US20130126920A1 - Light-Emitting Diode Chip with Current Spreading Layer - Google Patents

Light-Emitting Diode Chip with Current Spreading Layer Download PDF

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US20130126920A1
US20130126920A1 US13/640,037 US201113640037A US2013126920A1 US 20130126920 A1 US20130126920 A1 US 20130126920A1 US 201113640037 A US201113640037 A US 201113640037A US 2013126920 A1 US2013126920 A1 US 2013126920A1
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layer
current spreading
light
emitting diode
diode chip
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Petrus Sundgren
Elmar Baur
Martin Hohenadler
Clemens Hofmann
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Ams Osram International GmbH
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/14—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/112—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H01L33/305—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table characterised by the doping materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H01L33/38—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes with a particular shape
    • H01L33/382—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes with a particular shape the electrode extending partially in or entirely through the semiconductor body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H01L33/40—Materials therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/483—Containers
    • H01L33/486—Containers adapted for surface mounting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates generally to optical devices and, in particular embodiments, to a light-emitting diode chip with a current spreading layer.
  • a comparatively thick current spreading layer composed of a semiconductor material having good electrical conductivity is generally arranged between the electrical contact and the light-emitting semiconductor layer sequence, in order to obtain as uniform a current flow as possible through the active layer.
  • the document U.S. Pat. No. 6,426,518 B1 discloses a light-emitting diode chip wherein the light-emitting region is based on a phosphide compound semiconductor.
  • a current spreading layer composed of p-AlGaAs is arranged between the electrical contact and the light-emitting region.
  • the current spreading layer has a thickness of between 1 ⁇ m and 10 ⁇ m.
  • the invention specifies a light-emitting diode chip which comprises a current spreading layer having low optical absorption and at the same time low sensitivity to moisture.
  • the light-emitting diode chip contains a semiconductor layer sequence comprising a phosphide compound semiconductor material.
  • the semiconductor layer sequence comprises a plurality of layers composed of In x Ga y Al 1-x-y P with 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 and x+y ⁇ 1.
  • the semiconductor layer sequence contains, in particular, a p-type phosphide compound semiconductor region, an n-type phosphide compound semiconductor region and an active layer arranged between the p-type phosphide compound semiconductor region and the n-type phosphide compound semiconductor region and serving for emitting electromagnetic radiation.
  • the active layer can be embodied e.g., as a pn junction, as a double heterostructure, as a multiple heterostructure, as a single quantum well structure or multiple quantum well structure.
  • the designation quantum well structure encompasses any structure in which charge carriers experience a quantization of their energy states as a result of confinement.
  • the designation quantum well structure does not include any indication about the dimensionality of the quantization. It therefore encompasses, inter alia, quantum wells, quantum wires or quantum dots and any combination of these structures.
  • the n-type semiconductor region faces a radiation exit area of the light-emitting diode chip
  • the p-type semiconductor region faces a carrier of the light-emitting diode chip.
  • the light-emitting diode chip is a so-called thin-film light-emitting diode chip, wherein a growth substrate used for the growth of the semiconductor layer sequence is detached from the light-emitting diode chip.
  • the original growth substrate can be detached, in particular, from the n-type semiconductor region of the semiconductor layer sequence.
  • the light-emitting diode chip is preferably connected to the carrier, for example by means of a soldering connection.
  • the carrier is different than a growth substrate of the semiconductor layers sequence and preferably comprises silicon, molybdenum or germanium.
  • the p-type semiconductor region faces the carrier and the n-type semiconductor region faces the radiation exit area.
  • a current spreading layer having a thickness of less than 500 nm is arranged between the carrier and the p-type semiconductor region, said current spreading layer consisting of one or a plurality of p-doped Al x Ga 1-x As layer(s) with 0.5 ⁇ x ⁇ 1.
  • the current spreading layer is arranged between the carrier and the p-type semiconductor region, it is better protected against oxidation and/or the action of moisture than if it adjoined the ambient medium, in particular air, at the radiation exit side of the light-emitting diode chip.
  • a current spreading layer having a thickness of less than 500 nm has lower sensitivity to oxidation and/or moisture than comparatively thick current spreading layers. This is possibly based on the fact that the volume of an AlGaAS layer increases if the layer partly oxidizes. In the case of the current spreading layer only having a thickness of less than 500 nm, this effect is less pronounced than in the case of a thicker layer.
  • the required growth time for the current spreading layer is advantageously reduced by virtue of the small thickness of the current spreading layer of less than 500 nm. Since the growth of the current spreading layer takes place at elevated temperatures, the reduction of the growth time also reduces the diffusion of impurities from the adjacent semiconductor layer sequence into the current spreading layer, for example the diffusion of dopants such as Mg and Zn from the p-type semiconductor region of the semiconductor layer sequence.
  • the small thickness of the current spreading layer of less than 500 nm furthermore advantageously reduces the optical absorption in the current spreading layer.
  • Radiation emitted in the active layer of the semiconductor layer sequence which radiation is firstly emitted in the direction of the current spreading layer and the carrier, is therefore absorbed in the current spreading layer to a lesser extent than in the case of a significantly thicker current spreading layer.
  • the radiation emitted in the direction of the carrier is preferably reflected by a mirror layer arranged on the carrier in the direction toward a radiation exit side of the light-emitting diode chip.
  • the optical absorption in the current spreading layer is therefore advantageously also comparatively low since the one or the plurality of p-doped Al x Ga 1-x As layers forming the current spreading layer have a proportion of aluminum x>0.5. On account of the comparatively large proportion of aluminum, the current spreading layer has a comparatively large electronic band gap which reduces the absorption of the radiation.
  • the current spreading layer has a thickness of less than 300 nm. This further improves the stability of the layer with respect to oxidation and/or action of moisture and reduces the optical absorption.
  • the current spreading layer can be an individual layer composed of Al x Ga 1-x As or a plurality of partial layers composed of Al x Ga 1-x As.
  • the advantageous configurations of the current spreading layer as described here and hereinafter apply to the totality of the partial layers.
  • the thickness of a current spreading layer composed of a plurality of partial layers is overall less than 500 nm or particularly preferably even overall less than 300 nm.
  • the current spreading layer advantageously has a dopant concentration of more than 1 ⁇ 10 19 cm ⁇ 3 .
  • the dopant concentration in the current spreading layer is at least 5 ⁇ 10 19 cm ⁇ 3 .
  • a high electrical conductivity in the current spreading layer is advantageously obtained as a result of a high dopant concentration.
  • the current spreading layer comprises C as dopant. It has advantageously been found that high dopant concentrations with good reproducibility can be obtained with C as dopant in AlGaAs layers.
  • the current spreading layer including its side flanks is provided with an encapsulation layer.
  • the encapsulation layer can contain, in particular, silicon oxide, silicon nitride, a transparent conductive oxide such as, for example, zinc oxide or a metal.
  • the current spreading layer can be structured, for example, before the encapsulation layer is applied. During the structuring, by way of example, edge regions of the current spreading layer can be removed, such that an encapsulation layer subsequently applied by means of a coating method also covers the side flanks of the current spreading layer.
  • the encapsulation layer further reduces, in particular, the sensitivity of the current spreading layer toward environmental influences, in particular toward oxidation and/or the action of moisture. It is possible for the encapsulation layer to contain different materials in different partial regions.
  • the encapsulation layer can be formed from an electrically insulating material such as silicon oxide or silicon nitride, for example, in partial regions, while it is formed from an electrically conductive material such as zinc oxide, for example, or from a metal in other regions.
  • the electrically conductive partial regions of the encapsulation layer serve in particular, for impressing current into the current spreading layer.
  • the current spreading layer has oblique side flanks, which are inclined by an angle of between 20° and 70° inclusive with respect to the layer plane of the current spreading layer.
  • the coupling-out of radiation from the optoelectronic component can be improved in this way.
  • the oblique side flanks of the current spreading layer can function as microprisms by which radiation emitted in the active layer, said radiation being emitted in the direction of the carrier, is reflected toward the radiation exit side of the light-emitting diode chip. It is possible for the oblique side flanks to extend right into the phosphide compound semiconductor layer sequence, such that one or a plurality of layers of the semiconductor layer sequence also have oblique side flanks.
  • At least one trench is formed in the current spreading layer.
  • the at least one trench is preferably filled with silicon nitride, silicon oxide, zinc oxide or a metal.
  • the filling material directly adjoins the p-type semiconductor region. Through the trench it is possible to define, in a targeted manner, a current path through the semiconductor layer sequence. It is advantageously also possible for the at least one trench to extend right into the p-type phosphide compound semiconductor region.
  • the at least one AlGaAs layer in the current spreading layer may contain a small proportion of one or a plurality of further elements.
  • the proportion of the one or of the plurality of further elements in the current spreading layer is less than 10% in this case.
  • the one or the plurality of further elements can be dopants, or small amounts of a further material of the third or fifth main group of the periodic system.
  • FIG. 1 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a first exemplary embodiment
  • FIG. 2 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a second exemplary embodiment
  • FIG. 3 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a third exemplary embodiment
  • FIG. 4 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a fourth exemplary embodiment
  • FIG. 5 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a fifth exemplary embodiment.
  • the thin-film light-emitting diode chip illustrated in FIG. 1 contains a semiconductor layer sequence 5 comprising a p-type semiconductor region 2 and an n-type semiconductor region 4 .
  • An active layer 3 is arranged between the p-type semiconductor region 2 and the n-type semiconductor region 4 .
  • the active layer 3 preferably has a single or multiple quantum well structure.
  • the semiconductor layer sequence 5 is based on a phosphide compound semiconductor, that is to say that the semiconductor layers contained in the semiconductor layer sequence 5 comprise, in particular, In x Ga y Al 1-x-y P where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 and x+y ⁇ 1.
  • the p-type semiconductor region 2 , the active layer 3 and the n-type semiconductor region are formed from phosphide compound semiconductor materials.
  • the light-emitting diode chip is a so-called thin-film LED, wherein a growth substrate used for the growth of the semiconductor layer sequence 5 has been detached from the semiconductor layer sequence 5 .
  • the growth substrate can be detached from the n-type semiconductor region 4 , which now has the radiation exit area 6 of the light-emitting diode chip.
  • the light-emitting diode chip is connected to a carrier 7 , which preferably comprises silicon, germanium or molybdenum.
  • the n-type semiconductor region 4 faces the radiation exit area 6 and the p-type semiconductor region 2 faces the carrier 7 .
  • a current spreading layer 1 is arranged between the carrier 7 and the p-type phosphide compound semiconductor region 2 .
  • the current spreading layer 1 is a p-doped Al x Ga 1-x As layer where 0.5 ⁇ x ⁇ 1, which has a thickness of less than 500 nm.
  • the thickness of the current spreading layer 1 is even only less than 300 nm.
  • 0.6 ⁇ x ⁇ 0.8 preferably holds true.
  • the current spreading layer 1 adjoins an electrical contact 9 at least in partial regions at a side facing the carrier 7 . At least one further electrical contact 9 of the light-emitting diode chip is arranged, for example, on the radiation exit side 6 of the light-emitting diode chip, said radiation exit side being opposite the carrier.
  • the current spreading layer 1 preferably has a dopant concentration of more than 1 ⁇ 10 19 cm ⁇ 3 and particularly preferably of more than 5 ⁇ 10 19 cm ⁇ 3 . A high transverse conductivity of the current spreading layer 1 is obtained in this way, such that a current flows through the semiconductor layer sequence 5 comparatively homogeneously even when the rear-side contact 9 is applied, for example, only to a small central region of the current spreading layer 1 .
  • the current spreading layer 1 On account of its small thickness of less than 500 nm or preferably of less than 300 nm and on account of the high aluminum content of more than 0.5, the current spreading layer 1 has advantageously low optical absorption. Furthermore, it has been found that such a thin current spreading layer 1 is less sensitive to oxidation or the action of moisture than comparatively thick conventional current spreading layers that typically have a thickness of 1 um or more. Despite the small thickness, good current spreading is obtained with the current spreading layer 1 , wherein it is advantageous if the current spreading layer 1 has a dopant concentration of at least 1 ⁇ 10 19 cm ⁇ 3 and particularly preferably of at least 5 ⁇ 10 19 cm ⁇ 3 .
  • the current spreading layer 1 adjoining the p-type semiconductor region 2 is arranged between the carrier 7 and the p-type semiconductor region 2 since with this arrangement it is better protected against external influences such as oxidation or moisture than if it adjoined the ambient medium at the surface of the light-emitting diode chip.
  • the current spreading layer 1 is composed of a plurality of partial layers (not illustrated) made of Al x Ga 1-x As where in each case 0.5 ⁇ x ⁇ 1, wherein the partial layers can differ from one another for example in terms of their dopant concentration and/or in terms of their aluminum content.
  • the totality of the partial layers is regarded as the current spreading layer 1 , such that, in particular, the total thickness of all the partial layers is less than 500 nm and preferably less than 300 nm. It is also conceivable for the current spreading layer 1 or the partial layers of the current spreading layer to have small amounts of additional materials, the proportion of which, however, overall is less than 10%.
  • said current spreading layer preferably including its side flanks 11 is provided with an encapsulation layer 8 .
  • the encapsulation layer 8 can comprise, in particular, a transparent dielectric material such as, for example, silicon nitride or silicon oxide. Alternatively, however, it is also possible for the encapsulation layer 8 to comprise a transparent conductive oxide such as, for example, zinc oxide or a metal. Particularly in the case of an encapsulation layer 8 composed of a dielectric material, the electrical contact 9 for the current spreading layer 1 can be arranged in a cutout of the encapsulation layer 8 .
  • a layer sequence 10 composed of a metal or a metal alloy is arranged between the encapsulation layer 8 , the electrical contact layer 9 and the carrier 7 .
  • the metallic layers 10 can contain, for example, a minor layer for reflecting the radiation emitted from the active layer 3 in the direction of the carrier 7 .
  • the metallic layers 10 can also comprise a solder layer for connecting the light-emitting diode chip to the carrier 7 .
  • the exemplary embodiment of a light-emitting diode chip as illustrated in FIG. 2 differs from the exemplary embodiment in FIG. 1 in that the current spreading layer 1 has oblique side flanks 12 .
  • the oblique side flanks 12 preferably form an angle of between 20° and 70° inclusive with the layer plane of the current spreading layer 1 . It has been found that the coupling-out of radiation from the light-emitting diode chip can be improved by means of the oblique side flanks 12 of the current spreading layer 1 .
  • the oblique side flanks 12 act as reflectors that can reflect radiation in the direction toward the radiation exit area 6 .
  • the opposite oblique side flanks 12 of the current spreading layer 1 it is possible for the opposite oblique side flanks 12 of the current spreading layer 1 to form a microprism. It is also possible for the oblique side flanks 12 to extend right into the semiconductor layer sequence 5 (not illustrated).
  • the exemplary embodiment illustrated in FIG. 2 corresponds to the first exemplary embodiment.
  • the exemplary embodiment of a light-emitting diode chip as illustrated in FIG. 3 differs from the exemplary embodiment illustrated in FIG. 1 in that the metallic layer sequence 10 in the region of the side flanks of the light-emitting diode chip reaches as far as the p-type semiconductor region 2 . Consequently, the current spreading layer 1 including its side flanks 11 is enclosed by the encapsulation layer 8 , and the encapsulation layer 8 is enclosed by the metallic layer sequence 10 . Particularly good resistance of the current spreading layer 1 to oxidation or the action of moisture is obtained in this way.
  • the exemplary embodiment illustrated in FIG. 3 furthermore differs from the exemplary embodiment illustrated in FIG. 1 in that an In x Ga y Al 1-x-y As layer 14 where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 and x+y ⁇ 1 adjoins the current spreading layer 1 , and has a lower dopant concentration and a smaller band gap than the current spreading layer 1 .
  • the layer 14 is preferably arranged between the current spreading layer 1 and the p-type semiconductor region 2 . At the interface with the more highly doped current spreading layer 1 the layer 14 forms a potential well in which free charge carriers in the form of holes accumulate. The holes form a so-called two-dimensional hole gas in the layer 14 . In this way, a particularly high transverse conductivity is obtained in the layer 14 .
  • two trenches 13 are formed in the current spreading layer 1 , into which the encapsulation layer 8 projects. That region of the current spreading layer 1 which is arranged between the trenches 13 is electrically connected by means of the electrical contact 9 and the metallic layer sequence 10 . By contrast, the edge regions 1 a , 1 b of the current spreading layer 1 are not electrically connected. Generation of radiation in the regions of the semiconductor chip which are arranged below the contacts 9 arranged in the edge regions on the radiation exit area of the light-emitting diode chip is reduced in this way.
  • FIG. 5 illustrates a further exemplary embodiment of a light-emitting diode chip wherein two trenches 13 are formed in the current spreading layer 1 .
  • the metallic layer sequence 10 extends right into the p-type semiconductor region 2 .
  • the metallic layer sequence 10 is insulated from the current spreading layer 1 outside the region of the contact 9 by the encapsulation layer 8 .

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Abstract

A light-emitting diode chip includes a semiconductor layer sequence having a phosphide compound semiconductor material. The semiconductor layer sequence contains a p-type semiconductor region, an n-type semiconductor region, and an active layer arranged between the p-type semiconductor region and the n-type semiconductor region. The active region serves to emit electromagnetic radiation. The n-type semiconductor region faces a radiation exit area of the light-emitting diode chip, and the p-type semiconductor region faces a carrier of the light-emitting diode chip. A current spreading layer having a thickness of less than 500 nm is arranged between the carrier and the p-type semiconductor region. The current spreading layer has one or a plurality of p-doped AlxGa1-xAs layers with 0.5<x≦1.

Description

  • This patent application is a national phase filing under section 371 of PCT/EP2011/055566, filed Apr. 8, 2011, which claims the priority of German patent application 10 2010 014 667.6, filed Apr. 12, 2010, each of which is incorporated herein by reference in its entirety.
    • TECHNICAL FIELD
  • The present invention relates generally to optical devices and, in particular embodiments, to a light-emitting diode chip with a current spreading layer.
    • BACKGROUND
  • In light-emitting diode chips, a comparatively thick current spreading layer composed of a semiconductor material having good electrical conductivity is generally arranged between the electrical contact and the light-emitting semiconductor layer sequence, in order to obtain as uniform a current flow as possible through the active layer.
  • By way of example, the document U.S. Pat. No. 6,426,518 B1 discloses a light-emitting diode chip wherein the light-emitting region is based on a phosphide compound semiconductor. A current spreading layer composed of p-AlGaAs is arranged between the electrical contact and the light-emitting region. The current spreading layer has a thickness of between 1 μm and 10 μm.
  • It has been found that with such comparatively thick current spreading layers composed of AlGaAs, a good current spreading layer can be obtained, but on the other hand a not inconsiderable proportion of the emitting radiation is also absorbed. The absorption by a thick current spreading layer is non-negligible in particular when the emitted radiation has a short wavelength and/or the proportion of aluminum in the current spreading layer is low. Furthermore, it has been found that an increase in the portion of aluminum in the current spreading layer increases the sensitivity of the light-emitting diode chip to moisture.
    • SUMMARY OF THE INVENTION
  • In one aspect, the invention specifies a light-emitting diode chip which comprises a current spreading layer having low optical absorption and at the same time low sensitivity to moisture.
  • In accordance with at least one embodiment, the light-emitting diode chip contains a semiconductor layer sequence comprising a phosphide compound semiconductor material. In particular, the semiconductor layer sequence comprises a plurality of layers composed of InxGayAl1-x-yP with 0≦x≦1, 0≦y≦1 and x+y≦1.
  • The semiconductor layer sequence contains, in particular, a p-type phosphide compound semiconductor region, an n-type phosphide compound semiconductor region and an active layer arranged between the p-type phosphide compound semiconductor region and the n-type phosphide compound semiconductor region and serving for emitting electromagnetic radiation.
  • The active layer can be embodied e.g., as a pn junction, as a double heterostructure, as a multiple heterostructure, as a single quantum well structure or multiple quantum well structure. In this case, the designation quantum well structure encompasses any structure in which charge carriers experience a quantization of their energy states as a result of confinement. In particular, the designation quantum well structure does not include any indication about the dimensionality of the quantization. It therefore encompasses, inter alia, quantum wells, quantum wires or quantum dots and any combination of these structures.
  • In the case of the light-emitting diode chip, the n-type semiconductor region faces a radiation exit area of the light-emitting diode chip, and the p-type semiconductor region faces a carrier of the light-emitting diode chip. Preferably, the light-emitting diode chip is a so-called thin-film light-emitting diode chip, wherein a growth substrate used for the growth of the semiconductor layer sequence is detached from the light-emitting diode chip. The original growth substrate can be detached, in particular, from the n-type semiconductor region of the semiconductor layer sequence. At the side of the p-type semiconductor region opposite the original growth substrate, the light-emitting diode chip is preferably connected to the carrier, for example by means of a soldering connection. In this case, the carrier is different than a growth substrate of the semiconductor layers sequence and preferably comprises silicon, molybdenum or germanium. In contrast to conventional LEDs, wherein generally the n-type semiconductor region faces the substrate and the p-type semiconductor region faces the radiation exit area, in the case of the light-emitting diode chip the p-type semiconductor region faces the carrier and the n-type semiconductor region faces the radiation exit area.
  • A current spreading layer having a thickness of less than 500 nm is arranged between the carrier and the p-type semiconductor region, said current spreading layer consisting of one or a plurality of p-doped AlxGa1-xAs layer(s) with 0.5<x≦1.
  • By virtue of the fact that the current spreading layer is arranged between the carrier and the p-type semiconductor region, it is better protected against oxidation and/or the action of moisture than if it adjoined the ambient medium, in particular air, at the radiation exit side of the light-emitting diode chip.
  • It has furthermore been found that a current spreading layer having a thickness of less than 500 nm has lower sensitivity to oxidation and/or moisture than comparatively thick current spreading layers. This is possibly based on the fact that the volume of an AlGaAS layer increases if the layer partly oxidizes. In the case of the current spreading layer only having a thickness of less than 500 nm, this effect is less pronounced than in the case of a thicker layer.
  • Furthermore, the required growth time for the current spreading layer is advantageously reduced by virtue of the small thickness of the current spreading layer of less than 500 nm. Since the growth of the current spreading layer takes place at elevated temperatures, the reduction of the growth time also reduces the diffusion of impurities from the adjacent semiconductor layer sequence into the current spreading layer, for example the diffusion of dopants such as Mg and Zn from the p-type semiconductor region of the semiconductor layer sequence.
  • The small thickness of the current spreading layer of less than 500 nm furthermore advantageously reduces the optical absorption in the current spreading layer. Radiation emitted in the active layer of the semiconductor layer sequence, which radiation is firstly emitted in the direction of the current spreading layer and the carrier, is therefore absorbed in the current spreading layer to a lesser extent than in the case of a significantly thicker current spreading layer. The radiation emitted in the direction of the carrier is preferably reflected by a mirror layer arranged on the carrier in the direction toward a radiation exit side of the light-emitting diode chip.
  • The optical absorption in the current spreading layer is therefore advantageously also comparatively low since the one or the plurality of p-doped AlxGa1-xAs layers forming the current spreading layer have a proportion of aluminum x>0.5. On account of the comparatively large proportion of aluminum, the current spreading layer has a comparatively large electronic band gap which reduces the absorption of the radiation.
  • In one preferred configuration, the current spreading layer has a thickness of less than 300 nm. This further improves the stability of the layer with respect to oxidation and/or action of moisture and reduces the optical absorption.
  • It is particularly advantageous if, for the proportion of aluminum x in the current spreading layer 0.6≦x≦0.8 holds true. In particular, low optical absorption in the current spreading layer can be obtained in this case.
  • The current spreading layer can be an individual layer composed of AlxGa1-xAs or a plurality of partial layers composed of AlxGa1-xAs. For the case where the current spreading layer is composed of a plurality of partial layers, the advantageous configurations of the current spreading layer as described here and hereinafter apply to the totality of the partial layers. In particular, the thickness of a current spreading layer composed of a plurality of partial layers is overall less than 500 nm or particularly preferably even overall less than 300 nm.
  • The current spreading layer advantageously has a dopant concentration of more than 1×1019 cm−3. Particularly preferably, the dopant concentration in the current spreading layer is at least 5×1019 cm−3. A high electrical conductivity in the current spreading layer is advantageously obtained as a result of a high dopant concentration.
  • In one preferred configuration, the current spreading layer comprises C as dopant. It has advantageously been found that high dopant concentrations with good reproducibility can be obtained with C as dopant in AlGaAs layers.
  • In a further preferred configuration, the current spreading layer including its side flanks is provided with an encapsulation layer. The encapsulation layer can contain, in particular, silicon oxide, silicon nitride, a transparent conductive oxide such as, for example, zinc oxide or a metal. In order also to be able to provide the side flanks of the current spreading layer with an encapsulation layer, the current spreading layer can be structured, for example, before the encapsulation layer is applied. During the structuring, by way of example, edge regions of the current spreading layer can be removed, such that an encapsulation layer subsequently applied by means of a coating method also covers the side flanks of the current spreading layer. The encapsulation layer further reduces, in particular, the sensitivity of the current spreading layer toward environmental influences, in particular toward oxidation and/or the action of moisture. It is possible for the encapsulation layer to contain different materials in different partial regions. By way of example, the encapsulation layer can be formed from an electrically insulating material such as silicon oxide or silicon nitride, for example, in partial regions, while it is formed from an electrically conductive material such as zinc oxide, for example, or from a metal in other regions. In this case, the electrically conductive partial regions of the encapsulation layer, serve in particular, for impressing current into the current spreading layer.
  • In a further preferred configuration, the current spreading layer has oblique side flanks, which are inclined by an angle of between 20° and 70° inclusive with respect to the layer plane of the current spreading layer. The coupling-out of radiation from the optoelectronic component can be improved in this way. In particular, the oblique side flanks of the current spreading layer can function as microprisms by which radiation emitted in the active layer, said radiation being emitted in the direction of the carrier, is reflected toward the radiation exit side of the light-emitting diode chip. It is possible for the oblique side flanks to extend right into the phosphide compound semiconductor layer sequence, such that one or a plurality of layers of the semiconductor layer sequence also have oblique side flanks.
  • In a further advantageous configuration, at least one trench is formed in the current spreading layer. The at least one trench is preferably filled with silicon nitride, silicon oxide, zinc oxide or a metal. In the region of the trench of the current spreading layer, the filling material directly adjoins the p-type semiconductor region. Through the trench it is possible to define, in a targeted manner, a current path through the semiconductor layer sequence. It is advantageously also possible for the at least one trench to extend right into the p-type phosphide compound semiconductor region.
  • In a further advantageous configuration, at least one layer composed of InxGayAl1-x-yAs where 0≦x≦1, 0≦y≦1 and x+y≦1 adjoins the current spreading layer, and has a smaller band gap and a lower dopant concentration than the current spreading layer. At the interface between the current spreading layer and the layer having the smaller band gap and lower dopant concentration, in this case a bending of the band edges of the conduction band and of the valence band respectively occurs, which leads to the formation of a two-dimensional hole gas having a high conductivity. In this way, regions having high charge carrier concentration and charge carrier mobility can be produced in a targeted manner.
  • It is possible for the at least one AlGaAs layer in the current spreading layer to contain a small proportion of one or a plurality of further elements. The proportion of the one or of the plurality of further elements in the current spreading layer is less than 10% in this case. The one or the plurality of further elements can be dopants, or small amounts of a further material of the third or fifth main group of the periodic system.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The invention is explained in greater detail below on the basis of exemplary embodiments in connection with FIGS. 1 to 5.
  • FIG. 1 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a first exemplary embodiment;
  • FIG. 2 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a second exemplary embodiment;
  • FIG. 3 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a third exemplary embodiment;
  • FIG. 4 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a fourth exemplary embodiment; and
  • FIG. 5 shows a schematic illustration of a cross section through a light-emitting diode chip in accordance with a fifth exemplary embodiment.
    •
  • Identical or identically acting elements are provided with the same reference signs in the figures. The sizes of the individual elements and the size relationships of the elements among one anther should not be regarded as true to scale.
    • DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
  • The thin-film light-emitting diode chip illustrated in FIG. 1 contains a semiconductor layer sequence 5 comprising a p-type semiconductor region 2 and an n-type semiconductor region 4. An active layer 3 is arranged between the p-type semiconductor region 2 and the n-type semiconductor region 4. The active layer 3 preferably has a single or multiple quantum well structure.
  • The semiconductor layer sequence 5 is based on a phosphide compound semiconductor, that is to say that the semiconductor layers contained in the semiconductor layer sequence 5 comprise, in particular, InxGayAl1-x-yP where 0≦x≦1, 0≦y≦1 and x+y≦1. In particular, the p-type semiconductor region 2, the active layer 3 and the n-type semiconductor region are formed from phosphide compound semiconductor materials.
  • The light-emitting diode chip is a so-called thin-film LED, wherein a growth substrate used for the growth of the semiconductor layer sequence 5 has been detached from the semiconductor layer sequence 5. In particular, the growth substrate can be detached from the n-type semiconductor region 4, which now has the radiation exit area 6 of the light-emitting diode chip. At a side opposite the original growth substrate and the radiation exit area 6, the light-emitting diode chip is connected to a carrier 7, which preferably comprises silicon, germanium or molybdenum. In the case of the thin-film light-emitting diode chip, therefore the n-type semiconductor region 4 faces the radiation exit area 6 and the p-type semiconductor region 2 faces the carrier 7.
  • A current spreading layer 1 is arranged between the carrier 7 and the p-type phosphide compound semiconductor region 2. The current spreading layer 1 is a p-doped AlxGa1-xAs layer where 0.5<x≦1, which has a thickness of less than 500 nm.
  • Preferably, the thickness of the current spreading layer 1 is even only less than 300 nm. For the proportion of aluminum x in the current spreading layer 1, 0.6≦x≦0.8 preferably holds true.
  • The current spreading layer 1 adjoins an electrical contact 9 at least in partial regions at a side facing the carrier 7. At least one further electrical contact 9 of the light-emitting diode chip is arranged, for example, on the radiation exit side 6 of the light-emitting diode chip, said radiation exit side being opposite the carrier. The current spreading layer 1 preferably has a dopant concentration of more than 1×1019 cm−3 and particularly preferably of more than 5×1019 cm−3. A high transverse conductivity of the current spreading layer 1 is obtained in this way, such that a current flows through the semiconductor layer sequence 5 comparatively homogeneously even when the rear-side contact 9 is applied, for example, only to a small central region of the current spreading layer 1.
  • On account of its small thickness of less than 500 nm or preferably of less than 300 nm and on account of the high aluminum content of more than 0.5, the current spreading layer 1 has advantageously low optical absorption. Furthermore, it has been found that such a thin current spreading layer 1 is less sensitive to oxidation or the action of moisture than comparatively thick conventional current spreading layers that typically have a thickness of 1 um or more. Despite the small thickness, good current spreading is obtained with the current spreading layer 1, wherein it is advantageous if the current spreading layer 1 has a dopant concentration of at least 1×1019 cm−3 and particularly preferably of at least 5×1019 cm−3.
  • It is furthermore advantageous that the current spreading layer 1 adjoining the p-type semiconductor region 2 is arranged between the carrier 7 and the p-type semiconductor region 2 since with this arrangement it is better protected against external influences such as oxidation or moisture than if it adjoined the ambient medium at the surface of the light-emitting diode chip.
  • It is possible for the current spreading layer 1 to be composed of a plurality of partial layers (not illustrated) made of AlxGa1-xAs where in each case 0.5<x≦1, wherein the partial layers can differ from one another for example in terms of their dopant concentration and/or in terms of their aluminum content. In this case, in the context of this application, the totality of the partial layers is regarded as the current spreading layer 1, such that, in particular, the total thickness of all the partial layers is less than 500 nm and preferably less than 300 nm. It is also conceivable for the current spreading layer 1 or the partial layers of the current spreading layer to have small amounts of additional materials, the proportion of which, however, overall is less than 10%.
  • In order to protect the current spreading layer 1 even better against external influences, said current spreading layer preferably including its side flanks 11 is provided with an encapsulation layer 8. The encapsulation layer 8 can comprise, in particular, a transparent dielectric material such as, for example, silicon nitride or silicon oxide. Alternatively, however, it is also possible for the encapsulation layer 8 to comprise a transparent conductive oxide such as, for example, zinc oxide or a metal. Particularly in the case of an encapsulation layer 8 composed of a dielectric material, the electrical contact 9 for the current spreading layer 1 can be arranged in a cutout of the encapsulation layer 8.
  • A layer sequence 10 composed of a metal or a metal alloy is arranged between the encapsulation layer 8, the electrical contact layer 9 and the carrier 7. The metallic layers 10 can contain, for example, a minor layer for reflecting the radiation emitted from the active layer 3 in the direction of the carrier 7. Furthermore, the metallic layers 10 can also comprise a solder layer for connecting the light-emitting diode chip to the carrier 7.
  • The exemplary embodiment of a light-emitting diode chip as illustrated in FIG. 2 differs from the exemplary embodiment in FIG. 1 in that the current spreading layer 1 has oblique side flanks 12. The oblique side flanks 12 preferably form an angle of between 20° and 70° inclusive with the layer plane of the current spreading layer 1. It has been found that the coupling-out of radiation from the light-emitting diode chip can be improved by means of the oblique side flanks 12 of the current spreading layer 1. On account of the difference in refractive index between the current spreading layer 1 and the encapsulation layer 8, the oblique side flanks 12 act as reflectors that can reflect radiation in the direction toward the radiation exit area 6. In particular, it is possible for the opposite oblique side flanks 12 of the current spreading layer 1 to form a microprism. It is also possible for the oblique side flanks 12 to extend right into the semiconductor layer sequence 5 (not illustrated).
  • With regard to the further advantageous configurations, the exemplary embodiment illustrated in FIG. 2 corresponds to the first exemplary embodiment.
  • The exemplary embodiment of a light-emitting diode chip as illustrated in FIG. 3 differs from the exemplary embodiment illustrated in FIG. 1 in that the metallic layer sequence 10 in the region of the side flanks of the light-emitting diode chip reaches as far as the p-type semiconductor region 2. Consequently, the current spreading layer 1 including its side flanks 11 is enclosed by the encapsulation layer 8, and the encapsulation layer 8 is enclosed by the metallic layer sequence 10. Particularly good resistance of the current spreading layer 1 to oxidation or the action of moisture is obtained in this way.
  • The exemplary embodiment illustrated in FIG. 3 furthermore differs from the exemplary embodiment illustrated in FIG. 1 in that an InxGayAl1-x-yAs layer 14 where 0≦x≦1, 0≦y≦1 and x+y≦1 adjoins the current spreading layer 1, and has a lower dopant concentration and a smaller band gap than the current spreading layer 1. The layer 14 is preferably arranged between the current spreading layer 1 and the p-type semiconductor region 2. At the interface with the more highly doped current spreading layer 1 the layer 14 forms a potential well in which free charge carriers in the form of holes accumulate. The holes form a so-called two-dimensional hole gas in the layer 14. In this way, a particularly high transverse conductivity is obtained in the layer 14.
  • In the case of the exemplary embodiment of a light-emitting diode chip as illustrated in FIG. 4, two trenches 13 are formed in the current spreading layer 1, into which the encapsulation layer 8 projects. That region of the current spreading layer 1 which is arranged between the trenches 13 is electrically connected by means of the electrical contact 9 and the metallic layer sequence 10. By contrast, the edge regions 1 a, 1 b of the current spreading layer 1 are not electrically connected. Generation of radiation in the regions of the semiconductor chip which are arranged below the contacts 9 arranged in the edge regions on the radiation exit area of the light-emitting diode chip is reduced in this way.
  • FIG. 5 illustrates a further exemplary embodiment of a light-emitting diode chip wherein two trenches 13 are formed in the current spreading layer 1. In the trenches, the metallic layer sequence 10 extends right into the p-type semiconductor region 2. The metallic layer sequence 10 is insulated from the current spreading layer 1 outside the region of the contact 9 by the encapsulation layer 8.
  • The invention is not restricted by the description on the basis of the exemplary embodiments. Rather, the invention encompasses any novel feature and also any combination of features, which in particular includes any combination of features in the patent claims, even if this feature or this combination itself is not explicitly specified in the patent claims or exemplary embodiments.

Claims (19)

1-15. (canceled)
16. A light-emitting diode chip comprising a semiconductor layer sequence comprising a phosphide compound semiconductor material, wherein the semiconductor layer sequence comprises:
a p-type semiconductor region, wherein the p-type semiconductor region faces a carrier of the light-emitting diode chip;
an n-type semiconductor region, wherein the n-type semiconductor region faces a radiation exit area of the light-emitting diode chip;
an active layer arranged between the p-type semiconductor region and the n-type semiconductor region, the active layer configured to emit electromagnetic radiation; and
a current spreading layer having a thickness of less than 500 nm arranged between the carrier and the p-type semiconductor region, the current spreading layer comprising a p-doped AlxGa1-xAs layer, where 0.5<x≦1.
17. The light-emitting diode chip according to claim 16, wherein the current spreading layer has a thickness of less than 300 nm.
18. The light-emitting diode chip according to claim 16, wherein 0.6≦x≦0.8.
19. The light-emitting diode chip according to claim 16, wherein the current spreading layer comprises a plurality of p-doped AlxGa1-xAs layers.
20. The light-emitting diode chip according to claim 16, wherein the current spreading layer has a dopant concentration of more than 1*1019 cm−3.
21. The light-emitting diode chip according to claim 16, wherein the current spreading layer has a dopant concentration of at least 5*1019 cm−3.
22. The light-emitting diode chip according to claim 16, wherein the current spreading layer is doped with carbon.
23. The light-emitting diode chip according to claim 16, further comprising an encapsulation layer overlying the current spreading layer including side flanks of the current spreading layer.
24. The light-emitting diode chip according to claim 23, wherein the encapsulation layer contains silicon oxide, silicon nitride, zinc oxide or a metal.
25. The light-emitting diode chip according to claim 16, wherein the current spreading layer has oblique side flanks that are inclined at an angle of between 20° and 70° inclusive with respect to a layer plane of the current spreading layer.
26. The light-emitting diode chip according to claim 16, wherein a trench is formed in the current spreading layer.
27. The light-emitting diode chip according to claim 26, wherein the trench is filled with silicon nitride, silicon oxide, zinc oxide or a metal.
28. The light-emitting diode chip according to claim 26, wherein the trench extends into the p-type semiconductor region.
29. The light-emitting diode chip according to claim 16, further comprising a further layer composed of InxGayAl1-x-yAs, where 0≦x≦1, 0≦y≦1 and x+y≦1, adjoining the current spreading layer, the further layer having a smaller band gap and a lower dopant concentration than the current spreading layer.
30. The light-emitting diode chip according to claim 16, wherein a growth substrate is detached from the semiconductor layer sequence and the carrier is different than a growth substrate of the semiconductor layer sequence.
31. The light-emitting diode chip according to claim 30, wherein the carrier comprises silicon, molybdenum or germanium.
32. A light-emitting diode chip comprising a semiconductor layer sequence comprising a phosphide compound semiconductor material, wherein the semiconductor layer sequence comprises:
a p-type semiconductor region, wherein the p-type semiconductor region faces a carrier of the light-emitting diode chip;
an n-type semiconductor region, wherein the n-type semiconductor region faces a radiation exit area of the light-emitting diode chip;
an active layer arranged between the p-type semiconductor region and the n-type semiconductor region, the active layer configured to emit electromagnetic radiation;
a current spreading layer having a thickness of less than 500 nm arranged between the carrier and the p-type semiconductor region, the current spreading layer having a p-doped AlxGa1-xAs layer with 0.5<x≦1; and
a further layer composed of InxGayAl1-x-yAs, where 0≦x≦1, 0≦y≦1 and x+y≦1, adjoining the current spreading layer, the further layer having a smaller band gap and a lower dopant concentration than the current spreading layer.
33. A light-emitting diode chip comprising a semiconductor layer sequence comprising a phosphide compound semiconductor material, wherein the semiconductor layer sequence comprises:
a p-type semiconductor region, wherein the p-type semiconductor region faces a carrier of the light-emitting diode chip;
an n-type semiconductor region, wherein the n-type semiconductor region faces a radiation exit area of the light-emitting diode chip;
an active layer arranged between the p-type semiconductor region and the n-type semiconductor region, the active layer configured to emit electromagnetic radiation; and
a current spreading layer having a thickness of less than 500 nm arranged between the carrier and the p-type semiconductor region, the current spreading layer having one or a plurality of p-doped AlxGa1-xAs layers with 0.5<x≦1, wherein the current spreading layer has oblique side flanks, that are inclined at an angle of between 20° and 70° inclusive with respect to a layer plane of the current spreading layer.
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CN105206731A (en) 2015-12-30
EP2559076A1 (en) 2013-02-20
CN102834937A (en) 2012-12-19
DE102010014667A1 (en) 2011-10-13
JP6124973B2 (en) 2017-05-10
JP2016048785A (en) 2016-04-07
EP3131127A1 (en) 2017-02-15
EP3131127B1 (en) 2018-01-31
CN102834937B (en) 2015-08-26
JP2013524547A (en) 2013-06-17
KR20130060189A (en) 2013-06-07
CN105206731B (en) 2018-01-19
WO2011128277A1 (en) 2011-10-20
EP2559076B1 (en) 2016-09-21
JP5943904B2 (en) 2016-07-05
US20150357516A1 (en) 2015-12-10

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