Plasmonic Nanoparticle Enhanced Light Absorption in GaN/InGaN/GaN Quantum Well Solar Cells
Applied Physics Letters
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Applied Physics Letters
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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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Advanced materials
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Journal of Applied Phyiscs
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Applied Physics Letters
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Proposed for publication in the Journal of Crystal Growth.
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.
Journal of Crystal Growth
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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