WO2020022684A1 - 아연 산화물층을 구비하는 발광 다이오드 및 그것을 제조하는 방법 - Google Patents
아연 산화물층을 구비하는 발광 다이오드 및 그것을 제조하는 방법 Download PDFInfo
- Publication number
- WO2020022684A1 WO2020022684A1 PCT/KR2019/008738 KR2019008738W WO2020022684A1 WO 2020022684 A1 WO2020022684 A1 WO 2020022684A1 KR 2019008738 W KR2019008738 W KR 2019008738W WO 2020022684 A1 WO2020022684 A1 WO 2020022684A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- zno
- light emitting
- conductive semiconductor
- semiconductor layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/83—Electrodes
- H10H20/832—Electrodes characterised by their material
- H10H20/833—Transparent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/01—Manufacture or treatment
- H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
- H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
- H10H20/0133—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials with a substrate not being Group III-V materials
- H10H20/01335—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials with a substrate not being Group III-V materials the light-emitting regions comprising nitride materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/01—Manufacture or treatment
- H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
- H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
- H10H20/0137—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials the light-emitting regions comprising nitride materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/01—Manufacture or treatment
- H10H20/032—Manufacture or treatment of electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/81—Bodies
- H10H20/819—Bodies characterised by their shape, e.g. curved or truncated substrates
- H10H20/82—Roughened surfaces, e.g. at the interface between epitaxial layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/83—Electrodes
- H10H20/831—Electrodes characterised by their shape
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/84—Coatings, e.g. passivation layers or antireflective coatings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H29/00—Integrated devices, or assemblies of multiple devices, comprising at least one light-emitting semiconductor element covered by group H10H20/00
- H10H29/10—Integrated devices comprising at least one light-emitting semiconductor component covered by group H10H20/00
- H10H29/14—Integrated devices comprising at least one light-emitting semiconductor component covered by group H10H20/00 comprising multiple light-emitting semiconductor components
- H10H29/142—Two-dimensional arrangements, e.g. asymmetric LED layout
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/81—Bodies
- H10H20/822—Materials of the light-emitting regions
- H10H20/824—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP
- H10H20/825—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP containing nitrogen, e.g. GaN
Definitions
- the present invention relates to a light emitting diode having a zinc oxide (ZnO) layer, and more particularly to a light emitting diode in which the zinc oxide layer is used as a transparent electrode.
- ZnO zinc oxide
- III-N Group III-nitride (III-N) based lasers or light emitting diodes have greatly changed the fields of lighting, display and data storage and continue to expand their applications.
- the typically low electrical conductivity of the p-type layer results in current concentration in the light emitting diode, causing low light efficiency.
- ITO In order to overcome this limitation of ITO, a technique has been used which employs a relatively thin thickness ITO film and further introduces an extension electrode extending from the electrode pads. In this case, however, an increase in sheet resistance of ITO concentrates current under the electrode pads and the extension electrode, and thus, a current block layer has been added under the ITO film near the electrode pads and the extension electrode. However, the introduction of the current block layer complicates the light emitting diode manufacturing process, and also increases the forward voltage of the light emitting diode by reducing the contact area between the ITO film and the p-GaN layer.
- ZnO has a lower light absorption than ITO and can be formed relatively thicker. Accordingly, it is expected that ZnO can evenly distribute current over a large area, thereby lowering forward voltage.
- the ZnO film uses a source gas different from GaN, there is a problem in mass productivity, for example, excessive process time is required when using a conventional CVD technique.
- the problem to be solved by the present invention to adopt a ZnO transparent electrode, to provide a light emitting diode with high productivity and reliability and a method of manufacturing the same.
- Another object of the present invention is to provide a light emitting diode that is operable under high current and high voltage, and is capable of uniformly distributing current in a plurality of light emitting cells.
- a light emitting diode including a gallium nitride-based first conductive semiconductor layer, a gallium nitride-based second conductive semiconductor layer, and an active layer interposed therebetween; And a ZnO transparent electrode layer positioned on the second conductive semiconductor layer, wherein the ZnO transparent electrode layer includes a ZnO seed layer and a ZnO bulk layer formed on the ZnO seed layer, and the ZnO bulk layer is the ZnO seed.
- the interface between the ZnO seed layer and the second conductivity type semiconductor layer is flatter than the interface between the ZnO seed layer and the ZnO bulk layer, and between the ZnO seed layer and the ZnO bulk layer
- the interface has an irregular irregular shape.
- a light emitting diode in another embodiment, includes: a light emitting structure including a gallium nitride based first conductive semiconductor layer, a gallium nitride based second conductive semiconductor layer, and an active layer interposed therebetween; And a ZnO transparent electrode layer on the second conductive semiconductor layer, wherein the ZnO transparent electrode layer comprises a ZnO seed layer and a ZnO bulk layer formed on the ZnO seed layer, and the ZnO seed layer is a sol-gel method. Is formed on the gallium nitride-based second conductive semiconductor layer, and the ZnO bulk layer is grown on the ZnO seed layer by hydrothermal synthesis, and the ZnO bulk layer is larger than the ZnO seed layer. It is porous.
- a light emitting diode manufacturing method includes growing a first conductive semiconductor layer, an active layer, and a second conductive semiconductor layer on a substrate, wherein the first conductive semiconductor layer and the second conductive semiconductor layer are grown. Is a gallium nitride-based semiconductor layer, a ZnO seed layer is formed on the gallium nitride-based second conductive semiconductor layer by using a sol-gel method, and a ZnO bulk layer is formed on the ZnO seed layer by hydrothermal synthesis. Growth.
- a ZnO seed layer is formed using a sol-gel method, and a ZnO bulk layer is grown thereon using a hydrothermal synthesis method so that the ZnO transparent electrode layer can be formed at low temperature and low cost, which is suitable for mass production of light emitting diodes.
- the ZnO seed layer using the sol-gel method the forward voltage of the light emitting diode can be lowered and the reliability can be improved.
- FIG. 1 is a schematic plan view illustrating a light emitting diode according to an embodiment of the present invention.
- FIG. 2B is a cross-sectional view taken along cut line B-B of FIG. 1.
- FIG. 2C is a cross-sectional view taken along the line C-C of FIG. 1.
- FIG. 2D is a cross-sectional view taken along the line D-D of FIG. 1.
- FIG. 3 is an enlarged plan view illustrating a portion of the first electrode pad of FIG. 1.
- FIG. 4 is a partial cross-sectional view for describing a transparent electrode layer of a light emitting diode according to an embodiment of the present invention.
- 5A is a scanning electron micrograph for explaining a ZnO transparent electrode layer according to a comparative example.
- Figure 5b is a runner electron micrograph for explaining the ZnO transparent electrode layer according to an embodiment of the present invention.
- FIG. 6 is a graph illustrating a change in forward voltage according to a use time of light emitting diodes according to Comparative Examples and Examples.
- a light emitting diode including a gallium nitride-based first conductive semiconductor layer, a gallium nitride-based second conductive semiconductor layer, and an active layer interposed therebetween; And a ZnO transparent electrode layer positioned on the second conductive semiconductor layer, wherein the ZnO transparent electrode layer includes a ZnO seed layer and a ZnO bulk layer formed on the ZnO seed layer, and the ZnO bulk layer is the ZnO seed.
- the interface between the ZnO seed layer and the second conductivity type semiconductor layer is flatter than the interface between the ZnO seed layer and the ZnO bulk layer, and between the ZnO seed layer and the ZnO bulk layer
- the interface has an irregular irregular shape.
- the contact resistance between the transparent electrode layer and the second conductive semiconductor layer can be reduced, thereby reducing the forward voltage.
- the contact resistance between the transparent electrode layer and the second conductive semiconductor layer can be reduced, thereby reducing the forward voltage.
- the ZnO bulk layer may include larger cavities in a region adjacent to the ZnO seed layer than its upper surface. As the ZnO bulk layer grows, crystallinity may be improved, and thus the cavity becomes smaller or thinner toward the top surface.
- the ZnO seed layer may be formed on the gallium nitride based second conductive semiconductor layer using a sol-gel method, and the ZnO bulk layer may be grown on the ZnO seed layer using a hydrothermal synthesis method.
- a sol-gel method and the hydrothermal synthesis method By using the sol-gel method and the hydrothermal synthesis method, a large amount of transparent electrode layers can be formed at a relatively low temperature and at low cost.
- the interface characteristics between the ZnO seed layer and the second conductive semiconductor layer can be improved.
- the transparent electrode layer may have a thickness within the range of 1000 ⁇ to 1um. Within this thickness range, the transparent electrode layer may have good light transmittance and current dispersing performance, thereby providing a light emitting diode capable of driving under high current.
- the light emitting diode may further include a substrate, and the light emitting structure may be disposed on the substrate.
- the light emitting structure may include a plurality of light emitting cells spaced apart from each other, and the ZnO transparent electrode layer may be disposed on the second conductive semiconductor layers of the light emitting cells, respectively.
- the light emitting diode may further include: a first electrode pad electrically connected to a first conductivity type semiconductor layer of at least one light emitting cell; And a second electrode pad electrically connected to a second conductive semiconductor layer of at least one light emitting cell, wherein the light emitting cells may be connected in series between the first electrode pad and the second electrode pad.
- the light emitting diode the first electrode extending portion disposed on the first conductive semiconductor layer of each light emitting cell; And a second electrode extension part disposed on the transparent electrode layer of each light emitting cell.
- the light emitting diode may further include connecting portions for electrically connecting neighboring light emitting cells to each other.
- the second conductive semiconductor layer of each light emitting cell may be surrounded by an upper surface of the first conductive semiconductor layer exposed by mesa etching. Accordingly, when the separation region is formed to separate the light emitting cells from each other, the second conductive semiconductor layer and the transparent electrode may be prevented from being damaged.
- the transparent electrode layer may be disposed in an upper region of the second conductive semiconductor layer, and a lower surface of the transparent electrode layer may have a smaller area than an upper surface of the second conductive semiconductor layer.
- the transparent electrode layer and the mesa forming process may be patterned using the same photoresist pattern.
- the ZnO transparent electrode layer may be patterned by wet etching, and the second conductive semiconductor layer and the active layer may be patterned through dry etching. Since the ZnO transparent electrode layer is also etched in the horizontal direction by wet etching, the ZnO transparent electrode layer is formed to have a smaller area than the second conductivity type semiconductor layer.
- a light emitting diode in another embodiment, includes: a light emitting structure including a gallium nitride based first conductive semiconductor layer, a gallium nitride based second conductive semiconductor layer, and an active layer interposed therebetween; And a ZnO transparent electrode layer on the second conductive semiconductor layer, wherein the ZnO transparent electrode layer comprises a ZnO seed layer and a ZnO bulk layer formed on the ZnO seed layer, and the ZnO seed layer is a sol-gel method. Is formed on the gallium nitride-based second conductive semiconductor layer, and the ZnO bulk layer is grown on the ZnO seed layer by hydrothermal synthesis, and the ZnO bulk layer is larger than the ZnO seed layer. It is porous.
- the ZnO bulk layer may include larger cavities in a region adjacent the ZnO seed layer than its top surface.
- the light emitting diode may further include a substrate, and the light emitting structure may be disposed on the substrate.
- the light emitting structure may include a plurality of light emitting cells spaced apart from each other, and the ZnO transparent electrode layer may be disposed on second conductive semiconductor layers of the light emitting cells, respectively.
- the second conductive semiconductor layer of each light emitting cell may be surrounded by an upper surface of the first conductive semiconductor layer exposed by mesa etching.
- a light emitting diode manufacturing method includes growing a first conductive semiconductor layer, an active layer, and a second conductive semiconductor layer on a substrate, wherein the first conductive semiconductor layer and the second conductive semiconductor layer are grown. Is a gallium nitride-based semiconductor layer, a ZnO seed layer is formed on the gallium nitride-based second conductive semiconductor layer by using a sol-gel method, and a ZnO bulk layer is formed on the ZnO seed layer by hydrothermal synthesis. Growth.
- the ZnO bulk layer may be more porous than the ZnO seed layer.
- an interface between the ZnO seed layer and the second conductive semiconductor layer may be flatter than an interface between the ZnO seed layer and the ZnO bulk layer.
- FIG. 1 is a plan view illustrating a light emitting diode according to an embodiment of the present invention
- FIGS. 2A, 2B, 2C, and 2D are schematic cross-sectional views taken along the cutting lines AA, BB, CC, and DD of FIG. 1, respectively.
- 3 is an enlarged plan view of a portion of the first electrode pad 35 of FIG. 1.
- a light emitting diode includes a substrate 21, a light emitting structure 30, a transparent electrode 29, insulating layers 31a, 31b, 31c, and 31d.
- the first electrode pad 35, the second electrode pad 37, the first extensions 35a, the second extensions 37a, and the third extensions 37b are included.
- the light emitting structure 30 is separated into a plurality of light emitting cells C1, C2, and C3, and first to third extension parts 35a, 37a, and 37b are disposed on the light emitting cells.
- the substrate 21 is not particularly limited as long as it is a substrate capable of growing a gallium nitride based semiconductor layer.
- Examples of the substrate 21 may include a sapphire substrate, a gallium nitride substrate, a SiC substrate, and the like, and may be a patterned sapphire substrate.
- the substrate 21 may have a rectangular or square outer shape as shown in the plan view of FIG. 1, but is not limited thereto.
- the size of the substrate 21 is not particularly limited and may be variously selected.
- the light emitting structure 30 is positioned on the substrate 21 and includes a first conductive semiconductor layer 23, an active layer 25, and a second conductive semiconductor layer 27.
- the first conductivity-type semiconductor layer 23 may be an n-type semiconductor layer
- the second conductivity-type semiconductor layer 27 may be a p-type semiconductor layer, or may be a semiconductor layer that is conductively opposite to each other.
- An active layer 25 is interposed between the first conductive semiconductor layer 23 and the second conductive semiconductor layer 27.
- the first conductive semiconductor layer 23, the active layer 25, and the second conductive semiconductor layer 27 may be formed of a gallium nitride-based compound semiconductor material, that is, (Al, In, Ga) N.
- the active layer 25 may have a composition element and a composition ratio determined so as to emit light of a desired wavelength, and the first conductive semiconductor layer 23 and the second conductive semiconductor layer 27 are compared with the active layer 25.
- the band gap may be formed of a large material.
- each of the first conductive semiconductor layer 23 and the second conductive semiconductor layer 27 may be formed as a single layer, or may be formed as multiple layers.
- the active layer 25 may have a single quantum well or multiple quantum well structures.
- a buffer layer may be interposed between the substrate 21 and the first conductivity-type semiconductor layer 23.
- the light emitting structure 30 may be formed using MOCVD or MBE technology, and the first conductive semiconductor layer 23 may be etched by etching the second conductive semiconductor layer 27 and the active layer 25 using photolithography and etching processes. Some areas of) may be exposed.
- the light emitting structure 30 is separated into a plurality (n) of light emitting cells by the cell separation regions I1 and I2.
- n may be an integer of 2 or more, in particular an integer of 3 or more.
- the light emitting cells C1, C2, and C3 have an elongated rectangular shape and may be disposed in parallel with each other. Accordingly, even-numbered light emitting cells are disposed between odd-numbered light emitting cells. For example, as shown in FIG. 1, the second light emitting cell C2 is disposed between the first and third light emitting cells C1 and C3.
- Both sidewalls of the cell isolation regions I1 and I2 are formed using a photolithography and an etching process, and have a relatively smooth shape in consideration of the reliability of the connection parts 36.
- the sides of the substrate 21 can be formed using laser scribing, unlike the cell isolation regions I1 and I2, and thus, relatively steep slopes.
- the substrate 21 and the first conductivity-type semiconductor layer 23 can be separated together from other light emitting diodes using laser scribing, and thus, the substrate 21 and the first conductivity-type semiconductor layer 23 can be separated.
- Sides can be parallel to each other.
- an upper surface of the first conductive semiconductor layer 23 is exposed along the edges of the light emitting cells C1, C2, and C3. That is, the second conductivity type semiconductor layer 27 is surrounded by the upper surface of the exposed first conductivity type semiconductor layer 23. An upper surface of the first conductive semiconductor layer 23 may be exposed along the entire circumference of the second conductive semiconductor layer 27.
- the transparent electrode layer 29 is positioned on the second conductive semiconductor layer 27 of each of the light emitting cells C1, C2, and C3.
- the transparent electrode layer 29 is made of ZnO and contacts the second conductive semiconductor layer 27. That is, the transparent electrode layer 29 is in electrical contact with the second conductivity type semiconductor layer 27 and has a lower specific resistance than the second conductivity type semiconductor layer 27 to disperse current over a wide area of the light emitting diode.
- the ZnO transparent electrode layer 29 has substantially the same planar shape as the second conductivity type semiconductor layer 27. However, the ZnO transparent electrode layer 29 may have a smaller area than the second conductivity type semiconductor layer 27. The lower surface of the ZnO transparent electrode layer 29 may be in contact with the upper surface of the second conductive semiconductor layer 27.
- the ZnO transparent electrode layer 29 may comprise any material as long as Zn and O make up the majority of the compound and retain the ZulO crystal structure.
- the ZnO transparent electrode layer 29 includes aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), and indium doped zinc oxide (IZO).
- ZnO transparent electrode 29 also includes materials having small amounts of other dopants and / or other impurities or inclusion materials, as well as materials that are nonstoichiometric due to the presence of vacancy and insertion-based material defects. .
- the ZnO transparent electrode layer 29 may have a thickness of at least about five times the general thickness of the ITO film.
- the ITO film is generally formed to a thickness of about 500 kPa or less due to the water absorption rate, but the ZnO transparent electrode layer 29 may have a thickness of 1000 kPa or more and more than about 5000 kPa because of the low water absorption.
- the upper limit of the ZnO transparent electrode layer 29 is not particularly limited, but may be about 1 ⁇ m or less.
- the ZnO transparent electrode layer 29 can be formed thick, so that the sheet resistance can be reduced, thus distributing current more easily.
- the specific structure and formation method of ZnO will be described later in detail with reference to FIG. 4.
- the first electrode pad 35 may be disposed on the first light emitting cell C1, and the second electrode pad 37 may be disposed on the third light emitting cell.
- the first electrode pad 35 may be disposed on the top surface of the exposed first conductive semiconductor layer 23.
- the present invention is not limited thereto, and the first electrode pad 35 may be disposed on the second conductive semiconductor layer 27 via the insulating layer.
- the first electrode pad 35 may be disposed near one edge of the first light emitting cell C1.
- the first extension part 35a is electrically connected to the first conductive semiconductor layer 23 exposed through the mesa etching process.
- the first extension part 35a on the first light emitting cell C1 may extend from the first electrode pad 35, and the other first extension parts 35a on the light emitting cells C1 and C2 may be connected to each other. From 36).
- the second extension part 37a and the third extension part 37b on each of the light emitting cells C1, C2, and C3 surround the first extension part 35a. It may be located on (29).
- the second electrode pad 37 is not disposed on all the light emitting cells C1 to C3, all of the second extension parts 37a and the third extension parts 37b are the second electrode. It does not extend from the pad 37.
- the second extension portion 37a and the third extension portion 37b on the third light emitting cell C3 extend from the second electrode pad 37, but the first and second light emitting cells are extended.
- the second extension part 37a and the third extension part 37b on the C1 and C2 are spaced apart from the second electrode pad 37 and extend from the connection part 36 that electrically connects the light emitting cells.
- the second extension parts 37a and the third extension parts 37b are positioned on the transparent electrode layers 29 on the light emitting cells C1 to C3 and electrically connected to the transparent electrode layers 29, respectively.
- connection parts 36 electrically connect neighboring light emitting cells. Specifically, the connection parts 36 connect the first extension part 35a of one light emitting cell to the second and third extension parts 37a and 37b of the neighboring light emitting cell. As shown in FIG. 2B, one end of the connection part 36 is positioned on the first conductivity type semiconductor layer 23 and connected to the first extension part 35a, and the other end thereof is the second conductivity type semiconductor layer ( 27). As shown in FIG. 1, the other end of the connection portion 36 positioned on the second conductivity-type semiconductor layer 27 is connected to the second and third extension portions 37a and 37b.
- connection parts 36 are disposed near corners in the diagonal direction.
- the connection part 36 connected to the first light emitting cell C1 is disposed near a corner of the diagonal direction facing the first electrode pad 35
- the connection part 36 connected to the third light emitting cell C3 is the second electrode. It is arranged near the edge in the diagonal direction opposite the pad 37.
- the first, second and third extensions 35a, 37a and 37b on the first light emitting cell C1 and the first, second and third extensions on the second light emitting cell C2 have a generally similar shape.
- the first, second and third extensions 35a, 37a and 37b on the second light emitting cell C2 and the first, second and third extensions on the third light emitting cell C3 also have a generally similar shape.
- the first to third extensions 35a, 37a, and 37b on neighboring light emitting cells are arranged in an inverted shape to each other, thereby forming the first extension 35a relatively long with a single line, and the second extension.
- the lengths of the 37a and the third extension 37b may be designed to be substantially the same or similar, and thus, a substantially uniform current distribution may be achieved on both sides of the first extension 35a.
- the first electrode pad 35, the second electrode pad 37, the first extensions 35a, the connecting portions 36, the second extensions 37a and the third extensions 37b. ) May be formed together of the same material in the same process.
- the present invention is not limited thereto, and they may be formed of different materials in different processes.
- the first insulating layer 31a may be located under the first electrode pad 35.
- the first insulating layer 31a mitigates the direct flow of current from the first electrode pad 35 to the first conductive semiconductor layer 23 and contributes to current dispersion.
- the first insulating layer 31a may be disposed below a portion of the first electrode pad 35, and thus, FIG. An edge region of the first electrode pad 35 may be connected to the first conductive semiconductor layer 23.
- a third insulating layer under the connecting portion 36 is formed. 39c) may be intervened.
- the fourth insulating layer 31d may cover sidewalls of the active layer 25 and the second conductive semiconductor layer 27 exposed around the first electrode pad 35. .
- the fourth insulating layer 31d prevents the bonding wire from being short-circuited to the second conductive semiconductor layer 27 or the active layer 25.
- the fourth insulating layer 31d may be formed in a continuous curved shape, and the first extension part 35a may pass over the fourth insulating layer 31d.
- the present invention is not limited thereto, and a part of the fourth insulating layer 31d may be omitted, and the first extension part 35a may pass through the omitted portion of the fourth insulating layer 31d.
- the first to fourth insulating layers 31a, 31b, 31c, and 31d may be formed together with the same material in the same process.
- these insulating layers 31a, 31b, 31c, 31d may be formed using a lift off process, and may be formed with a distributed Bragg reflector.
- FIG. 4 is a partial cross-sectional view for describing a transparent electrode layer 29 of a light emitting diode according to an embodiment of the present invention.
- the ZnO transparent electrode layer 29 is positioned on the second conductive semiconductor layer 27 and includes a ZnO seed layer 29a and a ZnO bulk layer 29b.
- the ZnO seed layer 29a may have a thickness in the range of approximately 5 nm to 20 nm.
- the ZnO seed layer 29a is formed of a continuous film and is distinct from the ZnO bulk layer 29b.
- the ZnO bulk layer 29b is a porous film containing a plurality of voids, whereas the ZnO seed layer 29a is a higher density film than the ZnO bulk layer 29b.
- the ZnO seed layer 29a is formed using the sol-gel method.
- the ZnO seed layer 29a can be formed on the second conductive semiconductor layer 27 as a continuous high density film.
- the second conductivity-type semiconductor layer 27 is a gallium nitride-based semiconductor layer having a woolite crystal structure
- the ZnO seed layer 29a having the woolite crystal structure is formed on the second conductive semiconductor layer 27. It can be easily formed.
- the ZnO bulk layer 29b can be formed using hydrothermal synthesis, and therefore, the ZnO bulk layer 29b can be formed at a relatively low temperature at low cost.
- a method of forming a ZnO seed layer by spin coating a solution in which ZnO powder is dissolved in ammonia to form a ZnO film has been studied.
- the porous ZnO seed layer does not completely cover the semiconductor layer and exposes the top surface of the semiconductor layer.
- the ZnO bulk layer is formed by hydrothermal synthesis on the porous ZnO seed layer, it is difficult to distinguish between the ZnO seed layer and the bulk layer, and a plurality of cavities are also formed at the interface between the semiconductor layer and the ZnO film.
- the cavity between the ZnO film and the semiconductor layer will increase the resistance and the cavity will increase as the use time increases, increasing the forward voltage.
- the ZnO seed layer 29a using the sol-gel method is formed of a relatively high density film compared to the ammonia-based ZnO seed layer, the ZnO seed layer 29a may cover the entire surface of the second conductive semiconductor layer 27. Accordingly, even when the ZnO bulk layer 29b is formed on the ZnO seed layer 29a by using hydrothermal synthesis, the ZnO seed layer 29a which is different from the ZnO bulk layer 29b remains, and the ZnO seed layer 29a is retained. The cavity can be prevented from being formed between the second conductive semiconductor layer 27 and the second conductive semiconductor layer 27.
- the contact resistance between the ZnO transparent electrode layer 29 and the second conductive semiconductor layer 27 can be lowered, and thus the forward voltage can be lowered.
- it is possible to prevent the formation of a cavity at the interface between the ZnO transparent electrode layer 29 and the second conductivity-type semiconductor layer 27 can solve the problem that the forward voltage increases with use time.
- the ZnO seed layer 29a is formed by using a sol-gel method to form a sol by mixing a precursor such as zinc acetated dehydrate with an alcohol and a solvent such as ethanol, and the second conductive semiconductor layer 27. It can be formed by spin coating and heat treatment on. Since the sol is first formed and spin coated, a high density ZnO seed layer can be formed. To form the sol using the sol-gel method, the solution may be maintained for 20 minutes to 1 hour in a temperature range of approximately 50 to 60 ° C., and heat treatment after spin coating may be performed within a range of 300 to 700 ° C.
- the formation of the ZnO seed layer 29a using the sol-gel method enables the formation of the ZnO seed layer 29a in a large amount more quickly and at a lower cost than the formation of the seed layer using CVD or ALD, thereby enabling light emission having the ZnO transparent electrode layer 29. Suitable for mass production of diodes.
- the ZnO bulk layer 29b may be grown by immersing the substrate 21 in which the ZnO seed layer 29a is formed in an aqueous ammonia solution in a supercritical state.
- the ZnO bulk layer 29b is grown on the ZnO seed layer 29a, and a plurality of cavities may be formed in the ZnO bulk layer 29b.
- the ZnO bulk layer 29b includes fewer cavities and has a relatively higher density than the ZnO bulk layer grown on the ZnO seed layer of the ammonia substrate.
- 5A and 5B are scanning electron micrographs showing a ZnO transparent electrode layer 29 formed using a ZnO seed layer based on an aqueous ammonia solution and a ZnO seed layer using a sol-gel method, respectively.
- the ZnO bulk layers 29b were grown by hydrothermal synthesis under the same conditions.
- the ZnO seed layer 29a formed using the sol-gel method is distinguished from the porous ZnO bulk layer 29b, and the ZnO seed layer 29a and the second conductivity-type semiconductor layer 27 At the interface between the cavities is not observed.
- no cavity is observed in the ZnO seed layer 29a of FIG. 5B, and it can be seen that the density is higher than that of the ZnO bulk layer 29b.
- the cavities in the ZnO bulk layer 29b are also relatively smaller in size than the cavities in the bulk layer of FIG. 5A, and the ZnO bulk layer 29b of FIG. 5B is shown in FIG. 5B. It can be seen that it is denser than the bulk layer of 5a.
- the interface between the ZnO seed layer 29a and the second conductivity-type semiconductor layer 27 is more than the interface between the ZnO seed layer 29a and the ZnO bulk layer 29b. It can be seen that it is flat. Although the shape of the upper surface of the ZnO seed layer 29a is deformed during the growth of the ZnO bulk layer 29b, it is determined that the lower surface is maintained without being deformed. In particular, it can be seen that the interface between the ZnO seed layer 29a and the ZnO bulk layer 29b has an irregular concave-convex shape.
- the ZnO bulk layer 29b is porous and includes a plurality of cavities having different sizes therein.
- the ZnO bulk layer 29 includes larger cavities in a region adjacent to the ZnO seed layer 29b than its upper surface.
- FIG. 6 is a graph illustrating a change in forward voltage according to a use time of light emitting diodes according to Comparative Examples and Examples.
- a current of 200 mA was applied at a temperature of 120 ° C., and forward voltage over time was measured.
- Comparative Example 1 shows a forward voltage of a light emitting diode in which a ZnO transparent electrode layer is formed using a ZnO seed layer based on an aqueous ammonia solution
- Comparative Example 2 shows a forward voltage of a light emitting diode to which an ITO transparent electrode layer according to the prior art is applied.
- the example shows the forward voltage of the light emitting diode in which the ZnO transparent electrode layer was formed using the ZnO seed layer formed by the sol-gel method.
- the light emitting diode of Comparative Example 1 using the ZnO seed layer based on the aqueous ammonia solution was similar to the light emitting diode of Comparative Example 2 in which the initial forward voltage was applied to ITO, and the forward voltage rapidly increased with use time.
- the light emitting diode of Comparative Example 2 based on ITO showed a tendency to increase the forward voltage slightly over time.
- the light emitting diode of this embodiment had an initial forward voltage lower than that of the light emitting diodes of Comparative Examples 1 and 2, and the forward voltage decreased slightly as time increased. Therefore, the ZnO seed layer is formed using the sol-gel method, and the ZnO transparent electrode layer 29b is formed using the ZnO seed layer, and thus, it is expected that the forward voltage can be lowered and a light emitting diode having high reliability can be provided.
Landscapes
- Led Devices (AREA)
Abstract
Description
Claims (20)
- 질화갈륨 계열의 제1 도전형 반도체층, 질화갈륨 계열의 제2 도전형 반도체층, 및 이들 사이에 개재된 활성층을 포함하는 발광 구조체; 및상기 제2 도전형 반도체층 상에 위치하는 ZnO 투명 전극층을 포함하되,상기 ZnO 투명 전극층은 ZnO 씨드층 및 상기 ZnO 씨드층 상에 형성된 ZnO 벌크층을 포함하고,상기 ZnO 벌크층은 상기 ZnO 씨드층에 비해 다공성이며,상기 ZnO 씨드층과 상기 제2 도전형 반도체층 사이의 계면이 상기 ZnO 씨드층과 상기 ZnO 벌크층 사이의 계면보다 더 평평하고,상기 ZnO 씨드층과 상기 ZnO 벌크층 사이의 계면은 불규칙적인 요철 형상을 갖는 발광 다이오드.
- 청구항 1에 있어서,상기 ZnO 벌크층은 그 상면보다 상기 ZnO 씨드층에 인접한 영역에 상대적으로 더 큰 공동들을 포함하는 발광 다이오드.
- 청구항 1에 있어서,상기 ZnO 씨드층은 졸-겔법을 이용하여 상기 질화갈륨 계열의 제2 도전형 반도체층 상에 형성되고, 상기 ZnO 벌크층은 수열합성법을 이용하여 상기 ZnO 씨드층 상에 성장된 발광 다이오드.
- 청구항 1에 있어서,상기 투명 전극층은 1000Å 내지 1um 범위 내의 두께를 가지는 발광 다이오드.
- 청구항 1에 있어서,기판을 더 포함하고,상기 발광 구조체는 상기 기판 상에 배치된 발광 다이오드.
- 청구항 5에 있어서,상기 발광 구조체는 서로 이격된 복수의 발광셀들을 포함하고,상기 ZnO 투명 전극층은 상기 발광셀들의 제2 도전형 반도체층들 상에 각각 배치된 발광 다이오드.
- 청구항 6에 있어서,상기 복수의 발광셀들은 서로 평행하게 배치된 발광 다이오드.
- 청구항 6에 있어서,적어도 하나의 발광셀의 제1 도전형 반도체층에 전기적으로 접속된 제1 전극 패드; 및적어도 하나의 발광셀의 제2 도전형 반도체층에 전기적으로 접속된 제2 전극 패드를 포함하고,상기 발광셀들은 상기 제1 전극 패드와 제2 전극 패드 사이에서 직렬 연결된 발광 다이오드.
- 청구항 8에 있어서,각 발광셀의 제1 도전형 반도체층 상에 배치된 제1 전극 연장부; 및각 발광셀의 투명 전극층 상에 배치된 제2 전극 연장부를 더 포함하는 발광 다이오드.
- 청구항 9에 있어서,이웃하는 발광셀들을 서로 전기적으로 연결하기 위한 연결부들을 더 포함하는 발광 다이오드.
- 청구항 6에 있어서,각 발광셀의 제2 도전형 반도체층은 메사 식각에 의해 노출된 제1 도전형 반도체층의 상면으로 둘러싸인 발광 다이오드.
- 청구항 11에 있어서,상기 투명 전극층은 상기 제2 도전형 반도체층의 상부 영역 내에 배치되며,상기 투명 전극층의 하부면은 상기 제2 도전형 반도체층의 상부면보다 좁은 면적을 가지는 발광 다이오드.
- 질화갈륨 계열의 제1 도전형 반도체층, 질화갈륨 계열의 제2 도전형 반도체층, 및 이들 사이에 개재된 활성층을 포함하는 발광 구조체; 및상기 제2 도전형 반도체층 상에 위치하는 ZnO 투명 전극층을 포함하되,상기 ZnO 투명 전극층은 ZnO 씨드층 및 상기 ZnO 씨드층 상에 형성된 ZnO 벌크층을 포함하고,상기 ZnO 씨드층은 졸-겔법을 이용하여 상기 질화갈륨 계열의 제2 도전형 반도체층 상에 형성되고, 상기 ZnO 벌크층은 수열합성법을 이용하여 상기 ZnO 씨드층 상에 성장된 것으로, 상기 ZnO 벌크층이 상기 ZnO 씨드층에 비해 다공성인 발광 다이오드.
- 청구항 13에 있어서,상기 ZnO 벌크층은 그 상면보다 상기 ZnO 씨드층에 인접한 영역에 상대적으로 큰 공동들을 포함하는 발광 다이오드.
- 청구항 13에 있어서,기판을 더 포함하고,상기 발광 구조체는 상기 기판 상에 배치된 발광 다이오드.
- 청구항 15에 있어서,상기 발광 구조체는 서로 이격된 복수의 발광셀들을 포함하고,상기 ZnO 투명 전극층은 상기 발광셀들의 제2 도전형 반도체층들 상에 각각 배치된 발광 다이오드.
- 청구항 16에 있어서,각 발광셀의 제2 도전형 반도체층은 메사 식각에 의해 노출된 제1 도전형 반도체층의 상면으로 둘러싸인 발광 다이오드.
- 기판 상에 제1 도전형 반도체층, 활성층 및 제2 도전형 반도체층을 성장시키되, 제1 도전형 반도체층 및 제2 도전형 반도체층은 질화갈륨 계열의 반도체층이고,상기 질화갈륨 계열의 제2 도전형 반도체층 상에 졸-겔법을 이용하여 ZnO 씨드층을 형성하고,상기 ZnO 씨드층 상에 수열합성법을 이용하여 ZnO 벌크층을 성장시키는 것을 포함하는 발광 다이오드 제조 방법.
- 청구항 18에 있어서,상기 ZnO 벌크층은 상기 ZnO 씨드층에 비해 다공성인 발광 다이오드 제조 방법.
- 청구항 18에 있어서,상기 ZnO 씨드층과 상기 제2 도전형 반도체층 사이의 계면이 상기 ZnO 씨드층과 상기 ZnO 벌크층 사이의 계면보다 평평한 발광 다이오드 제조 방법.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR112019022721-0A BR112019022721A2 (pt) | 2018-07-24 | 2019-07-16 | Diodo emissor de luz e método de fabricação do mesmo |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2018-0085992 | 2018-07-24 | ||
| KR1020180085992A KR20200011187A (ko) | 2018-07-24 | 2018-07-24 | 아연 산화물층을 구비하는 발광 다이오드 및 그것을 제조하는 방법 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020022684A1 true WO2020022684A1 (ko) | 2020-01-30 |
Family
ID=69149128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2019/008738 Ceased WO2020022684A1 (ko) | 2018-07-24 | 2019-07-16 | 아연 산화물층을 구비하는 발광 다이오드 및 그것을 제조하는 방법 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US11063185B2 (ko) |
| KR (1) | KR20200011187A (ko) |
| CN (1) | CN110783437A (ko) |
| BR (1) | BR112019022721A2 (ko) |
| DE (1) | DE102019210949A1 (ko) |
| WO (1) | WO2020022684A1 (ko) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190189850A1 (en) * | 2017-12-19 | 2019-06-20 | Epistar Corporation | Light-emitting device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100047795A (ko) * | 2008-10-29 | 2010-05-10 | 서울옵토디바이스주식회사 | 발광 다이오드 |
| JP2011082479A (ja) * | 2009-10-05 | 2011-04-21 | Everlight Electronics Co Ltd | 白色発光装置、白色発光装置の製造方法および応用 |
| KR101256757B1 (ko) * | 2011-10-31 | 2013-04-23 | 한양대학교 산학협력단 | 다중 씨드층을 이용한 산화아연 나노구조체 제조방법 |
| KR101296265B1 (ko) * | 2012-06-12 | 2013-08-14 | 순천대학교 산학협력단 | 반도체 발광 소자, 반도체 발광 소자 패키지 및 그 제조 방법 |
| KR20170040112A (ko) * | 2015-10-02 | 2017-04-12 | 서울바이오시스 주식회사 | 아연 산화물층을 구비하는 발광 다이오드 소자 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100652864B1 (ko) * | 2005-12-16 | 2006-12-04 | 서울옵토디바이스주식회사 | 개선된 투명전극 구조체를 갖는 교류용 발광 다이오드 |
| US8268287B2 (en) * | 2010-05-12 | 2012-09-18 | National Chung Cheng University | Zinc oxide nanorod thin film and method for making same |
| KR102091831B1 (ko) * | 2013-01-08 | 2020-03-20 | 서울반도체 주식회사 | 발광 다이오드 및 그 제조방법 |
| US20160024688A1 (en) * | 2014-07-25 | 2016-01-28 | Seoul Semiconductor Co., Ltd. | Fabrication and/or application of zinc oxide crystals with internal (intra-crystalline) porosity |
| US9905729B2 (en) * | 2015-03-27 | 2018-02-27 | Seoul Viosys Co., Ltd. | Light emitting diode |
| CN105253852A (zh) * | 2015-09-02 | 2016-01-20 | 西安建筑科技大学 | 微纳复合结构模板的制造方法 |
| KR102364807B1 (ko) * | 2015-09-03 | 2022-02-21 | 서울바이오시스 주식회사 | 발광 소자 제조 방법 |
| US9935243B2 (en) * | 2015-09-15 | 2018-04-03 | The Regents Of The University Of California | Multistep deposition of zinc oxide on gallium nitride |
-
2018
- 2018-07-24 KR KR1020180085992A patent/KR20200011187A/ko not_active Ceased
-
2019
- 2019-07-16 WO PCT/KR2019/008738 patent/WO2020022684A1/ko not_active Ceased
- 2019-07-16 BR BR112019022721-0A patent/BR112019022721A2/pt not_active Application Discontinuation
- 2019-07-17 CN CN201910645670.1A patent/CN110783437A/zh not_active Withdrawn
- 2019-07-22 US US16/518,169 patent/US11063185B2/en active Active
- 2019-07-24 DE DE102019210949.7A patent/DE102019210949A1/de active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100047795A (ko) * | 2008-10-29 | 2010-05-10 | 서울옵토디바이스주식회사 | 발광 다이오드 |
| JP2011082479A (ja) * | 2009-10-05 | 2011-04-21 | Everlight Electronics Co Ltd | 白色発光装置、白色発光装置の製造方法および応用 |
| KR101256757B1 (ko) * | 2011-10-31 | 2013-04-23 | 한양대학교 산학협력단 | 다중 씨드층을 이용한 산화아연 나노구조체 제조방법 |
| KR101296265B1 (ko) * | 2012-06-12 | 2013-08-14 | 순천대학교 산학협력단 | 반도체 발광 소자, 반도체 발광 소자 패키지 및 그 제조 방법 |
| KR20170040112A (ko) * | 2015-10-02 | 2017-04-12 | 서울바이오시스 주식회사 | 아연 산화물층을 구비하는 발광 다이오드 소자 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20200035865A1 (en) | 2020-01-30 |
| US11063185B2 (en) | 2021-07-13 |
| DE102019210949A1 (de) | 2020-01-30 |
| BR112019022721A2 (pt) | 2020-05-12 |
| KR20200011187A (ko) | 2020-02-03 |
| CN110783437A (zh) | 2020-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2010101332A1 (ko) | 발광소자 | |
| WO2013015472A1 (ko) | 반도체 발광소자 및 그 제조방법 | |
| WO2017057978A1 (ko) | 발광소자 | |
| WO2011025291A2 (ko) | 요철 패턴 기판 상의 고품질 비극성/반극성 반도체 소자 및 그 제조 방법 | |
| WO2013024914A1 (ko) | 질화물 반도체 발광소자의 제조방법 및 이에 의해 제조된 질화물 반도체 발광소자 | |
| WO2014109454A1 (ko) | 발광 다이오드 및 그 제조방법 | |
| WO2021210919A1 (ko) | 단일칩 복수 대역 발광 다이오드 | |
| WO2016003205A1 (ko) | 발광 소자 | |
| WO2021158016A1 (ko) | 단일칩 복수 대역 발광 다이오드 | |
| WO2013165127A1 (ko) | 발광 다이오드 소자 및 그의 제조 방법 | |
| WO2009093846A2 (ko) | 발광소자의 제조방법 | |
| CN101840968B (zh) | 一种能够提升光取出率的半导体光电元件及其制造方法 | |
| WO2013137554A1 (ko) | 발광 소자 및 그 제조 방법 | |
| WO2013141421A1 (ko) | 수평형 파워 led 소자 및 그 제조방법 | |
| WO2020022684A1 (ko) | 아연 산화물층을 구비하는 발광 다이오드 및 그것을 제조하는 방법 | |
| KR100748247B1 (ko) | 질화물계 반도체 발광다이오드 및 그 제조방법 | |
| WO2016036067A1 (en) | Light emitting diode | |
| WO2015016507A1 (ko) | 발광 소자 제조용 템플릿 및 자외선 발광 소자 제조 방법 | |
| KR100495004B1 (ko) | 발광다이오드 및 그 제조방법 | |
| CN115336013A (zh) | 单芯片多带发光二极管 | |
| WO2013022129A1 (ko) | 질화물 반도체 발광소자 | |
| WO2012118251A1 (ko) | Wurtzite 파우더를 이용한 질화물계 발광소자 및 그 제조 방법 | |
| TWI789764B (zh) | 發光元件及其製造方法與發光裝置的製造方法 | |
| CN116613255A (zh) | 改善晶格失配的发光二极管及其制备方法 | |
| CN115241338A (zh) | 一种氮化物半导体结构及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112019022721 Country of ref document: BR |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19839943 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 112019022721 Country of ref document: BR Kind code of ref document: A2 Effective date: 20191030 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 19839943 Country of ref document: EP Kind code of ref document: A1 |