WO2015144023A1 - 基于lao衬底的非极性蓝光led外延片及其制备方法 - Google Patents
基于lao衬底的非极性蓝光led外延片及其制备方法 Download PDFInfo
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- WO2015144023A1 WO2015144023A1 PCT/CN2015/074828 CN2015074828W WO2015144023A1 WO 2015144023 A1 WO2015144023 A1 WO 2015144023A1 CN 2015074828 W CN2015074828 W CN 2015074828W WO 2015144023 A1 WO2015144023 A1 WO 2015144023A1
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- 239000000758 substrate Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 229910002704 AlGaN Inorganic materials 0.000 claims abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 230000004888 barrier function Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 39
- 230000000903 blocking effect Effects 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 11
- 239000010409 thin film Substances 0.000 description 7
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 6
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- 238000001194 electroluminescence spectrum Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005699 Stark effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- BDKUZSIDPZSPNX-UHFFFAOYSA-N aluminum;bismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Bi+3] BDKUZSIDPZSPNX-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005701 quantum confined stark effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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Definitions
- the invention relates to an LED epitaxial wafer and a preparation method thereof, in particular to a non-polar blue LED epitaxial wafer based on a LAO substrate and a preparation method thereof.
- the LED blue epitaxial wafer substrate is mainly sapphire.
- sapphire substrates There are two serious problems with LED technology based on sapphire substrates.
- the mismatch rate of sapphire and GaN lattice is as high as 17%.
- Such a high lattice mismatch makes the LED epitaxial wafer on sapphire have a high defect density, which greatly affects the luminous efficiency of the LED chip.
- sapphire substrates are very expensive, making nitride LEDs costly to produce.
- GaN-based LEDs have polarity.
- the most ideal material for manufacturing high-efficiency LED devices is GaN.
- GaN is a close-packed hexagonal crystal structure, and its crystal plane is divided into a polar plane c-plane [(0001) plane] and a non-polar plane a-plane [(11-20) plane] and an m-plane [(1-100) plane] .
- Currently, GaN-based LEDs are mostly constructed based on the polar faces of GaN.
- the centroids of the Ga atom set and the N atom set do not coincide, thereby forming an electric dipole, generating a spontaneous polarization field and a piezoelectric polarization field, thereby causing a quantum bound Stark effect (Quantum-confined) Starker Effect (QCSE), which separates electrons and holes, reduces the radiation recombination efficiency of carriers, and ultimately affects the luminous efficiency of LEDs and causes instability of LED emission wavelength.
- QSE quantum bound Stark effect
- the technical problem to be solved by the present invention is to provide a non-polar blue LED epitaxial wafer based on a LAO substrate and a preparation method thereof, which have the advantages of low defect density, good crystal quality, good luminescence performance, and low preparation cost.
- the technical solution adopted by the present invention to solve the above technical problem is to provide a non-polar blue LED epitaxial wafer based on a LAO substrate, comprising a substrate, wherein the substrate is a LAO substrate on the LAO substrate.
- a buffer layer, a first undoped layer, a first doped layer, a quantum well layer, an electron blocking layer, and a second doped layer are sequentially disposed.
- the above-mentioned LAO substrate-based non-polar blue LED epitaxial wafer wherein the buffer layer is a non-polar m-plane GaN buffer layer, and the first undoped layer is a non-polar non-doped u-GaN layer
- the first doped layer is non- a polar n-type doped GaN thin film, the quantum well layer being a non-polar InGaN/GaN quantum well layer, the electron blocking layer being a non-polar m-plane AlGaN electron blocking layer, and the second doped layer being non- Polar p-type doped GaN film.
- the present invention provides a method for preparing a non-polar blue LED epitaxial wafer based on a LAO substrate, which comprises the following steps: a) using a LAO substrate, selecting a crystal orientation, and performing surface cleaning on the LAO substrate. Processing; b) annealing the LAO substrate and forming an AlN seed layer on the surface of the LAO substrate; c) sequentially forming a non-polar m-plane GaN buffer layer by chemical vapor deposition of a metal organic compound on the LAO substrate, A non-polar undoped u-GaN layer, a non-polar n-type doped GaN thin film, a non-polar InGaN/GaN quantum well, a non-polar m-plane AlGaN electron blocking layer, and a non-polar p-type doped GaN thin film.
- step b) comprises the following steps: baking the LAO substrate at a high temperature of 900 to 1200 ° C for 1 to 4 hours, and then air cooling to room temperature Then, it is insulated by N2 plasma for 30 to 80 minutes, and an AlN seed layer is formed on the surface of the LAO substrate by radio frequency plasma enhanced organometallic chemical vapor deposition.
- the flow rate of the N plasma is 40 to 90 sccm, and plasma nitrogen is generated.
- the RF power is 200 to 500W.
- the above method for preparing a non-polar blue LED epitaxial wafer based on a LAO substrate, wherein the forming process of the non-polar m-plane GaN buffer layer in the step c) is as follows: reducing the temperature of the LAO substrate to 400-800 ° C
- the TMGa and N plasma are introduced to control the reaction chamber pressure to be 400-700 torr, the N plasma flow rate is 40 to 90 sccm, the plasma nitrogen generating RF power is 200 to 700 W, and the V/III ratio is 800 to 1200.
- the method for preparing a non-polar blue LED epitaxial wafer based on a LAO substrate, wherein the forming process of the non-polar non-doped u-GaN layer in the step c) is as follows: controlling the temperature of the LAO substrate to be 1000-1500 °C, TMGa is introduced, the pressure in the reaction chamber is controlled to 400 torr, and the V/III ratio is 180.
- the method for preparing a non-polar blue LED epitaxial wafer based on the LAO substrate, wherein the forming process of the non-polar n-type doped GaN film in the step c) is as follows: controlling the temperature of the LAO substrate to be 1000-1300 ° C , pass TMGa and SiH4, keep the flow rate of SiH4 60-100sccm, control the reaction chamber pressure to 240torr, V/III ratio is 160, doping electron concentration is 1.0 ⁇ 10 17 ⁇ 5.3 ⁇ 10 19 cm-3;
- Forming a barrier layer controlling the temperature of the LAO substrate to be 750-950 ° C, closing H2, introducing TEGa and ammonia gas, controlling the pressure of the reaction chamber to 200 torr, the ratio of V/III to 986, and the thickness of 10 to 15 nm;
- a well layer is formed, the temperature of the LAO substrate is controlled to be 750 to 950 ° C, H 2 is turned off, TEGa, TMIn and ammonia gas are introduced, and the pressure in the reaction chamber is controlled to 200 torr, the ratio of V/III is 1439, and the thickness is 2 to 4 nm.
- the above-mentioned method for preparing a non-polar blue LED epitaxial wafer based on a LAO substrate, wherein the formation process of the non-polar m-plane A1 GaN electron blocking layer in the step c) is as follows: raising the temperature of the LAO substrate to 900-1050 °C, TMGa and ammonia gas were introduced, and the pressure in the reaction chamber was controlled to 200 torr, and the V/III ratio was 986.
- the above method for preparing a non-polar blue LED epitaxial wafer based on a LAO substrate, wherein the forming process of the non-polar p-type doped GaN film in the step c) is as follows: controlling the temperature of the LAO substrate to be 900 to 1100 ° C , pass TMGa, CP2Mg and ammonia gas, keep the flow rate of CP2Mg to 250 ⁇ 450sccm, control the reaction chamber pressure to 200torr, V/III ratio is 1000 ⁇ 1250, doping hole concentration 1.0 ⁇ 10 16 ⁇ 2.2 ⁇ 10 18 cm -3.
- the present invention has the following beneficial effects: the LAO substrate-based non-polar blue LED epitaxial wafer and the preparation method thereof are provided by using the LAO substrate, and the buffer layer is sequentially disposed on the LAO substrate.
- the first undoped layer, the first doped layer, the quantum well layer, the electron blocking layer and the second doped layer have the advantages of low defect density, good crystal quality, good luminescence performance, and low preparation cost.
- FIG. 1 is a schematic structural view of a non-polar blue LED epitaxial wafer based on a LAO substrate according to the present invention
- FIG. 2 is a schematic structural view of a device for preparing a non-polar blue LED epitaxial wafer for a LAO substrate according to the present invention
- FIG. 3 is a schematic diagram of a preparation process of a non-polar blue LED epitaxial wafer based on a LAO substrate according to the present invention
- FIG. 4 is an XRD test chart of a non-polar blue LED epitaxial wafer grown on a (001) surface of a LAO substrate according to the present invention
- FIG. 5 is a PL spectrum test chart of a non-polar m-plane blue LED epitaxial wafer grown on a LAO substrate at a temperature of room temperature;
- Figure 6 is a graph showing the EL spectrum of a non-polar m-plane blue LED epitaxial wafer grown on a LAO substrate at room temperature.
- FIG. 1 is a schematic structural view of a non-polar blue LED epitaxial wafer based on a LAO substrate according to the present invention.
- a non-polar blue LED epitaxial wafer based on a LAO substrate includes a substrate, wherein the substrate is a LAO substrate, and a buffer layer is disposed on the LAO substrate in turn.
- the non-polar blue LED epitaxial wafer grown on the LAO substrate of the present invention which is also called a bismuth aluminum oxide substrate, and is composed of La, Al, O elements.
- the molecular formula is LaAlxOy. As shown in FIG.
- the non-polar blue LED epitaxial wafer provided by the present invention comprises a LAO substrate 10 arranged in order from bottom to top, a non-polar m-plane GaN buffer layer 11, and a non-polar non-doped u-GaN layer 12. a non-polar n-type doped GaN thin film 13, a non-polar InGaN/GaN quantum well layer 14, a non-polar m-plane AlGaN electron blocking layer 15, and a non-polar p-type doped GaN thin film 16.
- FIG. 2 is a schematic view showing the structure of a device for preparing a non-polar blue LED epitaxial wafer for a LAO substrate according to the present invention.
- MFC is a flow controller that controls the flow of gas to meet growing needs.
- FIG. 3 is a schematic diagram of a preparation process of a non-polar blue LED epitaxial wafer based on a LAO substrate according to the present invention.
- a method for preparing a non-polar blue LED epitaxial wafer grown on a LAO substrate of the present invention specifically includes the following steps:
- Step S1 using a LAO substrate, selecting a crystal orientation, and performing surface cleaning treatment on the LAO substrate;
- Step S2 annealing the LAO substrate, and forming an AlN seed layer on the surface of the LAO substrate;
- Step S3 sequentially forming a non-polar m-plane GaN buffer layer, a non-polar non-doped u-GaN layer, a non-polar n-type doped GaN film, and a non-polar layer on the LAO substrate by chemical vapor deposition of a metal organic compound.
- Annealing the substrate baking the substrate at 900-1200 ° C for 1 to 4 hours, then air cooling to room temperature, then passing through N2 plasma for 30 to 80 minutes to form AlN seed crystal on the surface of the substrate.
- the layer provides a template for the growth of the GaN film, the flow rate of the N plasma is 40 to 90 sccm, and the radio frequency power for generating the plasma nitrogen is 200 to 500 W;
- the non-polar m-plane GaN buffer layer is grown by radio frequency plasma (RF) enhanced organic metal chemical vapor deposition (MOCVD) under the following conditions: the substrate temperature is lowered to 400-800 ° C, and TMGa and N are introduced.
- RF radio frequency plasma
- MOCVD organic metal chemical vapor deposition
- Plasma The reaction chamber pressure is 400-700 torr
- the flow rate of the N plasma is 40-90 sccm
- the radio frequency power for generating plasma nitrogen is 200-700 W
- the V/III ratio is 800-1200;
- the non-polar undoped u-GaN layer is grown by the MOCVD process under the following conditions: the substrate temperature is 1000-1500 ° C, the TMGa is introduced, the reaction chamber pressure is 400 torr, and the V/III ratio is 180;
- the non-polar n-type doped GaN film is grown by MOCVD process under the following conditions: substrate temperature is 1000-1300 °C, TMGa and SiH4 are introduced, the flow rate of SiH4 is 60-100 sccm, and the pressure of the reaction chamber is 240 torr. , the V/III ratio is 160; the doping electron concentration is 1.0 ⁇ 10 17 to 5.3 ⁇ 10 19 cm-3;
- the non-polar InGaN/GaN quantum well is grown by MOCVD process.
- the process conditions are as follows: the barrier layer is formed, the substrate temperature is 750-950 ° C, H 2 is turned off, TEGa and ammonia gas are introduced, and the reaction chamber pressure is 200 torr, V.
- the ratio of /III is 986, the thickness is 10-15 nm; the well layer is formed, the substrate temperature is 750-950 ° C, H2 is turned off, TEGa, TMIn and ammonia gas are introduced, the reaction chamber pressure is 200 torr, and the V/III ratio is 1439. Thickness is 2 to 4 nm;
- the non-polar m-plane AlGaN electron blocking layer was grown by MOCVD process under the following conditions: the substrate temperature was raised to 900-1050 ° C, TMGa and ammonia gas were introduced, the reaction chamber pressure was 200 torr, and the V/III ratio was 986. ;
- the non-polar p-type doped GaN film is grown by MOCVD process under the following conditions: substrate temperature is 900-1100 °C, TMGa, CP2Mg and ammonia gas are introduced, and the flow rate of CP2Mg is maintained at 250-450 sccm.
- the pressure is 200 torr, the V/III ratio is 1000 to 1250, and the doping hole concentration is 1.0 ⁇ 10 16 -2.2 ⁇ 10 18 cm-3.
- FIG. 4 is an XRD test chart of a non-polar blue LED epitaxial wafer grown on a (001) surface of a LAO substrate of the present invention.
- the half-width (FWHM) value of the LED epitaxial wafer x-ray back-swing curve is obtained by the present invention, and the half-width (FWHM) value thereof is less than 0.1°, indicating that the non-polar blue LED epitaxial prepared by the present invention is epitaxial.
- the film has very good properties both in defect density and in crystalline quality.
- FIG. 5 is a PL spectrum test chart of a non-polar m-plane blue LED epitaxial wafer grown on a LAO substrate at a temperature of room temperature.
- the PL spectrum test at a temperature of 293 K of the present invention gave an emission peak wavelength of 460 nm and a half width of 23 nm. This indicates that the non-polar GaN film prepared by the present invention has very good optical properties.
- Figure 6 is a graph showing the EL spectrum of a non-polar m-plane blue LED epitaxial wafer grown on a LAO substrate at room temperature.
- the LAO substrate-based non-polar blue LED epitaxial wafer and the preparation method thereof are provided by using a LAO substrate and sequentially providing a non-polar m-plane GaN buffer layer on the LAO substrate.
- the invention has the advantages of simple growth process and low preparation cost, and the prepared non-polar blue LED epitaxial wafer has low defect density, good crystal quality, and good electrical and optical performance.
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Abstract
Description
Claims (10)
- 一种基于LAO衬底的非极性蓝光LED外延片,包括衬底,其特征在于,所述衬底为LAO衬底,所述LAO衬底上依次设置有缓冲层、第一非掺杂层、第一掺杂层、量子阱层、电子阻挡层和第二掺杂层。
- 如权利要求1所述的基于LAO衬底的非极性蓝光LED外延片,其特征在于,所述缓冲层为非极性m面GaN缓冲层,所述第一非掺杂层为非极性非掺杂u-GaN层,所述第一掺杂层为非极性n型掺杂GaN薄膜,所述量子阱层为非极性InGaN/GaN量子阱层,所述电子阻挡层为非极性m面AlGaN电子阻挡层,所述第二掺杂层为非极性p型掺杂GaN薄膜。
- 一种如权利要求2所述的基于LAO衬底的非极性蓝光LED外延片的制备方法,其特征在于,包括如下步骤:a)采用LAO衬底,选取晶体取向,并对LAO衬底进行表面清洁处理;b)对LAO衬底进行退火处理,并在LAO衬底表面形成AlN籽晶层;c)在LAO衬底上采用金属有机化合物化学气相淀积依次形成非极性m面GaN缓冲层、非极性非掺杂u-GaN层、非极性n型掺杂GaN薄膜、非极性InGaN/GaN量子阱、非极性m面AlGaN电子阻挡层和非极性p型掺杂GaN薄膜。
- 如权利要求3所述的基于LAO衬底的非极性蓝光LED外延片的制备方法,其特征在于,所述步骤b)包括如下过程:将LAO衬底在900~1200℃下高温烘烤1~4小时后空冷至室温,然后通入N2等离子体保温30~80分钟,在LAO衬底表面采用射频等离子体增强有机金属化学气相淀积形成AlN籽晶层,N等离子体的流量为40~90sccm,产生等离子体氮的射频功率为200~500W。
- 如权利要求3所述的基于LAO衬底的非极性蓝光LED外延片的制备方法,其特征在于,所述步骤c)中非极性m面GaN缓冲层的形成过程如下:将LAO衬底温度降为400~800℃,通入TMGa与N等离子体,控制反应室压力为400~700torr、N等离子体的流量为40~90sccm,产生等离子体氮的射频功率为200~700W,V/III比为800~1200。
- 如权利要求3所述的基于LAO衬底的非极性蓝光LED外延片的制备方法,其特征在于,所述步骤c)中非极性非掺杂u-GaN层的形成过程如下:控制LAO衬底 温度为1000~1500℃,通入TMGa,控制反应室压力为400torr,V/III比为180。
- 如权利要求3所述的基于LAO衬底的非极性蓝光LED外延片的制备方法,其特征在于,所述步骤c)中非极性n型掺杂GaN薄膜的形成过程如下:控制LAO衬底温度为1000~1300℃,通入TMGa和SiH4,保持SiH4的流量为60~100sccm,控制反应室压力为240torr,V/III比为160,掺杂电子浓度为1.0×1017~5.3×1019cm-3;
- 如权利要求3所述的基于LAO衬底的非极性蓝光LED外延片的制备方法,其特征在于,所述步骤c)中非极性InGaN/GaN量子阱的形成过程如下:形成垒层:控制LAO衬底温度为750~950℃,关闭H2,通入TEGa与氨气,控制反应室压力为200torr,V/III比为986,厚度为10~15nm;形成阱层,控制LAO衬底温度为750~950℃,关闭H2,通入TEGa、TMIn与氨气,控制反应室压力为200torr,V/III比为1439,厚度为2~4nm。
- 如权利要求3所述的基于LAO衬底的非极性蓝光LED外延片的制备方法,其特征在于,所述步骤c)中非极性m面AlGaN电子阻挡层的形成过程如下:将LAO衬底温度升至900~1050℃,通入TMGa与氨气,控制反应室压力为200torr,V/III比为986。
- 如权利要求3所述的基于LAO衬底的非极性蓝光LED外延片的制备方法,其特征在于,所述步骤c)中非极性p型掺杂GaN薄膜的形成过程如下:控制LAO衬底温度为900~1100℃,通入TMGa、CP2Mg与氨气,保持CP2Mg的流量为250~450sccm,控制反应室压力为200torr,V/III比为1000~1250,掺杂空穴浓度1.0×1016~2.2×1018cm-3。
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CA2942999A CA2942999C (en) | 2014-03-24 | 2015-03-23 | Non-polar blue led epitaxial wafer based on lao substrate and preparation method thereof |
JP2016574326A JP6326154B2 (ja) | 2014-03-24 | 2015-03-23 | LaAlxOy基板に基づく非極性青色LEDエピタキシャルウェハの製造方法 |
RU2016138668A RU2643176C1 (ru) | 2014-03-24 | 2015-03-23 | Неполярная светодиодная эпитаксиальная пластина синего свечения на подложке из lao и способ ее получения |
PL15769396T PL3107128T3 (pl) | 2014-03-24 | 2015-03-23 | Sposób wytwarzania niepolarnej płytki epitaksjalnej niebieskiej led bazującej na podłożu lao |
US15/128,639 US9978908B2 (en) | 2014-03-24 | 2015-03-23 | Non-polar blue light LED epitaxial wafer based on LAO substrate and preparation method thereof |
KR1020167026454A KR20160130411A (ko) | 2014-03-24 | 2015-03-23 | Lao 기판에 기반한 무극성 블루 led 에피 웨이퍼 및 그 제조 방법 |
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CA2942999C (en) | 2019-01-15 |
JP6326154B2 (ja) | 2018-05-16 |
EP3107128B1 (en) | 2018-04-18 |
US9978908B2 (en) | 2018-05-22 |
CN104600162A (zh) | 2015-05-06 |
PL3107128T3 (pl) | 2018-09-28 |
KR20160130411A (ko) | 2016-11-11 |
CA2942999A1 (en) | 2015-10-01 |
CN104600162B (zh) | 2016-01-27 |
US20170110627A1 (en) | 2017-04-20 |
JP2017513236A (ja) | 2017-05-25 |
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