Gallium—nitride-on-handle substrate materials and devices and method of manufacture

Information

  • Patent Grant
  • 8946865
  • Patent Number
    8,946,865
  • Date Filed
    Wednesday, June 11, 2014
    11 years ago
  • Date Issued
    Tuesday, February 3, 2015
    10 years ago
Abstract
A gallium and nitrogen containing substrate structure includes a handle substrate member having a first surface and a second surface and a transferred thickness of gallium and nitrogen material. The structure has a gallium and nitrogen containing active region grown overlying the transferred thickness and a recessed region formed within a portion of the handle substrate member. The substrate structure has a conductive material formed within the recessed region configured to transfer thermal energy from at least the transferred thickness of gallium and nitrogen material.
Description
BACKGROUND OF THE INVENTION

This invention generally relates to manufacture of materials and devices. More particularly, the present invention provides a method and device using wafer-bonded crystals or the like in combination with optical devices composed of a gallium-containing nitride crystal. More specifically, embodiments of the invention include techniques for fabricating a light emitting diode device using bulk gallium nitride containing materials, for example for application to optoelectronic devices. In other embodiments, the invention provides a method of manufacture using an epitaxial gallium containing crystal with a release layer. Such crystals and materials include GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, and others, for manufacture of bulk or patterned substrates.


Progress has been made during the past decade and a half in the performance of gallium nitride (GaN) based light emitting diodes (LEDs). Devices with a luminous efficiency higher than 100 lumens per watt have been demonstrated in the laboratory, and commercial devices have an efficiency that is already superior to that of incandescent lamps, and competitive with that of fluorescent lamps. Further improvements in efficiency are desired to reduce operating costs, reduce electricity consumption, and decrease emissions of carbon dioxide and other greenhouse gases produced in generating the energy used for lighting applications.


Silicon-on-insulator substrates are well known in the art, and convey certain advantages compared to standard silicon substrates. Several authors have demonstrated GaN-on-insulator substrates. Tauzin et al. [Electronics Letters 41, 668 (2005) transferred the topmost portion from a 4-μm-thick GaN-on-sapphire epilayer onto a second sapphire substrate by means of SmartCut™ layer-transfer technology. The crystalline quality of the transferred layer was not particularly high in this case. O. Moutanabbir and U. Gösele [J. Electronic Mater. 39, 482 (2010)] transferred a layer from a free-standing, pseudo-bulk GaN wafer of unspecified quality to sapphire. Sapphire, while readily available and convenient to work with, suffers from a relatively low thermal conductivity and has a significant mismatch in the coefficient of thermal expansion with respect to the GaN layer. In addition, in cases where the nitride crystal in a GaN-on-insulator wafer is spatially inhomogeneous, we are not aware of any teachings about the best way to arrange fabricated devices with respect to structures in the GaN layer.


What is needed is a more manufacturable solution for fabricating high-quality GaN-on-handle substrates or wafers that are optimized for down-stream device processing and device designs and processing methods that are optimized to take advantage of the properties of the wafer.


BRIEF SUMMARY OF THE INVENTION

In a specific embodiment, the present invention provides a gallium and nitrogen containing optical device. The device includes a handle substrate member portion having a surface region. The handle substrate portion is characterized by a first coefficient of thermal expansion parallel to the surface. The device has an adhesion material (e.g., dielectric, conductor) overlying the surface region. The device also has a gallium and nitrogen containing region formed overlying the adhesion material. The gallium and nitrogen containing region is characterized by a second coefficient of thermal expansion parallel to the surface. The second coefficient of thermal expansion is substantially similar to the first coefficient of thermal expansion. The gallium and nitrogen containing region is formed from a donor gallium and nitrogen containing material transferred to the handle substrate. The device also includes at least one active region formed overlying the gallium and nitrogen containing region and at least one p-type region formed epitaxially overlying the active region.


In an alternative specific embodiment, the present invention provides a gallium and nitrogen containing device. The device includes a handle substrate member having a first surface region and a second surface region and at least one n-contact region overlying the first surface region. The device has a gallium and nitrogen containing material overlying the second region. The gallium and nitrogen containing material is transferred overlying the second region. The gallium and nitrogen containing material includes a core region. As used herein, the core region refers to a commonly known entity of a dot core GaN substrate from Sumitomo Electric Industries, Ltd, of Japan, or others. The device has an interface region overlying the gallium and nitrogen containing material and at least one n-type epitaxial growth region overlying the interface region. The device also has a core structure extending from the core region within the overlying gallium and nitrogen containing material and configured to extend through the at least one n-type epitaxial growth region. The device has an active region overlying the at least one n-type epitaxial growth region, a p-type region overlying the first active region and the second active region, and at least one p-contact region overlying the p-type region. As an example, the dot core GaN is described in “Dislocation reduction in GaN crystal by advanced-DEEP,” in the names of Motoki, et al., and published in Journal of Crystal Growth 305 (2007) 377-383, which is incorporated by reference herein.


In other embodiments, the invention provides a gallium and nitrogen containing device. The device has a handle substrate member having a first surface region, with gallium and nitrogen containing material overlying the first region. The gallium and nitrogen containing material is transferred overlying the first region. The gallium and nitrogen containing material comprises a core region. The device has an interface region overlying the gallium and nitrogen containing material and at least one n-type epitaxial growth region overlying the interface region. The device has a core structure extending from the core region within the overlying gallium and nitrogen containing material and configured to extend through the at least one n-type epitaxial growth region. The device has an active region overlying the at least one n-type epitaxial growth region and a p-type region overlying the first active region and the second active region. The device has a mesa structure, wherein material lateral to at least one mesa has been removed so as to expose at least one n-type epitaxial growth region. The device has at least one n-contact region overlying the exposed n-type region and at least one p-contact region overlying the p-type region.


Still further, the invention provides a method of processing a gallium and nitrogen containing material. The method includes providing a handle substrate having a surface region. The method includes transferring a thickness of gallium and nitrogen containing substrate material comprising at least one core region therein overlying the surface region. The device has depositing a gallium and nitrogen containing material using at least epitaxial growth overlying the thickness of gallium and nitrogen containing substrate material to form a thickness of epitaxially grown material comprising a core structure formed overlying the core region. The method includes subjecting the core structure to at least an etching process.


Moreover, the invention provides a gallium and nitrogen containing device. The device has a handle substrate member having a first surface region and a second surface region. The handle substrate member is conductive in characteristic and an exposed region characterizing the first surface region. The device has a gallium and nitrogen containing material overlying the second surface region. The gallium and nitrogen containing material is transferred overlying the second region. The gallium and nitrogen containing material comprises a core region. The device has an interface region overlying the gallium and nitrogen containing material. The device has at least one n-type epitaxial growth region overlying the interface region and a conductive structure extending from the core region and configured through portion between the two n-type epitaxial growth regions. The device has an active region formed overlying the n-type epitaxial growth region and a p-type region formed overlying the active region. The device has an n-type contact region formed overlying the conductive structure.


Still further, the present invention provides a gallium and nitrogen containing substrate structure. The structure includes a handle substrate member having a first surface and a second surface and a transferred thickness of gallium and nitrogen material. The structure has a gallium and nitrogen containing active region grown overlying the transferred thickness of gallium and nitrogen containing material and a recessed region formed within a portion of the handle substrate member. The substrate structure has a conductive material formed within the recessed region and is configured to transfer thermal energy from at least the transferred thickness of gallium and nitrogen material.


Still further, the present invention provides a gallium and nitrogen containing substrate structure. The substrate structure includes a handle substrate member having a first surface and a second surface and comprising a plurality of energy conversion materials and a transferred thickness of gallium and nitrogen material. The substrate structure includes a gallium and nitrogen containing active region grown overlying the transferred thickness of gallium and nitrogen containing material.


The present device and method provides for an improved gallium and nitrogen containing material and resulting device structures for optical and electronic devices. In other embodiments, the present method and resulting structure are easier to implement using conventional technologies. The invention provides a high quality GaN substrate and resulting devices. These and other benefits are further described below in conjunction with the attached drawings.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a diagram of a nitride crystal and a handle substrate according to an embodiment of the present invention;



FIG. 2 is a diagram of a wafer-bonded nitride crystal and handle substrate according to an embodiment of the present invention;



FIG. 3 is a diagram of a wafer-bonded nitride crystal and handle substrate after removal of portion of the nitride crystal according to an embodiment of the present invention;



FIG. 4 is a diagram of a device structure according to an embodiment of the present invention;



FIG. 5 is a diagram of a vertical device structure according to an embodiment of the present invention;



FIG. 6 is a diagram of a lateral device structure according to an embodiment of the present invention;



FIG. 7 is a diagram of a vertical device structure having a roughened or patterned interface according to an embodiment of the present invention;



FIG. 8 is a diagram of a lateral device structure having a roughened or patterned interface according to an embodiment of the present invention;



FIGS. 9A-9C are diagrams of a vertical device structure on a patterned substrate according to an embodiment of the present invention;



FIGS. 10A and 10B are diagrams of a lateral device structure on a patterned substrate according to an embodiment of the present invention;



FIG. 11 is a diagram of a device structure on a patterned substrate illustrating singulation methods according to an embodiment of the present invention;



FIGS. 12A and 12B are diagrams of an alternative device structure on a patterned substrate illustrating singulation methods according to an embodiment of the present invention;



FIGS. 13A-13D are diagrams of additional device structures on a patterned substrate illustrating singulation methods according to an embodiment of the present invention;



FIG. 14 is a diagram showing a side view of a flip-chip device structure according to an embodiment of the present invention;



FIG. 15 is a diagram showing a top view of a flip-chip device structure according to an embodiment of the present invention;



FIG. 16 is a diagram showing a sandwiched vertical device structure according to an embodiment of the present invention;



FIG. 17 is a cross-sectional view diagram of a vertical thin-film device structure having a removed handle substrate in one or more embodiments;



FIG. 18 is a cross-sectional view diagram of a vertical thin-film device structure having a removed handle substrate in one or more embodiments;



FIG. 19 is a diagram showing a processing sequence of a substrate according to an embodiment of the present invention;



FIGS. 20A-20C are diagrams showing configurations of vias within a substrate according to an embodiment of the present invention; and



FIGS. 21A and 21B are diagrams showing a substrate comprising light emitting entities according to an embodiment of the present invention.





DETAILED DESCRIPTION OF THE INVENTION

Referring to FIG. 1, in one set of embodiments the starting point for the present invention is a donor substrate 101 consisting essentially of a high quality nitride crystal or wafer. The nitride crystal comprises nitrogen and has a threading dislocation density below about 108 cm−2. The nitride crystal or wafer may comprise AlxInyGa1-x-yN, where 0≦x, y, x+y≦1, for example, GaN. In a preferred embodiment, the nitride crystal is substantially free of low-angle grain boundaries, or tilt boundaries, over a length scale of at least 3 millimeters.


The nitride crystal or wafer may have a large-surface orientation within ten degrees, within five degrees, within two degrees, within one degree, within 0.5 degree, or within 0.2 degree of (0 0 0 1), (0 0 0 −1), {1 −1 0 0}, {1 1 −2 0}, {1 −1 0 ±1}, {1 −1 0 ±2}, {1 −1 0 ±3}, {2 0 −2 ±1}, or {1 1 −2 ±2}. In one specific embodiment, the nitride crystal has a semipolar large-surface orientation, which may be designated by (hkil) Bravais-Miller indices, where i=−(h+k), l is nonzero and at least one of h and k are nonzero. The nitride crystal may have a dislocation density below 107 cm−2, below 106 cm−2, below 105 cm−2, below 104 cm−2, below 103 cm−2, or below 102 cm−2. The nitride crystal may have a stacking-fault concentration below 103 cm−1, below 102 cm−1, below 10 cm−1 or below 1 cm−1. The nitride crystal or wafer may have an optical absorption coefficient below 100 cm−1, below 50 cm−1, below 5 cm−1, below 2 cm−1, below 1 cm−1, or below 0.3 cm−1 at wavelengths between about 390 nm and about 700 nm. The nitride crystal may have an optical absorption coefficient below 100 cm−1, below 50 cm−1, below 5 cm−1, below 2 cm−1, below 1 cm−1, or below 0.3 cm−1 at wavelengths between about 700 nm and about 3077 nm and at wavelengths between about 3333 nm and about 6667 nm. The top surface of the nitride crystal may have an x-ray diffraction w-scan rocking curve full-width-at-half-maximum (FWHM) less than about 300 arc sec, less than about 200 arc sec, less than about 100 arc sec, less than about 50 arcsec, less than about 40 arcsec, less than about 30 arcsec, less than about 20 arcsec, or less than about 10 arcsec for the lowest-order symmetric and non-symmetric reflections. In some embodiments, the threading dislocations in the top surface of the nitride crystal are approximately uniformly distributed. In other embodiments, the threading dislocations in the top surface of the nitride crystal are arranged inhomogeneously as a one-dimensional array of rows of relatively high- and relatively low-concentration regions or as a two-dimensional array of high-dislocation-density regions within a matrix of low-dislocation-density regions. The relatively high-dislocation-density regions in a two-dimensional array may be referred to as cores or core regions and the nitride crystal may be referred to as a dot-core crystal or substrate.


Nitride crystal 101 may have a crystallographic radius of curvature greater than 0.1 meter, greater than 1 meter, greater than 10 meters, greater than 100 meters, or greater than 1000 meters, in at least one, at least two, or in three independent or orthogonal directions. Nitride crystal 101 may comprise regions having a relatively high concentration of threading dislocations separated by regions having a relatively low concentration of threading dislocations. The concentration of threading dislocations in the relatively high concentration regions may be greater than about 106 cm−2, greater than about 107 cm−2, or greater than about 108 cm−2. The concentration of threading dislocations in the relatively low concentration regions may be less than about 106 cm−2, less than about 105 cm−2, or less than about 104 cm−2. Nitride crystal 101 may have a thickness between about 100 microns and about 100 millimeters, or between about 1 millimeter and about 10 millimeters. Nitride crystal 101 may have a diameter of at least about 0.5 millimeter, at least about 1 millimeter, at least about 2 millimeters, at least about 5 millimeters, at least about 10 millimeters, at least about 15 millimeters, at least about 20 millimeters, at least about 25 millimeters, at least about 35 millimeters, at least about 50 millimeters, at least about 75 millimeters, at least about 100 millimeters, at least about 150 millimeters, or at least about 200 millimeters. The crystallographic orientation may be constant to less than about 2 degrees, less than about 1 degree, less than about 0.5 degree, less than about 0.2 degree, less than about 0.1 degree, or less than about 0.05 degree across the top surface of the nitride crystal.


The nitride crystal may be fabricated by hydride vapor phase epitaxy (HVPE), as described in U.S. Pat. No. 6,468,347, in US Patent Application US 2006/0228870A1, or by Fujito et al., J. Cryst. Growth, 311, 3011 (2009), by ammonothermal growth, as described in U.S. Pat. Nos. 6,656,615, 7,078,731, and 7,642,122, US Patent Application 2010/0031875, or U.S. patent application Ser. Nos. 12/988,772, 61/360,819, or 61/386,879, or by flux growth, as described by M. Imade et al., Applied Physics Express 3, 075501 (2010), each of which is hereby incorporated by reference in its entirety. In some embodiments the nitride crystal is doped, for example, with Si or O to form n-type material, with a dopant concentration between about 1017 cm−3 and 1020 cm−3.


Referring again to FIG. 1, in one set of embodiments surface 105 of nitride crystal 101 is implanted with ions, forming an implanted/damaged region 103 according to methods that are known in the art. The ion implantation may be performed with at least one of H+, H2+, He+, Ne+, Ar+, Kr+, Xe+, N+, or N2+. The implantation energy be between about 10 keV and about 10 MeV, or preferably between about 20 keV and about 2 MeV. The ion fluence or dose may be between about 1016 cm−2 and about 1019 cm−2, between about 1017 cm−2 and about 1018 cm−2, or between about 2×1017 cm−2 and about 4×1017 cm−2. In some embodiments, the back side of crystal 101 is also implanted with ions, forming a second implanted/damaged region (not shown), with a similar ion composition, energy, and fluence, so as to minimize bow in crystal 101, as described by O. Moutanabbir and U. Gösele, J. Electronic Mater. 39, 482 (2010), which is hereby incorporated by reference in its entirety


Referring again to FIG. 1, a handle substrate 117 having surface 115 is also provided. Handle substrate 117 may comprise a single crystal, polycrystalline or amorphous material. Handle substrate 117 may comprise sapphire, aluminum oxide, mullite, silicon, silicon nitride, germanium, gallium arsenide, silicon carbide, MgAl2O4 spinel, zinc oxide, indium tin oxide (ITO), indium oxide, tin oxide, indium phosphide, beryllium oxide, chemical-vapor-deposition (CVD) diamond, single crystal diamond, YAG:Ce, gallium nitride, indium nitride, gallium aluminum indium nitride, aluminum oxynitride, or aluminum nitride. Other materials comprising transparent phosphors are described in U.S. Provisional Application No. 61/167,447 filed Apr. 7, 2009, commonly assigned, and hereby incorporated by reference herein. Handle substrate 117 may comprise an electrical insulator, a conducting oxide, a conducting transparent oxide, a luminescent material, a distributed bragg reflector (DBR) stack, a band-pass or an edge-pass filter stack, a semiconductor, a semimetal, or a metal. Handle substrate 117 may comprise substantially the same composition as crystal 101. In one specific embodiment, handle substrate 117 comprises crystals that have been merged or tiled together using another method. For example, handle substrate 117 may be formed using at least one of the tiling methods disclosed by Dwilinski et al. [US Patent Application No. 2008/0156254] or the method disclosed in U.S. patent application Ser. No. 12/635,645, which is hereby incorporated by reference in its entirety.


In one specific embodiment, handle substrate 117 comprises substantially the same composition as crystal 101 and has a crystallographic orientation within about 10 degrees, within about 5 degrees, within about 2 degrees, or within about 1 degree of that of crystal 101. Handle substrate 117 may comprise a glass, a glass-ceramic, or a ceramic. Handle substrate 117 may comprise an oxide of at least one of Si, Ge, Sn, Pb, B, Al, Ga, In, Tl, P, As, Sb, Pb, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ti, Zr, Hf, Mn, Zn, or Cd. In one specific embodiment, handle substrate 117 comprises oxygen-doped aluminum nitride. Handle substrate 117 may have a thermal expansion coefficient parallel to surface 115 between room temperature and about 700 degrees Celsius that is between about 2.5×10−6 K−1 and about 7×10−6 K−1. Handle substrate 117 may have a thermal expansion coefficient parallel to surface 115 between room temperature and about 700 degrees Celsius that is between about 5.5×10−6 K−1 and about 6.5×10−6 K−1. Handle substrate 117 may have a thermal expansion coefficient parallel to surface 115 between room temperature and about 700 degrees Celsius that within about 20%, within about 10% within about 5%, within about 2%, or within about 1% of that of nitride crystal 101. Handle substrate 117 may have a softening point, that is, where its viscosity has a value of about 108 Poise, at a temperature between about 500 degrees Celsius and about 1400 degrees Celsius. Handle substrate 117 may have a glass transition temperature between about 600 degrees Celsius and about 1200 degrees Celsius. Handle substrate 117 may have a softening point, that is, where its viscosity has a value of about 108 Poise, at a temperature between about 600 degrees Celsius and about 900 degrees Celsius. Surface 115 may be optically flat, with a deviation from flatness less than 1 micron, less than 0.5 micron, less than 0.2 micron, less than 0.1 micron, or less than 0.05 micron. Surface 115 may be very smooth, with a root-mean-square roughness less than 5 nanometers, less than 2 nanometers, less than 1 nanometer, less than 0.5 nanometer, less than 0.2 nanometer, less than 0.1 nanometer, or less than 0.05 nanometer, measured over an area of at least 10 microns×10 microns. Handle substrate 117 may be substantially transparent at visible wavelengths of light, such that one of ordinary skill in the art may be able to read printed words through handle substrate 117.


Adhesion layers 113 and 107 may be deposited on at least one of surface 115 of handle substrate 117 and surface 105 of donor substrate 101. Adhesion layers 113 and 107 may comprise at least one of SiOx, GeOx, SiNx, AlNx, GaOx, Al2O3, Sc2O3, Y2O3, B2O3, R2O3, where R is a rare earth element, MgO, CaO, SrO, HfO2, ZrO2, Ta2O5, or B, Al, Si, P, Zn, Ga, Si, Ge, Au, Ag, Ni, Ti, Cr, Zn, Cd, In, Sn, Sb, Tl, or Pb, or an oxide, nitride, or oxynitride thereof. Adhesion layers 113 and/or 107 may be electrically insulating. Adhesion layers 113 and 107 may further comprise hydrogen. The adhesion layers 113 and 107 may be deposited by thermal evaporation, electron-beam evaporation, sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, or the like, or by thermal oxidation of a deposited metallic film. The thickness of adhesion layers 113 and 107 may between about 1 nanometer and about 10 microns, or between about 10 nanometers and about 1 micron. The adhesion layer(s) may be annealed, for example, to a temperature between about 300 degrees Celsius and about 1000 degrees Celsius. In some embodiments, at least one adhesion layer is chemical-mechanically polished. In a preferred embodiment, the root-mean-square surface roughness of at least one adhesion layer is below about 0.5 nanometer, or below about 0.3 nanometer over a 20×20 μm2 area.


Referring again to FIG. 1 and also to FIG. 2, surfaces 109/209 of nitride crystal 101/201 or adhesion layer placed thereupon and surface 111/211 of handle substrate 117/217 or adhesion layer placed thereupon are placed in contract with one another and wafer-bonded. In a preferred embodiment, the wafer bonding operation is performed in a clean room, with less than 10,000, less than 1,000, less than 100, or less than 10 particles per cubic centimeter in the air. Particles may be removed from at least one of the surfaces immediately prior to wafer bonding by spraying, brushing, or rinsing with ionized nitrogen, a CO2 jet, CO2 snow, high-resistivity water, an organic solvent, such as methanol, ethanol, isopropanol, acetone, or the like. In some embodiments, surface 109/209 and surface 111/211 are brought into contact while immersed in a liquid. Optionally, at least one of the surfaces is exposed to a plasma to enhance wafer bonding.


Nitride crystal 101 may be pressed against handle substrate 117 with a pressure between about 0.1 megapascals and about 100 megapascals. In some embodiments, van der Waals forces are sufficient to obtain a good wafer bond and no additional applied force is necessary. Nitride crystal 101 and handle substrate 117 may be heated to a temperature between about 30 degrees Celsius and about 950 degrees Celsius, between about 30 degrees Celsius and about 400 degrees Celsius, or between about 30 degrees Celsius and about 200 degrees Celsius for a period between about 5 minutes and about 10 hours to strengthen the wafer bond. In some embodiments, heating of nitride crystal 101 and handle substrate 113 is performed while they are mechanically loaded against one another.


Referring again to FIG. 2 and to FIG. 3, in some embodiments, at least the surface region of bonded nitride crystal 201 having implanted/damaged region 203 and handle substrate 217/317 are heated to a temperature between about 200 degrees Celsius and about 800 degrees Celsius or between about 500 degrees Celsius and about 700 degrees Celsius to cause micro-bubbles, micro-cracks, micro-blisters, or other mechanical flaws within region 203. In one specific embodiment, surface region 306 is heated by means of optical or infrared radiation through handle substrate 217/317, and the distal portion 302 of crystal 201 may remain less than about 300 degrees Celsius, less than about 200 degrees Celsius, or less than about 100 degrees Celsius. In some embodiments, mechanical energy may be provided instead of or in addition to thermal energy. In some embodiments, an energy source such as a pressurized fluid is directed to a selected region, such as an edge, of bonded nitride crystal 201 to initiate a controlled cleaving action within region 203. After the application of energy, the distal portion 302 of nitride crystal 201 is removed, leaving a proximate portion 306 of nitride crystal 101 bonded to handle substrate 217/317.


In one set of embodiments, a release layer and a high quality epitaxial layer are functionally substituted for the ion-damaged layer, as described in U.S. Patent Application Ser. No. 61/386,879. The high quality epitaxial layer may be wafer-bonded to the handle substrate and may be separated from the nitride crystal by means of laser lift-off, preferential etching, photochemical etching, photoelectrochemical etching, or the like.


Referring again to FIG. 3, the newly exposed surface 304 of transferred layer 306 on GaN-on-handle wafer 320 may be polished, dry-etched, or chemical-mechanically polished according to methods that are known in the art to prepare an epi-ready surface.


In some embodiments, GaN-on-handle wafer 320 is used as a substrate for epitaxy. One or more edges of the wafer may be ground. The wafer may be placed in a suitable reactor and at least one epitaxial layer grown by MOCVD, MBE, HVPE, or the like. In a preferred embodiment, the epitaxial layer comprises GaN or AlxInyGa(1-x-y)N, where 0≦x, y≦1.


The GaN-on-handle wafer may be used as a substrate for fabrication into optoelectronic and electronic devices such as at least one of a light emitting diode (LED), a laser diode, a photodetector, an avalanche photodiode, a transistor, a rectifier, and a thyristor; one of a transistor, a rectifier, a Schottky rectifier, a thyristor, a p-i-n diode, a metal-semiconductor-metal diode, high-electron mobility transistor, a metal semiconductor field effect transistor, a metal oxide field effect transistor, a power metal oxide semiconductor field effect transistor, a power metal insulator semiconductor field effect transistor, a bipolar junction transistor, a metal insulator field effect transistor, a heterojunction bipolar transistor, a power insulated gate bipolar transistor, a power vertical junction field effect transistor, a cascode switch, an inner sub-band emitter, a quantum well infrared photodetector, a quantum dot infrared photodetector, a solar cell, and a diode for photoelectrochemical water splitting and hydrogen generation. Optionally, one or more devices may be flip-chip bonded for improved heat extraction.


In one specific embodiment, shown schematically in FIG. 4, the wafer is used to fabricate a high-voltage LED. In a preferred embodiment, nitride layer 401 is n-type doped, to a level between about 1017 cm−3 and about 3×1018 cm−3, and handle substrate 417 has a coefficient of thermal expansion that is approximately matched to that of nitride layer 401. In a preferred embodiment, handle substrate 417 is an electrical insulator. Nitride layer 401 and handle substrate 417 are bonded by means of adhesion layers 407 and 413. Active layer 431 and p-type layer 433 are deposited epitaxially on n-type nitride layer 401 according to methods that are known in the art, such as metalorganic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE). Mesa structures are formed to generate singulated devices or form arrayed layouts with the various pixels of the LEDs to be subsequently interconnected. Typically, this will be achieved by utilizing reactive ion etching (RIE) or inductively-coupled plasma (ICP) dry etching or photo-electrochemical (PEC) etching to etch through the active region to expose the n-GaN layer. A layer of n-type AlGaN may serve as an etch stop during the mesa-forming process. A second etch process is then performed to expose the electrically inactive adhesion layers 407/413 and/or handle substrate 417 and is desirable to prevent conduction between the n-electrodes of adjacent pixels. The adhesion layers 407/413 and/or handle substrate 417 may serve as a selective stop-etch layer. The p-electrodes 435 are then deposited upon the mesa tops and may be substantially transparent to allow for a top-emitting device configuration. Transparency should be coupled with sufficient current spreading and may be achieved by utilizing an indium tin oxide (ITO) or zinc oxide (ZnO) layer, a thin metal layer (Ni/Au, Pt/Au, Pd/Au, Ag, Pt/Ag), or a mesh grid (not shown) for the p-electrode. A second isolation (passivation) layer, which may consist of a dielectric material such as SiO2 or SixNy may then be deposited over the mesas. This layer isolates the interconnect metal from shorting an adjacent device and serves as a passivation mechanism for the active region sidewalls. Finally, a second metal layer 437 is deposited to provide the n-electrode of each device and to enable interconnection of adjacent pixels. Several common embodiments for the n-electrode are Al/Au, Ti/Au, Al/Ni/Au, or Ti/Al/Ni/Au. The contacts may be heat treated or annealed to form ohmic or near-ohmic contracts. At least two, three, four, five, six, eight, ten, twelve, 15, 20, 25, 30, 40, 50, 60, 75, or more LEDs may be interconnected in series by means of wire bonds 439 to form a multi-pixel high-voltage LED. The LED may be operated at a voltage greater than 10V, greater than 20V, greater than 40, or greater than 100V.


Optionally, the high-voltage LED may be flip-chip bonded to a carrier substrate for improved extraction of light and/or or heat. Handle substrate 401 may be shaped or removed for improved light extraction. Handle substrate 401 may be removed by methods that are known in the art, such as laser lift-off, grinding, or lapping. Adhesion layers 407 and 413 may be removed by chemical etching, electrochemical etching, anodization, lapping, or the like. The back side 441 of nitride layer 401 may be patterned or roughened by methods that are known in the art, such as chemical etching or photoelectrochemical etching to improve light extraction. Light extraction may be optimized by means of microcavity effects, surface roughening, or formation of a photonic lattice, as described in U.S. patent application Ser. Nos. 12/569,337; 12/569;841; and 12/569,844; each of which is incorporated by reference in their entirety. The high-voltage LED may be singulated and incorporated into a package according to methods that are known in the art. One or more high-voltage LEDs 400 may be mounted in a fixture and incorporated into a lighting system. High-voltage LED 400 may be further processed according to methods described in U.S. Patent Application Ser. No. 61/362,584, which is hereby incorporated by reference in its entirety.


In some embodiments, as noted above, the nitride crystal may have threading dislocations that are arranged inhomogeneously as a two-dimensional array of high-dislocation-density regions, which will be referred to as cores, within a matrix of low-dislocation-density regions. Devices may be arranged with specific spatial arrangements with respect to the cores in order to optimize the yield or performance of the devices. In other embodiments, the nitride crystal may have threading dislocations that are arranged inhomogeneously as a one-dimensional array of alternating high-dislocation-density stripes and low-dislocation-density stripes.



FIG. 5 shows an LED epi layer structure grown on a GaN-on-handle (GaNOH) wafer, where the handle substrate is electrically conductive. The layer structure consists of at least one n-type (Al,Ga,In)N layer grown on top of the GaNOH wafer, followed by an active region with at least one and more typically multiple (Al,Ga,In)N layers. The active region is followed by at least one p-type (Al,Ga,In)N layer. The layer structures can be grown by either metal-organic chemical vapor deposition (MOCVD) or atomic-layer chemical vapor deposition (ALCVD) or atomic layer epitaxy (ALE) or molecular beam epitaxy (MBE).


In one embodiment, the GaNOH wafer consists of a very low dislocation density GaN (<106-107 cm−2) layer. The low dislocation density GaN layer can be formed by either dislocation bundling into organized cores or by using nanomasking approaches resulting in randomized cores. The circular regions encircling the cores have a gradient in dislocation or defect density and are known as the shell region. The regions between the shells are referred to as interstitial regions. The dopants in the shell and interstitial regions could be the same or different. Typical dopants are Si, O, P, Mg, etc.



FIG. 6 shows an LED epi layer structure grown on a GaN-on-handle (GaNOH) wafer, where the handle substrate is electrically insulating. The layer structure consists of at least one n-type (Al,Ga,In)N layer grown on top of the GaNOH wafer, followed by an active region with at least one and more typically multiple (Al,Ga,In)N layers. The active region is followed by at least one p-type (Al,Ga,In)N layer. Mesas are formed by etching through portions of the p-type and active layers and n-type and p-type contacts placed in the troughs between mesas and on top of the mesas, respectively.



FIG. 7 shows an LED epi layer structure grown on a roughened or a patterned GaNOH wafer, where the handle substrate is electrically conductive. The roughened or the patterned GaNOH wafer allows light scattering at the back side and improves light extraction from the LED device. The epi layer structure is similar to the one described in FIG. 5.



FIG. 8 shows an LED epi layer structure grown on a roughened or a patterned GaNOH wafer, where the handle substrate is electrically insulating. The roughened or the patterned GaNOH wafer allows light scattering at the back side and improves light extraction from the LED device. The epi layer, mesa, and electrical contact structures are similar to the ones described in FIGS. 5 and 6.


In the case of a wafer with organized dislocation cores, in a preferred embodiment the devices are formed between the core regions. FIGS. 9A-9C show the device layout using a square pitch GaNOH substrate, where the handle substrate is electrically conductive. The position of the p-contact, mesa and streets are shown in the figure. The substrate can have different regions with different dopant species and with different doping concentrations. The shell region encircles the core region and the interstitial regions are the region between the shells. There may be a gradient in defect density from the core region to the interstitial region. The pitch is defined by the spacing between two adjacent (nearest) cores. In one configuration, the LED consists of a square p-contact and a square mesa. In another configuration, the LED consists of a dog-ear pattern next to the core regions for p-contact and mesa. The core region of the substrate have very high density of extended defects and they can easily form a vertical current path. The cores could therefore be utilized as a shunt path for reducing series resistance in lateral device geometries.



FIGS. 10A and 10B show a device layout using a square pitch GaNOH substrate, where the handle substrate is electrically insulating. The position of the p-contact, mesa and streets are shown in the figure. Mesas may be formed by etching around the regions that will form the p-contact through the active layer and into the n-type material (either above or below the regrowth interface), and n-type and p-type contacts deposited. In one specific embodiment, the p-type contacts may be located predominantly over the interstitial regions and the n-type contacts may overlap the cores. In some embodiments at least one of the p-type contacts and the n-type contacts are transparent or semi-transparent. After deposition of the contacts the die may be singulated by sawing or scribing and breaking along the dashed lines in FIG. 10B.


In another configuration, shown in FIG. 11, several square devices may be laid out between two adjacent core regions. Following the fabrication of the devices, the wafer may be diced in the direction shown in the figure for singulation. The preferred directions to dice or scribe are either parallel or perpendicular to the m-plane of the wurtzite-structure nitride layer.



FIGS. 12A and 12B show a device layout using a hexagonal or triangular pitch GaNOH substrate. The positions of the p-contact, mesa and streets are shown in the figure. The substrate can have different regions with different dopant species and with different doping concentrations. In one configuration, the LED consists of a triangular p-contact and a triangular mesa. In another configuration, the LED consists of a dog-ear pattern next to the core regions for p-contact and mesa. The streets and the dicing directions are also shown in the figure.


Several additional core and wafer configurations for hexagonal-pitch dot core wafers are shown in FIGS. 13A-13D. Singulation, by slicing, sawing, or cleaving, may be performed along m-planes or along a-planes.



FIG. 14 shows a device layout in a flip-chip configuration. In one specific embodiment with this configuration, vias are etched through the core region of the wafer. Etching may be performed by reaction-ion etching, inductively-coupled plasma etching, or the like. An insulating layer, for example, SiO2 or SiNx, may be deposited on the side walls of the vias and a metal deposited inside the vias to provide n-type contacts. In another specific embodiment, vias are etched around the core regions of the wafer but the cores themselves are not removed and serve as contacts to the n-type layer. The top side view is shown in FIG. 15. N-contacts are formed through the vias, and therefore both n- and p-contacts are formed on the same side of the wafer. Etching vias through the core region removes the defective region of the material and may make the devices more reliable and robust.



FIG. 16 shows a sandwiched vertical structure with a conducting carrier substrate on the p-side. This configuration can be used with transparent conducting substrates like Zinc Oxide, Indium Tin Oxide, Tin-oxide, or the like or reflecting conducting substrates like Ag-coated Silicon, or the like. The conducting carrier substrate could also comprise at least one of AlOx or CuOx. FIG. 17 is a cross-sectional view diagram of a vertical thin-film device structure having a removed handle substrate, which has been debonded, etched, polished/ground, or cleaved in one or more embodiments. In an alternative embodiment. FIG. 18 is a cross-sectional view diagram of a vertical thin-film device structure having a removed handle substrate, which has been debonded, etched, polished/ground, or cleaved in one or more embodiments.


Ion implantantion may lead to defect formation and an implantation annealing may be required post-implantation to recover the original material quality. An in situ annealing step is an attractive way to recover the material from implantation damage. FIG. 19 shows a flow-chart for performing in situ annealing in a MOCVD chamber. The annealing is carried out at high temperature in the presence of ammonia and hydrogen gas. Forming gas and ammonia mixture could also be used. Reactor pressures of approximately one atmosphere or above and temperatures in excess of about 1000 or 1100° C. are preferable for annealing. At least one epitaxial film may be grown following the in situ annealing process.


In some embodiments the handle substrate is approximately homogeneous in composition and thickness. In other embodiments, shown schematically in FIGS. 20A-20C, the handle substrate comprises two or more vias or recesses, which may be filled with a conductive material capable of electrical and/or thermal conduction. The vias and/or recesses may be formed either before or after wafer-bonding a nitride layer to the handle substrate. In one set of embodiments, recesses are created in the handle substrate that allow for enhanced thermal conductivity without allowing electrical contact between the material in the recess(es) and the semiconductor materials. The conductive material may comprise a metal, such as copper, silver, or gold, a metal matrix composite, a particle-filled epoxy, silicone, or thermoplastic resin, or another material having a higher thermal conductivity than that of the handle substrate itself. The particles in a composite filler material may comprise at least one of diamond, cubic boron nitride, hexagonal boron nitride, graphite, silver, copper, aluminum nitride, beryllium oxide, aluminum oxide, or silicon carbide. This former geometry may be advantageous by allowing for an integrated thermal path out of a device that would otherwise require special packaging and/or heat sinking.


In another set of embodiments, through-vias are formed that penetrate the handle substrate and allow electrical contact between the conductive material and the semiconductor. This latter geometry may be advantageous for heterogeneous integration of mixed semiconductor technology systems (GaN, GaAs, Si, SiC, etc.) in that it significantly reduces the chip-to-chip interconnection distance reducing power consumption, heating, and interconnect delay.


In another specific embodiment, shown schematically in FIGS. 21A and 21B, the handle substrate may further comprise a down-converting light-emitting material, such as a phosphor. This geometry may advantageous as it allows for an integrated light conversion material for generation of white light through photon mixing of different wavelength photons (blue+yellow, for example). In another embodiment, multiple wavelength down-conversion materials are embedded in the substrate. These materials may be able to generate complex spectra when excited by photon emission from the epitaxial light emitting structures grown on them. The handle substrate may further comprise particles or grains having a different index of refraction than the matrix material so as to provide enhanced light scattering.


In a specific embodiment, the one or more entities comprises a phosphor or phosphor blend selected from one or more of (Y, Gd, Tb, Sc, Lu, La)3(Al, Ga, In)5O12:Ce3+, SrGa2S4:Eu2+, SrS:Eu2+, and colloidal quantum dot thin films comprising CdTe, ZnS, ZnSe, ZnTe, CdSe, or CdTe. In other embodiments, the device may include a phosphor capable of emitting substantially red light. Such phosphor is selected from one or more of (Gd,Y,Lu,La)2O3:Eu3+, Bi3+; (Gd,Y,Lu,La)2O2S:Eu3+, Bi3+; (Gd,Y,Lu,La)VO4:Eu3+, Bi3+; Y2(O,S)3:Eu3+; Ca1-xMo1-ySiyO4:, where 0.05≦x≦0.5, 0≦y≦0.1; (Li,Na,K)5Eu(W,Mo)O4; (Ca,Sr)S:Eu2+; SrY2S4:Eu2−; CaLa2S4:Ce3+; (Ca,Sr)S:Eu2+; 3.5MgO*0.5MgF2*GeO2:Mn4+ (MFG); (Ba,Sr,Ca)MgxP2O7:Eu2+, Mn2+; (Y,Lu)2WO6:Eu3+, Mo6+; (Ba,Sr,Ca)3MgxSi2O8:Eu2+, Mn2+, wherein 1<x≦2; (RE1-yCey)Mg2-xLixSi3-xPxO12, where RE is at least one of Sc, Lu, Gd, Y, and Tb, 0.0001<x<0.1 and 0.001<y<0.1; (Y, Gd, Lu, La)2-xEuxW1-yMoyO6, where 0.5≦x.≦1.0, 0.01≦y≦1.0; (SrCa)1-xEuxSi5N8, where 0.01≦x≦0.3; SrZnO2:Sm13; MmOnX wherein M is selected from the group of Sc, Y, a lanthanide, an alkali earth metal and mixtures thereof; X is a halogen; 1≦m≦3; and 1≦n≦4, and wherein the lanthanide doping level can range from 0.1 to 40% spectral weight; and Eu3+ activated phosphate or borate phosphors; and mixtures thereof. Of course, there can be other variations, modifications, and alternatives.


In one or more embodiments, wavelength conversion materials can be ceramic, thin-film-deposited, or discrete particle phosphors, ceramic or single-crystal semiconductor plate down-conversion materials, organic or inorganic downconverters, nanoparticles, or any other materials which absorb one or more photons of a primary energy and thereby emit one or more photons of a secondary energy (“wavelength conversion”). As an example, the wavelength conversion materials can include, but are not limited to the following:

  • (Sr,Ca)10(PO4)6*DB2O3:Eu2+ (wherein 0<n1)
  • (Ba,Sr,Ca)5(PO4)3(Cl,F,Br,OH):Eu2+,Mn2+
  • (Ba,Sr,Ca)BPO5:Eu2+,Mn2+
  • Sr2Si3O8*2SrC12:Eu2+
  • (Ca,Sr,Ba)3MgSi2O8:Eu2+, Mn2+
  • BaA18O13:Eu2+
  • 2SrO*0.84P2O5*0.16B2O3:Eu2+
  • (Ba,Sr,Ca)MgAl10O17:Eu2+,Mn2+
  • (Ba,Sr,Ca)Al2O4:Eu2+
  • (Y,Gd,Lu,Sc,La)BO3:Ce3+,Tb3+
  • (Ba,Sr,Ca)2(Mg,Zn)Si2O7:Eu2+
  • (Mg,Ca,Sr, Ba,Zn)2Si1xO42x:Eu2+ (wherein 0<x=0.2)
  • (Sr,Ca,Ba)(Al,Ga,m)2S4:Eu2+
  • (Lu,Sc,Y,Tb)2uvCevCa1-uLiwMg2wPw(Si,Ge)3w012u/2 where —O.SSu^1; 0<v£Q.1; and OSw^O.2
  • (Ca,Sr)8(Mg,Zn)(SiO4)4C12:Eu2−,Mn2−
  • Na2Gd2B2O7:Ce3+,Tb3+
  • (Sr,Ca,Ba,Mg,Zn)2P2O7:Eu2+,Mn2+
  • (Gd,Y,Lu,La)2O3:Eu3+,Bi3+
  • (Gd,Y,Lu,La)2O2S:Eu3+,Bi3−
  • (Gd,Y,Lu,La)vO4:Eu3+,Bi3+
  • (Ca,Sr)S:Eu2+,Ce3+
  • (Y,Gd,Tb,La,Sm,Pr,Lu)3(Sc,Al,Ga)5uO123/2n:Ce3+ (wherein 0^0^0.5)
  • ZnS:Cu+,Cl˜
  • ZnS:Cu+,Al3+
  • ZnS:Ag+,Al3+
  • SrY2S4:Eu2+
  • CaLa2S4:Ce3+
  • (Ba,Sr,Ca)MgP2O7:Eu2+,Mn2+
  • (Y,Lu)2WO6:Eu3+,Mo6+
  • (Ba,Sr,Ca)nSinNn:Eu2− (wherein 2n+4=3n)
  • Ca3(SiO4)Cl2:Eu2+
  • ZnS:Ag+,Cl˜
  • (Y,Lu,Gd)2nCanSi4N6-nC1n:Ce3+, (wherein OSn^O.5)
  • (Lu,Ca,Li,Mg,Y)alpha-SiAlON doped with Eu2+ and/or Ce3+
  • (Ca,Sr,Ba)SiO2N2:Eu2+,Ce3+


For purposes of the application, it is understood that when a phosphor has two or more dopant ions (i.e., those ions following the colon in the above phosphors), this is to mean that the phosphor has at least one (but not necessarily all) of those dopant ions within the material. That is, as understood by those skilled in the art, this type of notation means that the phosphor can include any or all of those specified ions as dopants in the formulation. Of course, there can be other variations, modifications, and alternatives.


While the above is a full description of the specific embodiments, various modifications, alternative constructions and equivalents may be used. Therefore, the above description and illustrations should not be taken as limiting the scope of the present invention which is defined by the appended claims.

Claims
  • 1. A gallium and nitrogen containing device comprising: a gallium and nitrogen containing material, wherein, the gallium and nitrogen containing material comprises a first surface region, a second surface region, and at least one core region;the first surface region is opposite the second surface region; andthe at least one core region extends between the first surface region and the second surface region and through the gallium and nitrogen containing material;an interface region overlying the second surface region;at least one n-type epitaxial growth region overlying the interface region;a core structure extending from the at least one core region through the at least one n-type epitaxial growth region;an active region overlying the at least one n-type epitaxial growth region;a p-type region overlying the active region;a first handle substrate overlying the p-type region, wherein the first handle substrate is transparent, substantially transparent, or reflective; andat least one p-contact region overlying the first handle substrate.
  • 2. The device of claim 1, wherein the interface region is characterized by a defect density of less than about 106 cm−2 to 107 cm−2 within a matrix region between adjacent core regions.
  • 3. The device of claim 1, wherein the gallium and nitrogen containing material is provided from a dot core substrate.
  • 4. The device of claim 1, wherein the first surface region comprises a patterned, textured, or roughened surface structure.
  • 5. The device of claim 1, wherein, the at least one core region comprises a plurality of core regions; andthe plurality of core regions form a square array and a die is approximately square.
  • 6. The device of claim 1, wherein, the at least one core region comprises a plurality of core regions; andthe plurality of core regions form a hexagonal array and a die is approximately triangular.
  • 7. The device of claim 1, further comprising: an adhesion layer overlying the first surface region;a second handle substrate comprising a first surface region and a second surface region, wherein, the first surface region of the second handle substrate is opposite the second surface region of the second handle substrate; andthe second surface region of the second handle substrate overlies the adhesion layer; andat least one n-contact region overlying the first surface region of the second handle substrate.
  • 8. The device of claim 1, further comprising at least one n-contact region overlying the first surface region.
  • 9. The device of claim 1, wherein the first handle substrate comprises at least one through via or partial via.
  • 10. The device of claim 1, wherein the first handle substrate is transparent or substantially transparent and comprises a down-converting light-emitting material.
  • 11. A gallium and nitrogen containing device comprising: a gallium and nitrogen containing material, wherein, the gallium and nitrogen containing material comprises a first surface region, a second surface region, and at least one core region;the first surface region is opposite the second surface region; andthe at least one core region extends between the first surface region and the second surface region and through the gallium and nitrogen containing material;an interface region overlying the second surface region;at least one n-type epitaxial growth region overlying the interface region;a core structure extending from the at least one core region through the at least one n-type epitaxial growth region;an active region overlying the at least one n-type epitaxial growth region;a p-type region overlying the active region;one or more via or street structures providing an electrical barrier between adjacent core regions and a matrix region between the adjacent core regions;at least one electrical contact region overlying a core region surrounded by a via or street structure; andat least one handle substrate.
  • 12. The device of claim 11, wherein the interface region is characterized by a defect density of less than about 106 cm−2 to 107 cm−2 within the matrix region.
  • 13. The device of claim 11, wherein the gallium and nitrogen containing material is provided from a dot core substrate.
  • 14. The device of claim 11, wherein the first surface region comprises a patterned, textured, or roughened surface structure.
  • 15. The device of claim 11, wherein, the at least one core region comprises a plurality of core regions; andthe plurality of core regions form a square array and a die is approximately square.
  • 16. The device of claim 11, wherein, the at least one core region comprises a plurality of core regions; andthe plurality of core regions form a hexagonal array and a die is approximately triangular.
  • 17. The device of claim 11, further comprising: an adhesion layer overlying the first surface region; andat least one p-contact region overlying the p-type region, wherein, the at least one handle substrate comprises a first surface region and a second surface region;the first surface region is opposite the second surface region;the second surface region overlies the adhesion layer; andthe at least one electrical contact region comprises an n-type contact region.
  • 18. The device of claim 11, further comprising: at least one n-contact region overlying the first surface region; andat least one p-contact region overlying the at least one core region; andwherein the at least one handle substrate comprises a first transparent or reflective handle substrate overlying the at least one p-type region.
  • 19. The device of claim 11, wherein the at least one handle substrate comprises at least one through via or partial via.
  • 20. The device of claim 11, wherein, the at least one handle substrate is transparent or substantially transparent; andthe at least one handle substrate comprises a down-converting light-emitting material.
Parent Case Info

This application is a continuation of U.S. application Ser. No. 13/012,674, filed on Jan. 24, 2011, now allowed, which is incorporated by reference in its entirety.

US Referenced Citations (400)
Number Name Date Kind
3245760 Sawyer Apr 1966 A
3303053 Strong et al. Feb 1967 A
3335084 Hall Aug 1967 A
3647522 Single Mar 1972 A
4030966 Hornig et al. Jun 1977 A
4065688 Thornton Dec 1977 A
4430051 von Platen Feb 1984 A
4870045 Gasper et al. Sep 1989 A
5331654 Jewell et al. Jul 1994 A
5607899 Yoshida et al. Mar 1997 A
5632812 Hirabayashi May 1997 A
5685885 Khandros et al. Nov 1997 A
5764674 Hibbs-Brenner et al. Jun 1998 A
5813753 Vriens et al. Sep 1998 A
5868837 DiSalvo et al. Feb 1999 A
6090202 Klipov Jul 2000 A
6129900 Satoh et al. Oct 2000 A
6152977 D'Evelyn Nov 2000 A
6335771 Hiraishi Jan 2002 B1
6350191 D'Evelyn Feb 2002 B1
6372002 D'Evelyn et al. Apr 2002 B1
6398867 D'Evelyn et al. Jun 2002 B1
6406776 D'Evelyn Jun 2002 B1
6455877 Ogawa et al. Sep 2002 B1
6475254 Saak et al. Nov 2002 B1
6498355 Harrah et al. Dec 2002 B1
6501154 Morita et al. Dec 2002 B2
6509651 Matsubara et al. Jan 2003 B1
6533874 Vaudo et al. Mar 2003 B1
6541115 Pender et al. Apr 2003 B2
6547249 Collins, III et al. Apr 2003 B2
6596040 Saak et al. Jul 2003 B2
6596079 Vaudo et al. Jul 2003 B1
6639925 Niwa et al. Oct 2003 B2
6656615 Dwilinski et al. Dec 2003 B2
6680959 Tanabe et al. Jan 2004 B2
6734461 Shiomi et al. May 2004 B1
6764297 Godwin et al. Jul 2004 B2
6765240 Tischler et al. Jul 2004 B2
6784463 Camras et al. Aug 2004 B2
6787814 Udagawa Sep 2004 B2
6806508 D'Evelyn et al. Oct 2004 B2
6809781 Setlur et al. Oct 2004 B2
6858882 Tsuda et al. Feb 2005 B2
6860628 Robertson et al. Mar 2005 B2
6861130 D'Evelyn et al. Mar 2005 B2
6936488 D'Evelyn et al. Aug 2005 B2
6955719 Dmitriev et al. Oct 2005 B2
6956246 Epler et al. Oct 2005 B1
7001577 Zimmerman et al. Feb 2006 B2
7009199 Hall Mar 2006 B2
7009215 D'Evelyn et al. Mar 2006 B2
7012279 Wierer, Jr. et al. Mar 2006 B2
7026755 Setlur et al. Apr 2006 B2
7033858 Chai et al. Apr 2006 B2
7053413 D'Evelyn et al. May 2006 B2
7063741 D'Evelyn et al. Jun 2006 B2
7067407 Kostamo et al. Jun 2006 B2
7078731 D'Evelyn et al. Jul 2006 B2
7098487 D'Evelyn et al. Aug 2006 B2
7101433 D'Evelyn et al. Sep 2006 B2
7102158 Tysoe et al. Sep 2006 B2
7105865 Nakahata et al. Sep 2006 B2
7112829 Picard et al. Sep 2006 B2
7119372 Stokes et al. Oct 2006 B2
7122827 Alizadeh et al. Oct 2006 B2
7125453 D'Evelyn et al. Oct 2006 B2
7128849 Setlur et al. Oct 2006 B2
7160388 Dwili ski et al. Jan 2007 B2
7160531 Jacques et al. Jan 2007 B1
7175704 D'Evelyn et al. Feb 2007 B2
7198671 Ueda Apr 2007 B2
7208393 Haskell et al. Apr 2007 B2
7220658 Haskell et al. May 2007 B2
7252712 Dwilinski et al. Aug 2007 B2
7285801 Eliashevich et al. Oct 2007 B2
7291544 D'Evelyn et al. Nov 2007 B2
7303630 Motoki et al. Dec 2007 B2
7316746 D'Evelyn et al. Jan 2008 B2
7329371 Setlur et al. Feb 2008 B2
7335262 Dwilinski et al. Feb 2008 B2
7338828 Imer et al. Mar 2008 B2
7341880 Erchak et al. Mar 2008 B2
7348600 Narukawa et al. Mar 2008 B2
7358542 Radkov et al. Apr 2008 B2
7358543 Chua et al. Apr 2008 B2
7364619 Dwilinski et al. Apr 2008 B2
7368015 D'Evelyn et al. May 2008 B2
7381391 Spencer et al. Jun 2008 B2
7390359 Miyanaga et al. Jun 2008 B2
7419281 Porchia et al. Sep 2008 B2
7420261 Dwili ski et al. Sep 2008 B2
7470938 Lee et al. Dec 2008 B2
7483466 Uchida et al. Jan 2009 B2
7489441 Scheible et al. Feb 2009 B2
7518159 Masui et al. Apr 2009 B2
7566639 Kohda Jul 2009 B2
7572425 McNulty et al. Aug 2009 B2
7622742 Kim et al. Nov 2009 B2
7625446 D'Evelyn et al. Dec 2009 B2
7642122 Tysoe et al. Jan 2010 B2
7704324 D'Evelyn et al. Apr 2010 B2
7705276 Giddings et al. Apr 2010 B2
7733571 Li Jun 2010 B1
7759710 Chiu et al. Jul 2010 B1
7816238 Osada et al. Oct 2010 B2
7858408 Mueller et al. Dec 2010 B2
7862761 Okushima et al. Jan 2011 B2
7871839 Lee et al. Jan 2011 B2
7884538 Mitsuishi et al. Feb 2011 B2
7923741 Zhai et al. Apr 2011 B1
7976630 Poblenz et al. Jul 2011 B2
8021481 D'Evelyn Sep 2011 B2
8044412 Murphy et al. Oct 2011 B2
8048225 Poblenz et al. Nov 2011 B2
8097081 D'Evelyn Jan 2012 B2
8142566 Kiyomi et al. Mar 2012 B2
8148801 D'Evelyn Apr 2012 B2
8188504 Lee May 2012 B2
8198643 Lee et al. Jun 2012 B2
8207548 Nagai Jun 2012 B2
8207554 Shum Jun 2012 B2
8247886 Sharma et al. Aug 2012 B1
8247887 Raring et al. Aug 2012 B1
8252662 Poblenz et al. Aug 2012 B1
8284810 Sharma et al. Oct 2012 B1
8293551 Sharma et al. Oct 2012 B2
8299473 D'Evelyn et al. Oct 2012 B1
8303710 D'Evelyn Nov 2012 B2
8304265 Nakamura et al. Nov 2012 B2
8306081 Schmidt et al. Nov 2012 B1
8310143 Van De Ven et al. Nov 2012 B2
8314429 Raring et al. Nov 2012 B1
8323405 D'Evelyn Dec 2012 B2
8329511 D'Evelyn Dec 2012 B2
8350273 Vielemeyer Jan 2013 B2
8455894 D'Evelyn et al. Jun 2013 B1
8477259 Kubota et al. Jul 2013 B2
8502465 Katona et al. Aug 2013 B2
8524578 Raring et al. Sep 2013 B1
8575728 Raring et al. Nov 2013 B1
8686431 Batres et al. Apr 2014 B2
8786053 D'Evelyn et al. Jul 2014 B2
8791499 Sharma et al. Jul 2014 B1
20010009134 Kim et al. Jul 2001 A1
20010011935 Lee et al. Aug 2001 A1
20010043042 Murazaki et al. Nov 2001 A1
20010048114 Morita et al. Dec 2001 A1
20010055208 Kimura Dec 2001 A1
20020070416 Morse et al. Jun 2002 A1
20020096994 Iwafuchi et al. Jul 2002 A1
20020105986 Yamasaki Aug 2002 A1
20020127824 Shelton et al. Sep 2002 A1
20020155691 Lee et al. Oct 2002 A1
20020182768 Morse et al. Dec 2002 A1
20020189532 Motoki et al. Dec 2002 A1
20030000453 Unno et al. Jan 2003 A1
20030001238 Ban Jan 2003 A1
20030020087 Goto et al. Jan 2003 A1
20030027014 Johnson et al. Feb 2003 A1
20030047076 Liu Mar 2003 A1
20030080345 Motoki et al. May 2003 A1
20030140845 D'Evelyn et al. Jul 2003 A1
20030145784 Thompson et al. Aug 2003 A1
20030164507 Edmond et al. Sep 2003 A1
20030183155 D'Evelyn et al. Oct 2003 A1
20030209191 Purdy Nov 2003 A1
20030232512 Dickinson et al. Dec 2003 A1
20040000266 D'Evelyn et al. Jan 2004 A1
20040023427 Chua et al. Feb 2004 A1
20040070004 Eliashevich et al. Apr 2004 A1
20040080256 Hampden-Smith et al. Apr 2004 A1
20040104391 Maeda et al. Jun 2004 A1
20040116033 Ouderkirk et al. Jun 2004 A1
20040124435 D'Evelyn et al. Jul 2004 A1
20040161222 Niida et al. Aug 2004 A1
20040207998 Suehiro et al. Oct 2004 A1
20040222357 King et al. Nov 2004 A1
20040245543 Yoo Dec 2004 A1
20040251471 Dwilinski et al. Dec 2004 A1
20050001227 Niki et al. Jan 2005 A1
20050012446 Jermann et al. Jan 2005 A1
20050045894 Okuyama et al. Mar 2005 A1
20050087753 D'Evelyn et al. Apr 2005 A1
20050098095 D'Evelyn et al. May 2005 A1
20050109240 Maeta et al. May 2005 A1
20050121679 Nagahama et al. Jun 2005 A1
20050128459 Zwet et al. Jun 2005 A1
20050128469 Hall et al. Jun 2005 A1
20050152820 D'Evelyn et al. Jul 2005 A1
20050167680 Shei et al. Aug 2005 A1
20050191773 Suzuki et al. Sep 2005 A1
20050199899 Lin et al. Sep 2005 A1
20050205215 Giddings et al. Sep 2005 A1
20050214992 Chakraborty et al. Sep 2005 A1
20050224830 Blonder et al. Oct 2005 A1
20050232327 Nomura et al. Oct 2005 A1
20050263791 Yanagihara et al. Dec 2005 A1
20060030738 Vanmaele et al. Feb 2006 A1
20060032428 Dwilinski et al. Feb 2006 A1
20060037529 D'Evelyn et al. Feb 2006 A1
20060037530 Dwilinski et al. Feb 2006 A1
20060038193 Wu et al. Feb 2006 A1
20060038542 Park et al. Feb 2006 A1
20060048699 D'Evelyn et al. Mar 2006 A1
20060060131 Atanackovic Mar 2006 A1
20060060872 Edmond et al. Mar 2006 A1
20060079082 Bruhns et al. Apr 2006 A1
20060096521 D'Evelyn et al. May 2006 A1
20060118799 D'Evelyn et al. Jun 2006 A1
20060163589 Fan et al. Jul 2006 A1
20060166390 Letertre et al. Jul 2006 A1
20060169993 Fan et al. Aug 2006 A1
20060177362 D'Evelyn et al. Aug 2006 A1
20060186418 Edmond et al. Aug 2006 A1
20060189098 Edmond Aug 2006 A1
20060204865 Erchak et al. Sep 2006 A1
20060205199 Baker et al. Sep 2006 A1
20060207497 D'Evelyn et al. Sep 2006 A1
20060213429 Motoki et al. Sep 2006 A1
20060214287 Ogihara et al. Sep 2006 A1
20060228870 Oshima Oct 2006 A1
20060246687 Kaiser et al. Nov 2006 A1
20060255343 Ogihara et al. Nov 2006 A1
20060273339 Steigerwald et al. Dec 2006 A1
20060289386 Tysoe et al. Dec 2006 A1
20070015345 Baker et al. Jan 2007 A1
20070045200 Moon et al. Mar 2007 A1
20070057337 Kano et al. Mar 2007 A1
20070062440 Sato et al. Mar 2007 A1
20070072324 Krames et al. Mar 2007 A1
20070077674 Okuyama et al. Apr 2007 A1
20070093073 Farrell et al. Apr 2007 A1
20070096239 Cao et al. May 2007 A1
20070105351 Motoki et al. May 2007 A1
20070114569 Wu et al. May 2007 A1
20070121690 Fujii et al. May 2007 A1
20070131967 Kawaguchi et al. Jun 2007 A1
20070141819 Park et al. Jun 2007 A1
20070142204 Park et al. Jun 2007 A1
20070151509 Park et al. Jul 2007 A1
20070158785 D'Evelyn et al. Jul 2007 A1
20070164292 Okuyama Jul 2007 A1
20070166853 Guenther et al. Jul 2007 A1
20070178039 D'Evelyn et al. Aug 2007 A1
20070181056 D'Evelyn et al. Aug 2007 A1
20070190758 Kaeding et al. Aug 2007 A1
20070197004 Dadgar et al. Aug 2007 A1
20070202624 Yoon et al. Aug 2007 A1
20070210074 Maurer et al. Sep 2007 A1
20070215033 Imaeda et al. Sep 2007 A1
20070228404 Tran et al. Oct 2007 A1
20070231978 Kanamoto et al. Oct 2007 A1
20070234946 Hashimoto et al. Oct 2007 A1
20070252164 Zhong et al. Nov 2007 A1
20070264733 Choi et al. Nov 2007 A1
20070274359 Takeuchi et al. Nov 2007 A1
20070280320 Feezell et al. Dec 2007 A1
20070290224 Ogawa Dec 2007 A1
20080006831 Ng Jan 2008 A1
20080008855 D'Evelyn et al. Jan 2008 A1
20080023691 Jang et al. Jan 2008 A1
20080025360 Eichler et al. Jan 2008 A1
20080030976 Murazaki et al. Feb 2008 A1
20080054290 Shieh et al. Mar 2008 A1
20080073660 Ohno et al. Mar 2008 A1
20080083741 Giddings et al. Apr 2008 A1
20080083929 Fan et al. Apr 2008 A1
20080087919 Tysoe et al. Apr 2008 A1
20080099777 Erchak et al. May 2008 A1
20080106212 Yen et al. May 2008 A1
20080121906 Yakushiji May 2008 A1
20080121913 McKenzie et al. May 2008 A1
20080128752 Wu Jun 2008 A1
20080142781 Lee Jun 2008 A1
20080156254 Dwilinski et al. Jul 2008 A1
20080164489 Schmidt et al. Jul 2008 A1
20080164578 Tanikella et al. Jul 2008 A1
20080173884 Chitnis et al. Jul 2008 A1
20080179607 DenBaars et al. Jul 2008 A1
20080179610 Okamoto et al. Jul 2008 A1
20080193363 Tsuji Aug 2008 A1
20080194054 Lin et al. Aug 2008 A1
20080198881 Farrell et al. Aug 2008 A1
20080210958 Senda et al. Sep 2008 A1
20080211416 Negley et al. Sep 2008 A1
20080217745 Miyanaga et al. Sep 2008 A1
20080230765 Yoon et al. Sep 2008 A1
20080237569 Nago et al. Oct 2008 A1
20080261381 Akiyama et al. Oct 2008 A1
20080272462 Shimamoto et al. Nov 2008 A1
20080272463 Butcher et al. Nov 2008 A1
20080282978 Butcher et al. Nov 2008 A1
20080283851 Akita Nov 2008 A1
20080284346 Lee Nov 2008 A1
20080285609 Ohta et al. Nov 2008 A1
20080298409 Yamashita et al. Dec 2008 A1
20080303033 Brandes Dec 2008 A1
20090032828 Romano et al. Feb 2009 A1
20090065798 Masui et al. Mar 2009 A1
20090071394 Nakahata et al. Mar 2009 A1
20090072252 Son et al. Mar 2009 A1
20090078955 Fan et al. Mar 2009 A1
20090081857 Hanser et al. Mar 2009 A1
20090086475 Caruso et al. Apr 2009 A1
20090092536 Kawabata et al. Apr 2009 A1
20090140279 Zimmerman et al. Jun 2009 A1
20090146170 Zhong et al. Jun 2009 A1
20090155989 Uematsu et al. Jun 2009 A1
20090194796 Hashimoto et al. Aug 2009 A1
20090206354 Kitano et al. Aug 2009 A1
20090213593 Foley et al. Aug 2009 A1
20090218593 Kamikawa et al. Sep 2009 A1
20090227056 Kyono et al. Sep 2009 A1
20090250686 Sato et al. Oct 2009 A1
20090252191 Kubota et al. Oct 2009 A1
20090267098 Choi Oct 2009 A1
20090273005 Lin Nov 2009 A1
20090301387 D'Evelyn Dec 2009 A1
20090301388 D'Evelyn Dec 2009 A1
20090309110 Raring et al. Dec 2009 A1
20090315480 Yan et al. Dec 2009 A1
20090320744 D'Evelyn Dec 2009 A1
20090320745 D'Evelyn et al. Dec 2009 A1
20090321745 Kinoshita et al. Dec 2009 A1
20090321778 Chen et al. Dec 2009 A1
20100001300 Raring et al. Jan 2010 A1
20100003492 D'Evelyn Jan 2010 A1
20100006873 Raring et al. Jan 2010 A1
20100006876 Moteki et al. Jan 2010 A1
20100025656 Raring et al. Feb 2010 A1
20100031872 D'Evelyn Feb 2010 A1
20100031873 D'Evelyn Feb 2010 A1
20100031874 D'Evelyn Feb 2010 A1
20100031875 D'Evelyn Feb 2010 A1
20100031876 D'Evelyn Feb 2010 A1
20100032691 Kim Feb 2010 A1
20100055819 Ohba et al. Mar 2010 A1
20100108985 Chung et al. May 2010 A1
20100109030 Krames et al. May 2010 A1
20100117101 Kim et al. May 2010 A1
20100117106 Trottier May 2010 A1
20100117118 Dabiran et al. May 2010 A1
20100147210 D'Evelyn Jun 2010 A1
20100148145 Ishibashi et al. Jun 2010 A1
20100149814 Zhai et al. Jun 2010 A1
20100151194 D'Evelyn Jun 2010 A1
20100155746 Ibbetson et al. Jun 2010 A1
20100195687 Okamoto et al. Aug 2010 A1
20100200837 Zimmerman et al. Aug 2010 A1
20100219505 D'Evelyn Sep 2010 A1
20100220262 DeMille et al. Sep 2010 A1
20100240158 Ter-Hovhannissian Sep 2010 A1
20100290208 Pickard Nov 2010 A1
20100295088 D'Evelyn et al. Nov 2010 A1
20100309943 Chakraborty et al. Dec 2010 A1
20110017298 Lee Jan 2011 A1
20110056429 Raring et al. Mar 2011 A1
20110062415 Ohta et al. Mar 2011 A1
20110064103 Ohta et al. Mar 2011 A1
20110075694 Yoshizumi et al. Mar 2011 A1
20110100291 D'Evelyn May 2011 A1
20110101400 Chu et al. May 2011 A1
20110101414 Thompson et al. May 2011 A1
20110108081 Werthen et al. May 2011 A1
20110121331 Simonian et al. May 2011 A1
20110124139 Chang May 2011 A1
20110175200 Yoshida Jul 2011 A1
20110177631 Gardner et al. Jul 2011 A1
20110180781 Raring et al. Jul 2011 A1
20110182056 Trottier et al. Jul 2011 A1
20110183498 D'Evelyn Jul 2011 A1
20110186860 Enya et al. Aug 2011 A1
20110186874 Shum Aug 2011 A1
20110216795 Hsu et al. Sep 2011 A1
20110220912 D'Evelyn Sep 2011 A1
20110256693 D'Evelyn et al. Oct 2011 A1
20110262773 Poblenz et al. Oct 2011 A1
20110266552 Tu et al. Nov 2011 A1
20110279054 Katona et al. Nov 2011 A1
20110317397 Trottier et al. Dec 2011 A1
20120000415 D'Evelyn et al. Jan 2012 A1
20120007102 Feezell et al. Jan 2012 A1
20120073494 D'Evelyn Mar 2012 A1
20120091465 Krames et al. Apr 2012 A1
20120104412 Zhong et al. May 2012 A1
20120118223 D'Evelyn May 2012 A1
20120135553 Felker et al. May 2012 A1
20120137966 D'Evelyn et al. Jun 2012 A1
20120178215 D'Evelyn Jul 2012 A1
20120199841 Batres et al. Aug 2012 A1
20120199952 D'Evelyn et al. Aug 2012 A1
20120288974 Sharma et al. Nov 2012 A1
20130022758 Trottier Jan 2013 A1
20130026483 Sharma et al. Jan 2013 A1
20130044782 Raring Feb 2013 A1
20130112987 Fu et al. May 2013 A1
20130126902 Isozaki et al. May 2013 A1
20130234108 David et al. Sep 2013 A1
20140103356 Krames et al. Apr 2014 A1
Foreign Referenced Citations (17)
Number Date Country
2381490 Oct 2011 EP
06-334215 Dec 1994 JP
1997-082587 Mar 1997 JP
1999-340507 Dec 1999 JP
1999-340576 Dec 1999 JP
2001-177146 Jun 2001 JP
2003-031844 Jan 2003 JP
2005-289797 Oct 2005 JP
2007-039321 Feb 2007 JP
2007-110090 Apr 2007 JP
2008-084973 Apr 2008 JP
2008-172040 Jul 2008 JP
WO 2005121415 Dec 2005 WO
WO 2006062880 Jun 2006 WO
WO 2007004495 Jan 2007 WO
WO 2009001039 Dec 2008 WO
WO 2012016033 Feb 2012 WO
Non-Patent Literature Citations (194)
Entry
Aguilar, ‘Ohmic n-contacts to Gallium Nitride Light Emitting Diodes’, National Nanotechnologhy Infrastructure Network, 2007, p. 56-81.
Baker et al., ‘Characterization of Planar Semipolar Gallium Nitride Films on Spinel Substrates’, Japanese Journal of Applied Physics, vol. 44, No. 29, 2005, pp. L920-L922.
Benke et al., ‘Uncertainty in Health Risks from Artificial Lighting due to Disruption of Circadian Rythm and Melatonin Secretion: A Review’, Human and Ecological Risk Assessment: An International Journal, vol. 19, No. 4, 2013, pp. 916-929.
Byrappa et al., ‘Handbook of Hydrothermal Technology: A Technology for Crystal Growth and Materials Processing’, Noyes Publications, Park Ridge, New Jersey, 2001, pp. 94-96 and 152.
Callahan et al., ‘Synthesis and Growth of Gallium Nitride by the Chemical Vapor Reaction Process (CVRP)’, MRS Internet Journal Nitride Semiconductor Research, vol. 4, No. 10, 1999, pp. 1-6.
Chiang et al., ‘Luminescent Properties of Cerium-Activated Garnet Series Phosphor: Structure and Temperature Effects’, Journal of the Electrochemical Society, vol. 155, No. 6, 2008, pp. B517-B520.
Chiu et al., ‘Synthesis and Luminescence Properties of Intensely Red-Emitting M5Eu(WO4)4-x(MoO4)x(M=Li, Na, K) Phosphors’, Journal of the Electrochemical Society, vol. 155, No. 3, 2008, pp. J71-J78.
Choi et al., ‘2.51 microcavity InGaN light-emitting diodes fabricated by a selective dry-etch thinning process’, Applied Physics Letters, 2007, 91(6), 061120.
Cl et al., ‘Ca1-xMo1-ySiyO4:Eux3+: A Novel Red Phosphor for White Light Emitting Diodes’, Physica B, vol. 403, 2008, pp. 670-674.
Cich et al., ‘Bulk GaN based violet light-emitting diodes with high efficiency at very high current density’, Applied Physics Letters, Nov. 29, 2012, pp. 223509-1-223509-3.
D'Evelyn et al., ‘Bulk GaN Crystal Growth by the High-Pressure Ammonothermal Method’, Journal of Crystal Growth, vol. 300, 2007, pp. 11-16.
Dwilinski et al., ‘Ammono Method of BN, AIN and GaN Synthesis and Crystal Growth’, MRS Internet Journal Nitride Semiconductor Research, vol. 3, No. 25, 1998, pp. 1-5.
Dwilinski et al., ‘Excellent Crystallinity of Truly Bulk Ammonothermal GaN’, Journal of Crystal Growth, vol. 310, 2008, pp. 3911-3916.
Farrell et al., ‘Continuous-Wave Operation of AIGaN-Cladding-Free Nonpolar m-Plane InGaN/GaN Laser Diodes’, 2007, Japanese Journal of Applied Physics, vol. 46, No. 32, 2007, pp. L761-L763.
Feezell et al., ‘AIGaN-Cladding-Free Nonpolar InGaN/GaN Laser Diodes’, Japanese Journal of Applied Physics, vol. 46, No. 13, 2007, pp. L284-L286.
Founta et al., ‘Anisotropic Morphology of Nonpolar a-Plane GaN Quantum Dots and Quantum Wells’, Journal of Applied Physics, vol. 102, vol. 7, 2007, pp. 074304-1-074304-6.
Frayssinet et al., ‘Evidence of Free Carrier Concentration Gradient Along the c-Axis for Undoped GaN Single Crystals’, Journal of Crystal Growth, vol. 230, 2001, pp. 442-447.
Fukuda et al., ‘Prospects for the Ammonothermal Growth of Large GaN Crystal’, Journal of Crystal Growth, vol. 305, 2007, pp. 304-310.
Hanifin et al., ‘Photoreception for Circadian, Neuroendocrine, and Neurobehavioral Regulation’, Journal of Physiological Anthropology, vol. 26, 2007, pp. 87-94.
Happek, ‘Development of Efficient UV-LED Phosphor Coatings for Energy Saving Solid State Lighting’, University of Georgia, 2007, 22 pages.
Hashimoto et al., ‘A GaN bulk crystal with improved structural quality grown by the ammonothermal method’, Nature Materials, vol. 6, 2007, pp. 568-671.
Hashimoto et al., ‘Ammonothermal Growth of Bulk GaN’, Journal of Crystal Growth, vol. 310, 2008, pp. 3907-3910.
Haskell et al., ‘Defect Reduction in (1100) m-plane gallium nitride via lateral epitaxial overgrowth by hydride vapor phase epitaxy’, Applied Physics Letters 86, 111917 (2005), pp. 1-3.
Hoppe et al., ‘Luminescence in Eu2+-Doped Ba2Si5N8: Fluorescence, Thermoliminescence, and Upconversion’, Journal of Physics and Chemistry of Solids, vol. 61, 2000, pp. 2001-2006.
Iso et al., ‘High Brightness Blue InGaN/GaN Light Emitting Diode on Nonpolar m-Plane Bulk GaN Substrate’, Japanese Journal of Applied Physics, vol. 46, No. 40, 2007, pp. L960-L962.
Kim et al., ‘High Brightness Light Emitting Diodes Using Dislocation-Free Indium Gallium Nitride/Gallium Nitride Multiquantum—Well Nanorod Arrays’, Nano Letters, vol. 4, No. 6, 2004, pp. 1059-1062.
Kim et al, ‘Improved Electroluminescence on Nonpolar m-Plane InGaN/GaN Qantum Well LEDs’, Rapid Research Letters, vol. 1, No. 3, 2007, pp. 125-127.
Kojima et al., ‘Stimulated Emission at 474 nm From an InGaN Laser Diode Structure Grown on a (1122) GaN Substrate’, Applied Physics Letters, vol. 91, 2007, pp. 251107-251107-3.
Kolis et al., ‘Materials Chemistry and Bulk Crystal Growth of Group III Nitrides in Supercritical Ammonia’, Material Resources Society Symposium Proceedings, vol. 495, 1998, pp. 367-372.
Kolis et al., ‘Crystal Growth of Gallium Nitride in Supercritical Ammonia’, Journal of Crystal Growth, vol. 222, 2001, pp. 431-434.
Kubota et al., ‘Temperature Dependence of Polarized Photoluminescence From Nonpolar m-Plane InGaN Multiple Quantum Wells for Blue Laser Diodes’, Applied Physics Letter, vol. 92, 2008, pp. 011920-1-011920-3.
Li et al., ‘The Effect of Replacement of Sr by Ca OnThe Structural and Luminescence Properties of the Red-Emitting Sr2Si5N8:Eu2+ LED Conversion Phosphor’, Journal of Solid State Chemistry, vol. 181, 2007, pp. 515-524.
Lide et al., ‘Thermal Conductivity of Ceramics and Other Insulating Materials’, CRC Handbook of Chemistry and Physics, 91st Edition, 2010-2011, pp. 12-203 and 12-204.
Lu et al., ‘Etch-Pits of GaN Films with Different Etching Methods’, Journal of the Korean Physical Society, vol. 45, Dec. 2004, p. S673-S675.
Mastro et al., ‘Hydride vapor phase epitaxy-grown A1GaN/GaN high electron mobility tTransistors’, Solid-State Electronics, vol. 47, Issue 6, Jun. 2003, pp. 1075-1079.
http://www.matbase.com/material/non-ferrous-metals/other/molybdenum/properties, Data Table for: Non-Ferrous Metals: Other Metals: Molybdenum, Mar. 28, 2011, pp. 1.
Mirwald et al., ‘Low-Friction Cell for Piston-Cylinder High Pressure Apparatus’, Journal of Geophysical Research, vol. 80, No. 11, 1975, pp. 1519-1525.
Morkoc, ‘Handbook of Nitride Semiconductors and Devices’, vol. 1, 2008, p. 704.
Motoki et al., ‘Growth and Characterization of Freestanding GaN Substrates’, Journal of Crystal Growth, vol. 237-239, 2002, pp. 912-921.
Motoki et al., ‘Dislocation reduction in GaN crystal by advanced-DEEP’, Journal of Crystal Growth, vol. 305, Apr. 1, 2007, pp. 377-383.
Mueller-Mach et al., ‘Highly Efficient All-Nitride Phosphor-Converted White Light Emitting Diode’, Physica Status Solidi (a), vol. 202, 2005, pp. 1727-1732.
Murota et al., ‘Solid State Light Source Fabricated With YAG:Ce Single Crystal’, Japanese Journal of Applied Physics, vol. 41, Part 2, No. 8A, 2002, pp. L887-L888.
Okamoto et al., ‘Continuous-Wave Operation of m-Plane InGaN Multiple Quantum Well Laser Diodes’, Japanese Journal of Applied Physics, vol. 46, No. 9, 2007, pp. L187-L189.
Okamoto et al., ‘Pure Blue Laser Diodes Based on Nonpolar m-Plane Gallium Nitride With InGaN Waveguiding Layers’, Japanese Journal of Applied Physics, vol. 46, No. 35, 2007, pp. L820- L822.
Oshima et al., ‘Thermal and Optical Properties of Bulk GaN Crystals Fabricated Through Hydride Vapor Phase Epitaxy With Void-Assisted Separation’, Journal of Applied Physics, vol. 98, No. 10, Nov. 18, 2005, pp. 103509-1-103509-4.
Pattison et al., ‘Gallium Nitride Based Microcavity Light Emitting Diodes With 2? Effective Cavity Thickness’, Applied Physics Letters, vol. 90, Issue 3, 031111 (2007) 3pg.
International Search Report of PCT Application No. PCT/US2009/048489, dated Sep. 14, 2009, 12 pages total.
International Search Report & Written Opinion of PCT Application No. PCT/US2013/029453, dated Jul. 25, 2013, 11 pages total.
Peters, ‘Ammonothermal Synthesis of Aluminium Nitride’, Journal of Crystal Growth, vol. 104, 1990, pp. 411-418.
http://www.philipslumileds.com/products/luxeon-flash, ‘Luxeon Flash’, Philips Lumileds, Aug. 8, 2013, pp. 1-2.
Rea et al., ‘White Lighting’, COLOR Research and Application, vol. 38, No. 2, Sep. 3, 2011, pp. 82-92.
Rickert et al., ‘n-GaN Surface Treatments for Metal Contacts Studied Via X-ray Photoemission Spectroscopy’, Applied Physics Letters, vol. 80, No. 2, Jan. 14, 2002, p. 204-206.
Sarva et al., ‘Dynamic Compressive Strength of Silicon Carbide Under Uniaxial Compression’, Material Sciences and Engineering, vol. A317, 2001, pp. 140-144.
Sato et al., ‘High Power and High Efficiency Semipolar InGaN Light Emitting Diodes’, Journal of Light and Visible Environment, vol. 32, No. 2, Dec. 13, 2007, pp. 57-60.
Sato et al., ‘High Power and High Efficiency Green Light Emitting Diode on Free-Standing Semipolar (1122) Bulk GaN Substrate’, Physica Status Solidi (RRL), vol. 1, No. 4, 2007, pp. 162-164.
Sato et al., ‘Optical Properties of Yellow Light-Emitting Diodes Grown on Semipolar (1122) Bulk GaN Substrate’, Applied Physics Letters, vol. 92, No. 22, 2008, pp. 221110-1-221110-3.
Schmidt et al., ‘Demonstration of Nonpolar m-Plane InGaN/GaN Laser Diodes’, Japanese Journal of Applied Physics, vol. 46, No. 9, 2007, pp. L190-L191.
Selvanathan et al., ‘Investigation of Surface Treatment Schemes on n-type GaN and A1 0.20Ga0.80N’, Journal of Vacuum Science and Technology B, vol. 23, No. 6, May 10, 2005, p. 2538-2544.
Semendy et al., ‘Observation and Study of Dislocation Etch Pits in Molecular Beam Epitaxy Grown Gallium Nitride with the use of Phosphoric Acid and Molten Potassium Hydroxide’, Army Research Laboratory, Jun. 2007, 18 pages.
Setlur et al., ‘Crystal Chemistry and Luminescence of Ce3+-Doped (Lu2CaMg2(Si,Ge)3O12 and Its Use in LED Based Lighting’, Chemistry of Materials, vol. 18, 2006, pp. 3314-3322.
Sizov et al., ‘500-nm Optical Gain Anisotropy of Semipolar (1122) InGaN Quantum Wells’, Applied Physics Express, vol. 2, 2009, pp. 071001-1-071001-3.
Tsuda et al., ‘Blue Laser Diodes Fabricated on m-Plane GaN Substrates’, Applied Physics Express, vol. 1, 2008, pp. 011104-1-011104-3.
Tyagi et al., ‘Semipolar (1011) InGaN/GaN Laser Diodes on Bulk GaN Substrates’, Japanese Journal of Applied Physics, vol. 46, No. 19, 2007, pp. L444-L445.
Communication from the Japanese Patent Office re 2013515583 dated Feb. 27, 2014, (2 pages).
Communication from the Korean Patent Office re 10-2012-7009980 dated Apr. 15, 2013, (6 pages).
Communication from the Japanese Patent Office re 2012-529969, dated Oct. 15, 2013, (6 pages).
Wang et al , ‘Ammonothermal Growth of GaN Crystals in Alkaline Solutions’, Journal of Crystal Growth, vol. 287, 2006, pp. 376-380.
Wang et al., ‘Ammonothermal Synthesis of III-Nitride Crystals’, Crystal Growth & Design, vol. 6, No. 6, 2006, pp. 1227-1246.
Wang et al., ‘Synthesis of Dense Polycrystaline GaN of High Purity by the Chemical Vapor Reaction Process’, Journal of Crystal Growth, vol. 286, 2006, pp. 50-54.
Wang et al., ‘New Red Y0.85Bi0.1Eu0.05V1-yMyO4 (M=Nb, P) Phosphors for Light-Emitting Diodes’, Physica B, vol. 403, 2008, pp. 2071-2075.
Weaver et al., ‘Optical Properties of Selected Elements’, Handbook of Chemistry and Physics, 94th Edition, 2013-2014, pp. 12-126-12-150.
Weisbuch et al., ‘Recent results and latest views on microcavity LEDs’, Light-Emitting Diodes: Research, Manufacturing, and Applications VIII, ed. by S.A. Stockman et al., Proc. SPIE, vol. 5366, p. 1-19 (2004).
Yamamoto, ‘White LED Phosphors: The Next Step’, Proceeding of SPIE, 2010, pp. 1-10.
Yang et al., ‘Preparation and luminescence properties of LED conversion novel phosphors SrZn02:Sm’, Materials Letters, vol. 62, 2008, pp. 907-910.
Zhong et al., ‘High Power and High Efficiency Blue Light Emitting Diode on Freestanding Semipolar (1011) Bulk GaN Substrate’, Applied Physics Letter, vol. 90, No. 23, 2007, pp. 233504-1-233504-3.
Zhong et al., ‘Demonstration of High Power Blue-Green Light Emitting Diode on Semipolar (1122) Bulk GaN Substrate’, Electronics Letters, vol. 43, No. 15, 2007, pp. 825-826.
USPTO Office Action for U.S. Appl. No. 12/133,364 dated Nov. 26, 2010 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/133,364 dated Jun. 1, 2011 (7 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/133,364 dated Oct. 11, 2011 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/133,365 dated Jun. 9, 2011 (16 pages).
USPTO Office Action for U.S. Appl. No. 12/133,365 dated Oct. 18, 2011 (21 pages).
USPTO Office Action for U.S. Appl. No. 12/334,418 dated Apr. 5, 2011 (19 pages).
USPTO Office Action for U.S. Appl. No. 12/334,418 dated Oct. 19, 2011 (23 pages).
USPTO Office Action for U.S. Appl. No. 12/478,736 dated Sep. 27, 2011 (10 pages).
USPTO Office Action for U.S. Appl. No. 12/478,736 dated Feb. 7, 2012 (6 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/478,736 dated Apr. 23, 2012 (7 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/478,736 dated Oct. 9, 2012 (4 pages).
USPTO Office Action for U.S. Appl. No. 12/481,543 dated Jun. 27, 2011 (9 pages).
USPTO Office Action for U.S. Appl. No. 12/484,095 dated Nov. 10, 2010 (8 pages).
USPTO Office Action for U.S. Appl. No. 12/484,095 dated Jul. 8, 2011 (11 pages).
USPTO Office Action for U.S. Appl. No. 12/491,169 dated Oct. 22, 2010 (9 pages).
USPTO Office Action for U.S. Appl. No. 12/491,169 dated May 11, 2011 (9 pages).
USPTO Office Action for U.S. Appl. No. 12/491,176 dated Mar. 1, 2012 (9 pages).
USPTO Office Action for U.S. Appl. No. 12/497,289 dated Feb. 2, 2012 (6 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/497,289 dated May 22, 2012 (7 pages).
USPTO Office Action for U.S. Appl. No. 12/497,969 dated Feb. 2, 2012 (19 pages).
USPTO Office Action for U.S. Appl. No. 12/497,969 dated Jul. 5, 2012 (17 pages).
USPTO Office Action for U.S. Appl. No. 12/534,838 dated May 3, 2011 (11 pages).
USPTO Office Action for U.S. Appl. No. 12/534,838 dated Jan. 13, 2012 (12 pages).
USPTO Office Action for U.S. Appl. No. 12/534,838 dated Mar. 20, 2012 (12 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/534,838 dated Jun. 8, 2012 (8 pages).
USPTO Office Action for U.S. Appl. No. 12/534,843 dated Sep. 10, 2012 (9 pages).
USPTO Office Action for U.S. Appl. No. 12/534,844 dated Sep. 16, 2010 (8 pages).
USPTO Office Action for U.S. Appl. No. 12/534,844 dated Feb. 4, 2011 (9 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/534,849 dated Jul. 31, 2012 (11 pages).
USPTO Office Action for U.S. Appl. No. 12/534,857 dated Sep. 1, 2010 (10 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/534,857 dated May 27, 2011 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/546,458 dated Jul. 20, 2011 (4 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/546,458 dated Nov. 28, 2011 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/556,558 dated Sep. 16, 2010 (8 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/556,558 dated Mar. 22, 2011 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/556,562 dated Sep. 15, 2010 (7 pages).
USPTO Office Action for U.S. Appl. No. 12/556,562 dated Mar. 21, 2011 (5 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/556,562 dated Jul. 27, 2011 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/569,337 dated May 9, 2012 (18 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/569,337 dated Nov. 15, 2012 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/569,841 dated Dec. 23, 2011 (12 pages).
USPTO Office Action for U.S. Appl. No. 12/569,841 dated Mar. 26, 2013 (17 pages).
USPTO Office Action for U.S. Appl. No. 12/569,841 dated Aug. 13, 2013 (20 pages).
USPTO Office Action for U.S. Appl. No. 12/569,841 dated Feb. 14, 2014 (20 pages).
USPTO Office Action for U.S Appl. No. 12/569,844 dated Oct. 12, 2012 (12 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/569,844 dated Mar. 7, 2013 (9 pages).
USPTO Office Action for U.S. Appl. No. 12/634,665 dated Apr. 25, 2012 (10 pages).
USPTO Office Action for U.S. Appl. No. 12/634,665 dated Oct. 1, 2012 (10 pages).
USPTO Office Action for U.S. Appl. No. 12/634,665 dated Mar. 12, 2012 (9 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/720,593 dated Jul. 11, 2012 (7 pages).
USPTO Office Action for U.S. Appl. No. 12/724,983 dated Mar. 5, 2012 (20 pages).
USPTO Office Action for U.S. Appl. No. 12/749,466 dated Jul. 3, 2012 (18 pages).
USPTO Office Action for U.S. Appl. No. 12/749,476 dated Apr. 11, 2011 (14 pages).
USPTO Office Action for U.S. Appl. No. 12/749,476 dated Nov. 8, 2011 (11 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/749,476 dated May 4, 2012 (8 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/749,476 dated Jun. 26, 2012 (8 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/754,886 dated May 17, 2012 (19 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/754,886 dated Jun. 5, 2012 (16 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/754,886 dated Jun. 20, 2012 (14 pages).
USPTO Office Action for U.S. Appl. No. 12/785,404 dated Mar. 6, 2012 (9 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/785,404 dated Jul. 16, 2012 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/785,953 dated Apr. 12, 2012 (11 pages).
USPTO Office Action for U.S. Appl. No. 12/785,953 dated Jan. 11, 2013 (14 pages).
USPTO Office Action for U.S. Appl. No. 12/785,953 dated Oct. 3, 2013 (10 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/785,953 dated Mar. 20, 2014 (8 pages).
USPTO Office Action for U.S. Appl. No. 12/861,765 dated Jul. 2, 2012 (11 pages).
USPTO Office Action for U.S. Appl. No. 12/861,765 dated Mar. 7, 2013 (12 pages).
USPTO Office Action for U.S. Appl. No. 12/861,765 dated Sep. 17, 2013 (10 pages).
USPTO Office Action for U.S. Appl. No. 12/861,765 dated Mar. 28, 2014 (12 pages).
USPTO Office Action for U.S. Appl. No. 12/879,784 dated Jan. 25, 2012 (6 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/879,784 dated Apr. 3, 2012 (7 pages).
USPTO Office Action for U.S. Appl. No. 12/880,803 dated Feb. 22, 2012 (8 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/880,803 dated Jul. 18, 2012 (5 pages).
USPTO Office Action for U.S. Appl. No. 12/880,889 dated Feb. 27, 2012 (12 pages).
USPTO Office Action for U.S. Appl. No. 12/880,889 dated Sep. 19, 2012 (12 pages).
USPTO Office Action for U.S. Appl. No. 12/891,668 dated Sep. 25, 2012 (20 pages).
USPTO Office Action for U.S. Appl. No. 12/936,238 dated Aug. 30, 2012 (11 pages).
USPTO Office Action for U.S. Appl. No. 12/936,238 dated Jan. 30, 2013 (12 pages).
USPTO Notice of Allowance for U.S. Appl. No. 12/936,238 dated Apr. 16, 2013 (9 pages).
USPTO Office Action for U.S. Appl. No. 12/995,946 dated Mar. 28, 2012 (17 pages).
USPTO Office Action for U.S. Appl. No. 12/995,946 dated Jan. 29, 2013 (25 pages).
USPTO Office Action for U.S. Appl. No. 12/995,946 dated Aug. 2, 2013 (15 pages).
USPTO Office Action for U.S. Appl. No. 13/012,674 dated Jan. 17, 2014 (15 pages).
USPTO Notice of Allowance for U.S. Appl. No. 13/012,674 dated Apr. 30, 2014 (8 pages).
USPTO Office Action for U.S. Appl. No. 13/014,622 dated Nov. 28, 2011 (13 pages).
USPTO Office Action for U.S. Appl. No. 13/014,622 dated Apr. 30, 2012 (13 pages).
USPTO Office Action for U.S. Appl. No. 13/014,622 dated Jun. 20, 2014 (15 pages).
USPTO Office Action for U.S. Appl. No. 13/019,897 dated Mar. 30, 2012 (14 pages).
USPTO Office Action for U.S. Appl. No. 13/019,897 dated Jan. 16, 2013 (7 pages).
USPTO Office Action for U.S. Appl. No. 13/019,897 dated Dec. 2, 2013 (17 pages).
USPTO Office Action for U.S. Appl. No. 13/019,897 dated Jun. 12, 2014 (8 pages).
USPTO Office Action for U.S. Appl. No. 13/025,833 dated Jul. 12, 2012 (15 pages).
USPTO Office Action for U.S. Appl. No. 13/041,199 dated Nov. 30, 2012 (13 pages).
USPTO Notice of Allowance for U.S. Appl. No. 13/163,482 dated Jul. 31, 2012 (5 pages).
USPTO Office Action for U.S. Appl. No. 13/175,739 dated Dec. 7, 2012 (5 pages).
USPTO Office Action for U.S. Appl. No. 13/179,346 dated Aug. 17, 2012 (17 pages).
USPTO Office Action for U.S. Appl. No. 13/179,346 dated Dec. 13, 2012 (20 pages).
USPTO Office Action for U.S. Appl. No. 13/226,249 dated Oct. 10, 2012 (7 pages).
USPTO Office Action for U.S. Appl. No. 13/281,221 dated Jun. 21, 2013 (6 pages).
USPTO Notice of Allowance for U.S. Appl. No. 13/281,221 dated Nov. 12, 2013 (10 pages).
USPTO Office Action for U.S. Appl. No. 13/304,182 dated May 9, 2014 (12 pages).
USPTO Notice of Allowance for U.S. Appl. No. 13/304,182 dated Aug. 27, 2014 (8 pages).
USPTO Office Action for U.S. Appl. No. 13/328,978 dated May 15, 2013 (24 pages).
USPTO Office Action for U.S. Appl. No. 13/328,978 dated Sep. 26, 2013 (25 pages).
USPTO Office Action for U.S. Appl. No. 13/357,578 dated May 13, 2014 (8 pages).
USPTO Notice of Allowance for U.S. Appl. No. 13/425,304 dated Aug. 22, 2012 (7 pages).
USPTO Office Action for U.S. Appl. No. 13/465,976 dated Aug. 16, 2012 (16 pages).
USPTO Office Action for U.S. Appl. No. 13/465,976 dated Dec. 20, 2012 (16 pages).
USPTO Office Action for U.S. Appl. No. 13/465,976 dated Aug. 25, 2014 (21 pages).
USPTO Office Action for U.S. Appl. No. 13/548,635 dated Jun. 14, 2013 (5 pages).
USPTO Notice of Allowance for U.S. Appl. No. 13/548,635 dated Sep. 16, 2013 (6 pages).
USPTO Office Action for U.S. Appl. No. 13/548,770 dated Mar. 12, 2013 (5 pages).
USPTO Notice of Allowance for U.S. Appl. No. 13/548,770 dated Jun. 25, 2013 (6 pages).
USPTO Office Action for U.S. Appl. No. 13/553,691 dated Sep. 17, 2014 (14 pages).
USPTO Office Action for U.S. Appl. No. 13/629,366 dated Oct. 31, 2013 (7 pages).
USPTO Office Action for U.S. Appl. No. 13/629,366 dated Apr. 18, 2014 (7 pages).
USPTO Office Action for U.S. Appl. No. 13/723,968 dated Nov. 29, 2013 (23 pages).
USPTO Office Action for U.S. Appl. No. 14/054,234 dated Aug. 14, 2014 (24 pages).
Related Publications (1)
Number Date Country
20140346546 A1 Nov 2014 US
Continuations (1)
Number Date Country
Parent 13012674 Jan 2011 US
Child 14301520 US