and observe the simple periodic array exhibiting a non-linear relationship, indicative of lasing. We believe that the quasi-aperiodic approach studied here provides an alternate and promising strategy for shaping the emission pattern of nanoemitter systems.

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The ability to achieve deterministic placement of semiconductor quantum dots (QDs) opens up interesting possibilities for nanophotonic devices. By incorporating these QDs within microcavities, light-matter interaction can be tailored and enhanced, enabling phenomenon such as spontaneous emission enhancement, low threshold lasing, single photon emission and strong-coupling. The quality of these phenomena relies on the distribution of emission wavelengths of the emitter dipoles and the strength of their coupling to internal fields of the cavity. Therefore size-controlled fabrication of QDs and their deterministic placement become quite important. In this work we will describe a photoelectrochemical-based etching of III-nitride materials to achieve QDs with uniform emission wavelength. By patterning using electron beam lithography to create a nanopost structure in an epitaxially grown III-nitride based quantum well structure, we will show potential for deterministic placement. The photoluminescence response from the nanopost structure after photoelectrochemical etching reveals sharp lines indicative of quantum dot formation.

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Illumination by a narrow-band laser has been shown to enable photoelectrochemical (PEC) etching of InGaN thin films into quantum dots with sizes controlled by the laser wavelength. Here, we investigate and elucidate the influence of solution pH on such quantum-size-controlled PEC etch process. We find that although a pH above 5 is often used for PEC etching of GaN-based materials, oxides (In2O3 and/or Ga2O3) form which interfere with quantum dot formation. At pH below 3, however, oxide-free QDs with self-terminated sizes can be successfully realized.

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There is strong interest in minimizing the volume of lasers to enable ultracompact, low-power, coherent light sources. Nanowires represent an ideal candidate for such nanolasers as stand-alone optical cavities and gain media, and optically pumped nanowire lasing has been demonstrated in several semiconductor systems. Electrically injected nanowire lasers are needed to realize actual working devices but have been elusive due to limitations of current methods to address the requirement for nanowire device heterostructures with high material quality, controlled doping and geometry, low optical loss, and efficient carrier injection. In this project we proposed to demonstrate electrically injected single nanowire lasers emitting in the important UV to visible wavelengths. Our approach to simultaneously address these challenges is based on high quality III-nitride nanowire device heterostructures with precisely controlled geometries and strong gain and mode confinement to minimize lasing thresholds, enabled by a unique top-down nanowire fabrication technique.

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Atom probe tomography (APT) is used to characterize the influence of hydrogen dosing during GaN barrier growth on the indium distribution of InxGa1-xN quantum wells, and correlated micro-photoluminescence is used to measure changes in the emission spectrum and efficiency. Relative to the control growth, hydrogen dosing leads to a 50% increase in emission intensity arising from discontinuous quantum wells that are narrower, of lower indium content, and with more abrupt interfaces. Simulations of carrier distributions based on APT composition profiles indicate that the greater carrier confinement leads to an increased radiative recombination rate. Furthermore, APT analysis of quantum well profiles enables refinement of x-ray diffraction analysis for more accurate nondestructive measurements of composition.

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We report here the characteristics of photoelectrochemical (PEC) etching of epitaxial InGaN semiconductor thin films using a narrowband laser with a linewidth less than ∼1 nm. In the initial stages of PEC etching, when the thin film is flat, characteristic voltammogram shapes are observed. At low photo-excitation rates, voltammograms are S-shaped, indicating the onset of a voltage-independent rate-limiting process associated with electron-hole-pair creation and/or annihilation. At high photo-excitation rates, voltammograms are superlinear in shape, indicating, for the voltage ranges studied here, a voltage-dependent rate-limiting process associated with surface electrochemical oxidation. As PEC etching proceeds, the thin film becomes rough at the nanoscale, and ultimately the self-limiting etch kinetics lead to an ensemble of nanoparticles. This change in InGaN film volume and morphology leads to a characteristic dependence of PEC etch rate on time: an incubation time, followed by a rise, then a peak, then a slow decay.

The influence of a dilute InxGa1-xN (x ∼ 0.03) underlayer (UL) grown below a single In0.16Ga0.84N quantum well (SQW), within a light-emitting diode (LED), on the radiative efficiency and deep level defect properties was studied using differential carrier lifetime (DCL) measurements and deep level optical spectroscopy (DLOS). DCL measurements found that inclusion of the UL significantly improved LED radiative efficiency. At low current densities, the non-radiative recombination rate of the LED with an UL was found to be 3.9 times lower than the LED without an UL, while the radiative recombination rates were nearly identical. This suggests that the improved radiative efficiency resulted from reduced non-radiative defect concentration within the SQW. DLOS measurement found the same type of defects in the InGaN SQWs with and without ULs. However, lighted capacitance-voltage measurements of the LEDs revealed a 3.4 times reduction in a SQW-related near-mid-gap defect state for the LED with an UL. Quantitative agreement in the reduction of both the non-radiative recombination rate (3.9×) and deep level density (3.4×) upon insertion of an UL corroborates deep level defect reduction as the mechanism for improved LED efficiency.

InGaN/AlGaN/GaN-based multiple quantum wells (MQWs) with AlGaN interlayers (ILs) are investigated, specifically to examine the fundamental mechanisms behind their increased radiative efficiency at wavelengths of 530-590 nm. The AlzGa1-zN (z∼0.38) IL is ∼1-2 nm thick, and is grown after and at the same growth temperature as the ∼3 nm thick InGaN quantum well (QW). This is followed by an increase in temperature for the growth of a ∼10 nm thick GaN barrier layer. The insertion of the AlGaN IL within the MQW provides various benefits. First, the AlGaN IL allows for growth of the InxGa1-xN QW well below typical growth temperatures to achieve higher x (up to ∼0.25). Second, annealing the IL capped QW prior to the GaN barrier growth improves the AlGaN IL smoothness as determined by atomic force microscopy, improves the InGaN/AlGaN/GaN interface quality as determined from scanning transmission electron microscope images and x-ray diffraction, and increases the radiative efficiency by reducing nonradiative defects as determined by time-resolved photoluminescence measurements. Finally, the AlGaN IL increases the spontaneous and piezoelectric polarization induced electric fields acting on the InGaN QW, providing an additional red-shift to the emission wavelength as determined by Schrodinger-Poisson modeling and fitting to the experimental data. The relative impact of increased indium concentration and polarization fields on the radiative efficiency of MQWs with AlGaN ILs is explored along with implications to conventional longer wavelength emitters.

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We demonstrate a new route to the precision fabrication of epitaxial semiconductor nanostructures in the sub-10 nm size regime: quantum-size-controlled photoelectrochemical (QSC-PEC) etching. We show that quantum dots (QDs) can be QSC-PEC-etched from epitaxial InGaN thin films using narrowband laser photoexcitation, and that the QD sizes (and hence bandgaps and photoluminescence wavelengths) are determined by the photoexcitation wavelength. Low-temperature photoluminescence from ensembles of such QDs have peak wavelengths that can be tunably blue shifted by 35 nm (from 440 to 405 nm) and have line widths that narrow by 3 times (from 19 to 6 nm).

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The goal of this NETL funded program was to improve the IQE in green (and longer wavelength) nitride- based LEDs structures by using semi-polar GaN planar orientations for InGaN multiple quantum well (MQW) growth. These semi-polar orientations have the advantage of significantly reducing the piezoelectric fields that distort the QW band structure and decrease electron-hole overlap. In addition, semipolar surfaces potentially provide a more open surface bonding environment for indium incorporation, thus enabling higher indium concentrations in the InGaN MQW. The goal of the proposed work was to select the optimal semi-polar orientation and explore wafer miscuts around this orientation that produced the highest quantum efficiency LEDs. At the end of this program we had hoped to have MQWs active regions at 540 nm with an IQE of 50% and an EQE of 40%, which would be approximately twice the estimated current state-of-the-art.

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Vertically aligned InGaN/GaN nanorod light emitting diode (LED) arrays were created from planar LED structures using a new top-down fabrication technique consisting of a plasma etch followed by an anisotropic wet etch. The wet etch results in straight, smooth, well-faceted nanorods with controllable diameters and removes the plasma etch damage. 94% of the nanorod LEDs are dislocation-free and a reduced quantum confined Stark effect is observed due to reduced piezoelectric fields. Despite these advantages, the IQE of the nanorod LEDs measured by photoluminescence is comparable to the planar LED, perhaps due to inefficient thermal transport and enhanced nonradiative surface recombination.

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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.

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In this work, we model the carrier recombination mechanisms in GaInN/GaN light-emitting diodes as R=An+Bn²+Cn³+f(n), where f(n) represents carrier leakage out of the active region. The term f(n) is expanded into a power series and shown to have higher-than-third-order contributions to the recombination. The total third-order nonradiative coefficient (which may include an f(n) leakage contribution and an Auger contribution) is found to be 8×10^-29 cm⁶ s^-1. Finally, comparison of the theoretical ABC+f(n) model with experimental data shows that a good fit requires the inclusion of the f(n) term.

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The fundamental spontaneous emission rate for a photon source can be modified by placing the emitter inside a periodic dielectric structure allowing the emission to be dramatically enhanced or suppressed depending on the intended application. We have investigated the relatively unexplored realm of interaction between semiconductor emitters and three dimensional photonic crystals in the visible spectrum. Although this interaction has been investigated at longer wavelengths, very little work has been done in the visible spectrum. During the course of this LDRD, we have fabricated TiO{sub 2} logpile photonic crystal structures with the shortest wavelength band gap ever demonstrated. A variety of different emitters with emission between 365 nm and 700 nm were incorporated into photonic crystal structures. Time-integrated and time-resolved photoluminescence measurements were performed to measure changes to the spontaneous emission rate. Both enhanced and suppressed emission were demonstrated and attributed to changes to the photonic density of states.

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.

With no lattice matched substrate available, sapphire continues as the substrate of choice for GaN growth, because of its reasonable cost and the extensive prior experience using it as a substrate for GaN. Surprisingly, the high dislocation density does not appear to limit UV and blue LED light intensity. However, dislocations may limit green LED light intensity and LED lifetime, especially as LEDs are pushed to higher current density for high end solid state lighting sources. To improve the performance for these higher current density LEDs, simple growth-enabled reductions in dislocation density would be highly prized. GaN nucleation layers (NLs) are not commonly thought of as an application of nano-structural engineering; yet, these layers evolve during the growth process to produce self-assembled, nanometer-scale structures. Continued growth on these nuclei ultimately leads to a fully coalesced film, and we show in this research program that their initial density is correlated to the GaN dislocation density. In this 18 month program, we developed MOCVD growth methods to reduce GaN dislocation densities on sapphire from 5 x 10{sup 8} cm{sup -2} using our standard delay recovery growth technique to 1 x 10{sup 8} cm{sup -2} using an ultra-low nucleation density technique. For this research, we firmly established a correlation between the GaN nucleation thickness, the resulting nucleation density after annealing, and dislocation density of full GaN films grown on these nucleation layers. We developed methods to reduce the nuclei density while still maintaining the ability to fully coalesce the GaN films. Ways were sought to improve the GaN nuclei orientation by improving the sapphire surface smoothness by annealing prior to the NL growth. Methods to eliminate the formation of additional nuclei once the majority of GaN nuclei were developed using a silicon nitride treatment prior to the deposition of the nucleation layer. Nucleation layer thickness was determined using optical reflectance and the nucleation density was determined using atomic force microscopy (AFM) and Nomarski microscopy. Dislocation density was measured using X-ray diffraction and AFM after coating the surface with silicon nitride to delineate all dislocation types. The program milestone of producing GaN films with dislocation densities of 1 x 10{sup 8} cm{sup -2} was met by silicon nitride treatment of annealed sapphire followed by the multiple deposition of a low density of GaN nuclei followed by high temperature GaN growth. Details of this growth process and the underlying science are presented in this final report along with problems encountered in this research and recommendations for future work.

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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 report the initial use of lithographically defined carbon growth templates for use as an epitaxial lateral overgrowth (ELOG) mask for metalorganic chemical vapor deposition (MOCVD) heteroepitaxial GaN on sapphire. Interferometric lithography is used to define high aspect ratio structures in SU-8, which are then pyrolyzed in a reducing atmosphere up to 1200 °C. The resist structures convert to amorphous carbon, shrinking 80% in the vertical direction and 53% in the horizontal direction, but maintain their pattern geometry and adhesion to the substrate. These templates are capable of surviving GaN nucleation layer growth temperatures (∼530 °C), GaN crystal growth and high-temperature annealing up to 1050 °C. This new approach to ELOG offers several advantages, requiring fewer processing steps, and favorable selectivity tendencies as well as the capability to create growth masks which are difficult or impossible to fabricate using a top-down etching approach. © 2008 Elsevier B.V. All rights reserved.

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This senior council Tier 1 LDRD was focused on exploring the use of porous growth masks as a method for defect reduction during heteroepitaxial crystal growth. Initially our goal was to investigate porous silica as a growth mask, however, we expanded the scope of the research to include several other porous growth masks on various size scales, including mesoporous carbon, photolithographically patterned SU-8 and carbonized SU-8 structures. Use of photolithographically defined growth templates represents a new direction, unique in the extensive literature of patterned epitaxial growth, and presents the possibility of providing a single step growth mask. Additional research included investigation of pore viability via electrochemical deposition into high aspect ratio photoresist. This project was a small footprint research effort which, nonetheless, produced significant progress towards both the stated goal as well as unanticipated research directions.

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This one-year out-of-the-box LDRD was focused on exploring the use of porous growth masks as a method for defect reduction during heteroepitaxial crystal growth. Initially our goal was to investigate porous silica as a growth mask, however, we expanded the scope of the research to include several other porous growth masks on various size scales, including mesoporous carbon, and the UV curable epoxy, SU-8. Use of SU-8 as a growth mask represents a new direction, unique in the extensive literature of patterned epitaxial growth, and presents the possibility of providing a single step growth mask. Additional research included investigation of pore viability via electrochemical deposition into high aspect ratio photoresist patterns and pilot work on using SU-8 as a DUV negative resist, another significant potential result. While the late start nature of this project pushed some of the initial research goals out of the time table, significant progress was made. 3 Acknowledgements This work was performed in part at the Nanoscience @ UNM facility, a member of the National Nanotechnology Infrastructure Network, which is supported by the National Science Foundation (Grant ECS 03-35765). Sandia is multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United Stated Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000. This work was supported under the Sandia LDRD program (Project 99405). 4

This Report summarizes the first year progress (October 1, 2004 to September 30, 2005) made under a NETL funded project entitled ''Improved InGaN Epitaxy Yield by Precise Temperature Measurement''. This Project addresses the production of efficient green LEDs, which are currently the least efficient of the primary colors. The Project Goals are to advance IR and UV-violet pyrometry to include real time corrections for surface emissivity on multiwafer MOCVD reactors. Increasing wafer yield would dramatically reduce high brightness LED costs and accelerate the commercial manufacture of inexpensive white light LEDs with very high color quality. This work draws upon and extends our previous research (funded by DOE) that developed emissivity correcting pyrometers (ECP) based on the high-temperature GaN opacity near 400 nm (the ultraviolet-violet range, or UVV), and the sapphire opacity in the mid-IR (MIR) near 7.5 microns.

Based on the wurtzite crystal structure, large (MV/cm) polarization-induced electric fields are known to exist in InGaN single quantum wells (SQWs) grown perpendicular to the GaN c-axis, and these fields may impact optical device performance due to the quantum-confined Stark effect (QCSE). In general, the QCSE has experimentally been found to be smaller than the theoretical value expected for a coherently strained InGaN QW, and subsequently the InGaN/GaN QW polarization field is often under-estimated as well. In this study, we measure the QCSE in modulation-doped, InGaN/GaN SQW LEDs. The well-behaved capacitance-voltage (majority-carrier) characteristics of these devices allow us to unambiguously determine the applied field with bias. With this analysis, we de-couple the QCSE from the QW polarization field and show that although the applied field approaches the opposing QW polarization field theoretical value (i.e., flatband), the QCSE remains too small. We propose a localized-hole picture of the InGaN QW which explains our optical and electrical measurements. © 2006 Materials Research Society.

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.

The room-temperature velocity-field characteristics for n -type gallium nitride and AlGaNGaN heterostructures, grown epitaxially on sapphire, were determined experimentally. A pulsed voltage input and four-point measurements were used on special geometry samples to determine the electron drift velocity as a function of applied electric field in the basal plane. These measurements show apparent saturation velocities near 2.5× 107 cms at 180 kVcm for the n -type gallium nitride and 3.1× 107 cms at 140 kVcm for the AlGaNGaN heterostructures. A comparison of these studies shows that the experimental velocities are close to previously published simulations based upon Monte Carlo techniques. © 2005 American Institute of Physics.

Numerous technologies including solid-state lighting, displays, and traffic signals can benefit from efficient, color-selectable light sources that are driven electrically. Semiconductor nanocrystals are attractive types of chromophores that combine size-controlled emission colors and high emission efficiencies with excellent photostability and chemical flexibility. Applications of nanocrystals in light-emitting technologies, however, have been significantly hindered by difficulties in achieving direct electrical injection of carriers. Here we report the first successful demonstration of electroluminescence from an all-inorganic, nanocrystal-based architecture in which semiconductor nanocrystals are incorporated into a p-n junction formed from GaN injection layers. The critical step in the fabrication of these nanocrystal/GaN hybrid structures is the use of a novel deposition technique, energetic neutral atom beam lithography/epitaxy, that allows for the encapsulation of nanocrystals within a GaN matrix without adversely affecting either the nanocrystal integrity or its luminescence properties. We demonstrate electroluminescence (injection efficiencies of at least 1%) in both single- and two-color regimes using structures comprising either a single monolayer or a bilayer of nanocrystals.

We developed a pyrometer that operates near the high-temperature bandgap of GaN, thus solving the transparency problem once a {approx} 1 {micro}m thick GaN epilayer has been established. The system collects radiation in the near-UV (380-415 nm) and has an effective detection wavelength of {approx}405 nm. By simultaneously measuring reflectance we also correct for emissivity changes when films of differing optical properties (e.g. AlGaN) are deposited on the GaN template. We recently modified the pyrometer hardware and software to enable measurements in a multiwafer Veeco D-125 OMVPE system. A method of synchronizing and indexing the detection system with the wafer platen was developed; so signals only from the desired wafer(s) could be measured, while rejecting thermal emission signals from the platen. Despite losses in optical throughput and duty cycle we are able to maintain adequate performance from 700 to 1100 C.

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.

Abstract not provided.

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.

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.

Abstract not provided.

Abstract not provided.

Abstract not provided.

High-resolution, variable temperature PL experiments were performed in the spectral region associated with recombination processes involving the ground and excited states of the neutral donor bound excitons. High-resolution infrared measurements in combination with high-sensitive SIMS unambiguously identified Si and O shallow donors and yield their ground state binding energies. These binding energies are in excellent agreement with values obtained by the analysis of the two-electron-satellite PL spectra considering the participation of ground and excited state donor bound excitons. This work clarifies conflicting aspects existing in donor identification and the binding energies of the impurities and excitons.

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.

Using in situ wafer-curvature measurements of thin-film stress, we determine the critical thickness for strain relaxation in Al{sub x}Ga{sub 1-x}N/GaN heterostructures with 0.14 {le} x {le} 1. The surface morphology of selected films is examined by atomic force microscopy. Comparison of these measurements with critical-thickness models for brittle fracture and dislocation glide suggests that the onset of strain relaxation occurs by surface fracture for all compositions. Misfit-dislocations follow initial fracture, with slip-system selection occurring under the influence of composition-dependent changes in surface morphology.

Optically detected magnetic resonance (ODMR) has been performed on Si-doped GaN homoepitaxial layers grown by organometallic chemical vapor deposition on free-standing GaN templates. In addition to intense excitonic bandedge emission with narrow linewidths (<0.4 meV), these films exhibit strong shallow donor-shallow acceptor recombination at 3.27 eV. Most notably, ODMR on this photoluminescence band reveals a highly anisotropic resonance with g{sub {parallel}} = 2.193 {+-} 0.001 and g{sub {perpendicular}} {approx}0 as expected for effective-mass shallow acceptors in wurtzitic GaN from k {center_dot} p theory. This previously elusive result is attributed to the much reduced dislocation density and impurity levels compared to those typically found in the widely investigated Mg-doped GaN heteroepitaxial layers. The possible chemical origin of the shallow acceptors in these homoepitaxial films will be discussed.

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 relationship of GaN resistivity to film microstructure and impurity compensation are investigated using transmission electron microscopy, secondary ion mass spectroscopy, X-ray diffraction, and resistance measurements. Unintentionally doped GaN films grown by MOCVD at varying pressures exhibit increased grain size, reduced carbon and oxygen impurity incorporation, reduction in the density of threading dislocations (TDs) with an edge component, and reduced resistivity with increasing growth pressure. Variation in resistivity over eight orders of magnitude is observed as a result of varying the MOCVD growth pressure in a controlled experiment. Our results suggest that disclocations play an important role in the resistivity of GaN. Evidence is presented of impurities segregating at TDs having an edge component, and acting as compensating centers. The control of such compensation as a function of MOCVD growth conditions is outlined. Published by Elsevier B.V.

To observe the effects of polarization fields and screening, we have performed contacted electroreflectance (CER) measurements on In{sub 0.07}Ga{sub 0.93}N/GaN single quantum well light emitting diodes for different reverse bias voltages. Room-temperature CER spectra exhibited three features which are at lower energy than the GaN band gap and are associated with the quantum well. The position of the lowest-energy experimental peak, attributed to the ground-state quantum well transition, exhibited a limited Stark shift except at large reverse bias when a redshift in the peak energy was observed. Realistic band models of the quantum well samples were constructed using self-consistent Schroedinger-Poisson solutions, taking polarization and screening effects in the quantum well fully into account. The model predicts an initial blueshift in transition energy as reverse bias voltage is increased, due to the cancellation of the polarization electric field by the depletion region field and the associated shift due to the quantum-confined Stark effect. A redshift is predicted to occur as the applied field is further increased past the flatband voltage. While the data and the model are in reasonable agreement for voltages past the flatband voltage, they disagree for smaller values of reverse bias, when charge is stored in the quantum well, and no blueshift is observed experimentally. To eliminate the blueshift and screen the electric field, we speculate that electrons in the quantum well are trapped in localized states.

Abstract not provided.

Abstract not provided.

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.

Abstract not provided.

Epitaxial Si-doped GaN layers were studied using a low-energy positron beam, where the grain size varies from 0.2 to 2-5 μm. The concentration of the negatively charged Ga vacancies was found to be independent of the grain size, which showed that Ga vacancies exist in the grain interior. Positrons were also observed to get trapped also at other negatively charged centers.

Abstract not provided.