CN113471353B - Glass packaging method for improving LED light-emitting rate - Google Patents
Glass packaging method for improving LED light-emitting rate Download PDFInfo
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- CN113471353B CN113471353B CN202110705908.2A CN202110705908A CN113471353B CN 113471353 B CN113471353 B CN 113471353B CN 202110705908 A CN202110705908 A CN 202110705908A CN 113471353 B CN113471353 B CN 113471353B
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- 239000011521 glass Substances 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 83
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 140
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 138
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052751 metal Inorganic materials 0.000 claims abstract description 116
- 239000002184 metal Substances 0.000 claims abstract description 116
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- 238000012545 processing Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 103
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 57
- 239000004005 microsphere Substances 0.000 claims description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 44
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 41
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 39
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 38
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 34
- 229910021426 porous silicon Inorganic materials 0.000 claims description 29
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000004528 spin coating Methods 0.000 claims description 26
- 239000004793 Polystyrene Substances 0.000 claims description 24
- 229920002223 polystyrene Polymers 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 23
- 238000000016 photochemical curing Methods 0.000 claims description 22
- 238000003466 welding Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 18
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 18
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- 241000252506 Characiformes Species 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 9
- WCWRAWMYDYYCRZ-UHFFFAOYSA-N toluene;trichloro(octadecyl)silane Chemical compound CC1=CC=CC=C1.CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl WCWRAWMYDYYCRZ-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 claims description 6
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052709 silver Inorganic materials 0.000 abstract description 7
- 239000004332 silver Substances 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 20
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 10
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical group Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
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- -1 2,4, 6-trimethyl benzoyl ethyl Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- HXCHRJMJMALFHP-UHFFFAOYSA-N azanium;ethanol;hydroxide Chemical compound N.O.CCO HXCHRJMJMALFHP-UHFFFAOYSA-N 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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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
- H01L33/48—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
- 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
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/005—Processes relating to semiconductor body packages relating to encapsulations
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0058—Processes relating to semiconductor body packages relating to optical field-shaping elements
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Led Device Packages (AREA)
- Luminescent Compositions (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a glass packaging method for improving the light-emitting rate of an LED (light-emitting diode), which comprises the following steps of sequentially stacking a sapphire substrate, a gallium nitride layer, a metal conducting layer and a glass substrate from inside to outside; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer, a gallium nitride epitaxial light-emitting layer and a gallium nitride epitaxial P-type layer along the direction far away from the sapphire substrate; and processing a light reflecting layer on the back surface of the glass substrate. According to the invention, the light reflecting layer is processed on the back surface of the glass substrate, so that the front metal conducting layer plated with the silver reflecting layer is replaced, the use of noble metal silver is reduced, and the glass packaging cost is greatly reduced. And the light reflecting layer is fully covered on the glass substrate, so that light leakage is effectively reduced, and the light emitting rate of the LED is greatly improved.
Description
Technical Field
The invention relates to the technical field of illumination, in particular to a glass packaging method for improving the light-emitting rate of an LED.
Background
The LED, namely the light emitting diode, is a novel solid-state light source, has the advantages of high luminous efficiency, energy conservation, environmental protection, long service life and the like, and is the main development direction of the future lighting source market. LEDs are currently widely used in display backlights, automotive headlamps, indoor and outdoor lighting, and the like.
LEDs on the market are mainly based on GaN materials, and have gained wide attention and rapid development worldwide. In order to obtain a high-luminance LED, it is necessary to improve the external quantum efficiency of the LED. The external quantum efficiency is mainly determined by the internal quantum efficiency and the light extraction efficiency. The internal quantum efficiency of LEDs is already very high, so the light extraction efficiency becomes a key factor for determining the external quantum efficiency.
The main reasons for the low external quantum efficiency of LEDs are: the refractive index of GaN has a large difference with the refractive index of air, when photons generated by the active region are emitted into the light sparse medium air from the optically dense medium GaN in the emitting process, the emitted photons exceeding the angle are subjected to a total reflection phenomenon at the interface and cannot escape, and the reflected photons are absorbed by the material to generate heat, so that the luminous efficiency of the LED device is further reduced. Therefore, how to adopt an effective mode to enable the part of light to escape is a starting point for improving the output power of the GaN-based LED and is also a key point for popularization and application of the LED solid-state lighting source.
In the past, fluorescent powder and epoxy resin or silica gel are mixed and coated on the surface of an LED chip to realize LED packaging, but the epoxy resin or silica gel has poor heat resistance and ageing resistance, and recently, glass substrate packaging is used as a new packaging carrier mode. However, the upper surface and the lower surface of the LED packaging glass are flat and smooth, and the refractive index difference between the glass and the air is large, so that the interface has the problem of total emission. In order to improve the light extraction rate, a silver reflective layer is usually plated on the metal wiring (fig. 1), but the metal wiring occupies a small area of the glass substrate, so that complete specular reflection cannot be achieved, and a certain proportion of light still leaks from the other surface of the glass substrate.
Patent CN203883002U discloses a multi-surface display LED package structure, in which a silver-plated layer is disposed on an ITO conductive layer corresponding to an LED chip, on one hand, the cost problem is caused by the use of silver metal, and on the other hand, the light-emitting rate of the LED is still not ideal.
Disclosure of Invention
The invention aims to provide a glass packaging method for improving the LED light-emitting rate, which greatly reduces the glass packaging cost and greatly improves the LED light-emitting rate.
In order to achieve the purpose, the invention is realized by the following scheme:
a glass packaging method for improving the light-emitting rate of an LED comprises the steps of sequentially stacking a sapphire substrate, a gallium nitride layer, a metal conductive layer and a glass substrate from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer, a gallium nitride epitaxial light-emitting layer and a gallium nitride epitaxial P-type layer along the direction far away from the sapphire substrate; the method for processing the light reflecting layer on the back surface of the glass substrate comprises the following steps:
(1) firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material, then mixing zirconyl nitrate hydrate and the porous silicon dioxide microspheres to prepare slurry, forming a blank body through photocuring, and performing nitridation sintering treatment to obtain composite microspheres;
(2) then, preparing a premix by taking the composite microspheres and antimony oxide as raw materials for later use;
(3) then depositing a barium strontium titanate film on the back surface of the glass substrate, then spin-coating premix on the surface of the barium strontium titanate film, and performing post-treatment to form the light reflection layer.
Preferably, the metal conductive layer is divided into a region N and a region P, and is bonded to the glass substrate through metal adhesion layers respectively; respectively welding a metal electrode N and a metal electrode P on the region N and the region P through conductive welding materials, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer and the gallium nitride epitaxial light-emitting layer and is in contact with the gallium nitride epitaxial N-type layer, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer; and coating an inorganic insulating medium on the periphery of the gallium nitride layer, wherein the side surface of the metal electrode N penetrating through the gallium nitride layer part is also coated with the inorganic insulating medium.
Preferably, the metal adhesion layer is made of titanium nitride, and the inorganic insulating medium is aluminum nitride.
Preferably, in the step (1), the preparation method of the porous silica microspheres comprises the following steps: firstly, adding 1 part of polystyrene seeds into 12-15 parts of ammonia water ethanol solution, and uniformly stirring and dispersing to obtain a seed suspension; adding 2-3 parts of tetraethoxysilane into 6-8 parts of absolute ethyl alcohol, and stirring and dispersing uniformly to obtain an tetraethoxysilane solution; then simultaneously adding an ethyl orthosilicate solution and 5-7 parts of an ammonia water ethanol solution into the seed suspension, stirring and reacting for 3-4 hours, standing for 1-2 hours, centrifuging, washing, calcining, and recording to obtain the porous silicon dioxide microspheres; wherein the ammonia water ethanol solution is prepared by mixing 25% mass concentration ammonia water solution and absolute ethyl alcohol in a volume ratio of 1: 5 stirring and mixing evenly.
More preferably, the polystyrene seed has a particle size of 1.5 μm and CV of 3%.
Further preferably, the adding speed of the tetraethoxysilane solution and the ammonia water ethanol solution to the seed suspension is 3.5mL/min and 2mL/min respectively.
Preferably, in the step (1), the preparation method of the green body comprises the following steps: firstly, under the condition of keeping out of the sun, mixing and grinding 1 part of zirconyl nitrate hydrate, 0.3-0.5 part of porous silica microspheres, 0.2-0.3 part of polyethylene glycol 400, 0.03-0.05 part of ethyl 2,4, 6-trimethylbenzoylphosphonate and 5-7 parts of ethylene glycol to prepare slurry; then, dropwise adding the slurry into 15-17 parts of dimethyl silicone oil to form spherical liquid drops; and then irradiating by ultraviolet light, carrying out photocuring, centrifuging, washing and drying to obtain the blank.
Further preferably, the photocuring time is 10 to 15 minutes.
Preferably, in the step (1), the nitriding sintering treatment is specifically performed by: firstly, paving a blank at the bottom of a crucible, covering a graphite plate above the crucible, continuously introducing argon at the flow rate of 50mL/min, heating to 800 ℃, continuously introducing nitrogen at the flow rate of 200mL/min, continuously heating to 1500 ℃, preserving heat for 3-4 hours, and naturally cooling to room temperature.
Further preferably, the heating rate is 10 ℃/min, and the introduction of nitrogen gas is stopped when the temperature is naturally cooled to 300 ℃.
Preferably, the specific method of the step (2) comprises the following steps in parts by weight: adding 1 part of composite microspheres and 3-5 parts of antimony oxide into 10-12 parts of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
Preferably, in the step (3), the specific method for depositing the barium strontium titanate thin film on the back surface of the glass substrate in parts by weight is as follows: respectively preparing 0.05-0.06 part of barium nitrate, 0.17-0.18 part of strontium nitrate, 0.2-0.25 part of ammonium fluotitanate and 0.19-0.21 part of boric acid into corresponding solutions by using 100 parts of water, mixing and stirring the solutions uniformly, adjusting the pH value to be 3-3.2, vacuumizing until no air bubbles are discharged, and obtaining a premixed solution; then completely immersing the glass substrate into a Piranha solution, performing immersion treatment for 2 hours, cleaning with ethanol, drying with nitrogen, completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, performing immersion treatment for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 20-25 hours at 52-55 ℃, taking out and drying to realize the deposition of the barium strontium titanate film on the back surface of the glass substrate.
Preferably, in the step (3), the spin coating process conditions are as follows: the rotation speed is 6000 to 7000r/min, and the spin coating time is 40 to 50 s.
Preferably, in the step (3), the process conditions of the post-treatment are as follows: treating at 600-700 ℃ for 3-5 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention sequentially stacks a sapphire substrate, a gallium nitride layer, a metal conducting layer and a glass substrate from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer, a gallium nitride epitaxial light-emitting layer and a gallium nitride epitaxial P-type layer along the direction far away from the sapphire substrate; and processing a light reflecting layer on the back surface of the glass substrate. According to the invention, the light reflecting layer is processed on the back surface of the glass substrate, so that the front metal conducting layer plated with the silver reflecting layer is replaced, the use of noble metal silver is reduced, and the glass packaging cost is greatly reduced. And the light reflecting layer is fully covered on the glass substrate, so that light leakage is effectively reduced, and the light emitting rate of the LED is greatly improved.
(2) The specific method for processing the light reflecting layer on the back surface of the glass substrate comprises the following steps: firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material, then mixing zirconyl nitrate hydrate and the porous silicon dioxide microspheres to prepare slurry, forming a blank body through photocuring, and performing nitridation sintering treatment to obtain composite microspheres; then, preparing a premix by taking the composite microspheres and antimony oxide as raw materials for later use; then depositing a barium strontium titanate film on the back surface of the glass substrate, then spin-coating premix on the surface of the barium strontium titanate film, and performing post-treatment to form the light reflection layer. That is to say, the light reflection layer of the invention comprises two layers of a barium strontium titanate film and a premix spin coating, wherein the barium strontium titanate film has certain light reflectivity, the premix spin coating is prepared by taking composite microspheres and antimony oxide as raw materials, and the composite microspheres and antimony oxide have synergistic effect to further improve the light-emitting rate of the LED.
(3) When the composite microspheres are prepared, the porous silicon dioxide microspheres and zirconyl nitrate hydrate are mixed to prepare slurry, and the slurry is subjected to photocuring and nitridation sintering to obtain the composite microspheres, wherein the porous silicon dioxide microspheres have rich pores and large specific surface area, and have a good reflection effect on light.
Drawings
FIG. 1 is a longitudinal cross-sectional view of a conventional package structure of a glass substrate;
FIG. 2 is a longitudinal cross-sectional view of a glass package structure according to the present invention;
the solar cell comprises a sapphire substrate 1, a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3, a gallium nitride epitaxial P-type layer 4, an inorganic insulating medium 5, a metal electrode 6, a conductive welding material 7, a metal conductive layer 8, a metal adhesion layer 9, a glass substrate 10, a silver-plated reflecting layer 11 and a light reflecting layer 12.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A glass packaging method for improving LED light-emitting rate, as shown in figure 2, sequentially stacking a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8 and a glass substrate 10 from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1; the light reflecting layer 12 is processed on the back surface of the glass substrate 10 by the following specific method:
(1) firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material, then mixing zirconyl nitrate hydrate and the porous silicon dioxide microspheres to prepare slurry, forming a blank body through photocuring, and performing nitridation sintering treatment to obtain composite microspheres;
(2) then, preparing a premix by taking the composite microspheres and antimony oxide as raw materials for later use;
(3) then, a barium strontium titanate film is deposited on the back surface of the glass substrate 10, and then a premix is spin-coated on the surface of the barium strontium titanate film, and post-treatment is performed to form the light reflection layer 12.
The metal conductive layer 8 is divided into a region N and a region P which are respectively bonded to the glass substrate 10 through the metal adhesion layer 9; welding corresponding metal electrodes 6, namely a metal electrode N and a metal electrode P on the region N and the region P respectively through conductive welding materials 7, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and is in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is applied to the periphery of the gallium nitride layer, wherein the side of the metal electrode N that passes through the gallium nitride layer portion is also coated with the inorganic insulating medium.
The metal adhesion layer 9 is made of titanium nitride, and the inorganic insulating medium 5 is aluminum nitride.
In the step (1), the preparation method of the porous silica microspheres comprises the following steps: firstly, adding 1g of polystyrene seeds into 12g of ammonia water ethanol solution, and uniformly stirring and dispersing to obtain a seed suspension; adding 3g of tetraethoxysilane into 6g of absolute ethyl alcohol, and uniformly stirring and dispersing to obtain a tetraethoxysilane solution; then simultaneously adding the ethyl orthosilicate solution and 7g of ammonia water ethanol solution into the seed suspension, stirring and reacting for 3 hours, standing for 2 hours, centrifuging, washing and calcining to obtain the porous silicon dioxide microspheres; wherein the ammonia water ethanol solution is prepared by mixing 25% mass concentration ammonia water solution and absolute ethyl alcohol in a volume ratio of 1: 5 stirring and mixing evenly.
The polystyrene seed had a particle size of 1.5 μm with CV of 3%.
The adding speed of the ethyl orthosilicate solution and the ammonia water ethanol solution to the seed suspension is 3.5mL/min and 2mL/min respectively.
In the step (1), the preparation method of the blank body comprises the following steps: 1g of zirconyl nitrate hydrate, 0.3g of porous silica microspheres, 0.3g of polyethylene glycol 400, 0.03g of 2,4, 6-trimethylbenzoylphosphonic acid ethyl ester and 7g of ethylene glycol are mixed and ground under a dark condition to prepare slurry; then, dropwise adding the slurry into 15g of dimethyl silicone oil to form spherical liquid drops; and then irradiating by ultraviolet light, carrying out photocuring, centrifuging, washing and drying to obtain the blank.
The photocuring time was 15 minutes.
In the step (1), the specific method of the nitriding sintering treatment comprises the following steps: spreading the blank at the bottom of a crucible, covering a graphite plate above the crucible, continuously introducing argon at the flow rate of 50mL/min, heating to 800 ℃, continuously introducing nitrogen at the flow rate of 200mL/min, continuously heating to 1500 ℃, preserving heat for 3 hours, and naturally cooling to room temperature.
The heating rate is 10 ℃/min, and the nitrogen gas is stopped to be introduced when the temperature is naturally cooled to 300 ℃.
The specific method of the step (2) is as follows: and adding 1g of composite microspheres and 5g of antimony oxide into 10g of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
In the step (3), the specific method for depositing the barium strontium titanate film on the back surface of the glass substrate is as follows: preparing corresponding solutions of 0.06g of barium nitrate, 0.17g of strontium nitrate, 0.25g of ammonium fluotitanate and 0.19g of boric acid by respectively using 100g of water, mixing and stirring the solutions uniformly, adjusting the pH value to be 3.2, and vacuumizing until no bubbles are discharged to obtain a premixed solution; then completely immersing the glass substrate into a Piranha solution, soaking for 2 hours, cleaning with ethanol, drying with nitrogen, then completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, soaking for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 25 hours at 52 ℃, taking out and drying to deposit the barium strontium titanate film on the back surface of the glass substrate.
In the step (3), the spin coating process conditions are as follows: the rotating speed is 6000r/min, and the spin coating time is 50 s.
In the step (3), the post-treatment process conditions are as follows: the treatment was carried out at 600 ℃ for 5 hours.
Example 2
A glass packaging method for improving LED light-emitting rate, as shown in figure 2, sequentially stacking a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8 and a glass substrate 10 from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1; the light reflecting layer 12 is processed on the back surface of the glass substrate 10, specifically by the following method:
(1) firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material, then mixing zirconyl nitrate hydrate and the porous silicon dioxide microspheres to prepare slurry, forming a blank body through photocuring, and performing nitridation sintering treatment to obtain composite microspheres;
(2) then, preparing a premix by taking the composite microspheres and antimony oxide as raw materials for later use;
(3) then, a barium strontium titanate film is deposited on the back surface of the glass substrate 10, and then a pre-mixed material is spin-coated on the surface of the barium strontium titanate film, and post-treatment is performed to form the light reflection layer 12.
The metal conductive layer 8 is divided into a region N and a region P which are respectively bonded to the glass substrate 10 through the metal adhesion layer 9; respectively welding corresponding metal electrodes 6, namely a metal electrode N and a metal electrode P on the region N and the region P through conductive welding materials 7, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and is in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is applied to the periphery of the gallium nitride layer, wherein the side of the metal electrode N that passes through the gallium nitride layer portion is also coated with the inorganic insulating medium.
The metal adhesion layer 9 is made of titanium nitride, and the inorganic insulating medium 5 is aluminum nitride.
In the step (1), the preparation method of the porous silica microspheres comprises the following steps: firstly, adding 1g of polystyrene seeds into 15g of ammonia water ethanol solution, and uniformly stirring and dispersing to obtain a seed suspension; adding 2g of tetraethoxysilane into 8g of absolute ethyl alcohol, and uniformly stirring and dispersing to obtain a tetraethoxysilane solution; then simultaneously adding an ethyl orthosilicate solution and 5g of an ammonia water ethanol solution into the seed suspension, stirring and reacting for 4 hours, standing for 1 hour, centrifuging, washing and calcining to obtain the porous silicon dioxide microspheres; wherein the ammonia water ethanol solution is prepared by mixing 25% mass concentration ammonia water solution and absolute ethyl alcohol in a volume ratio of 1: 5 stirring and mixing evenly to obtain the product.
The polystyrene seed had a particle size of 1.5 μm and CV of 3%.
The adding speed of the ethyl orthosilicate solution and the ammonia water ethanol solution to the seed suspension is 3.5mL/min and 2mL/min respectively.
In the step (1), the preparation method of the blank body comprises the following steps: 1g of zirconyl nitrate hydrate, 0.5g of porous silica microspheres, 0.2g of polyethylene glycol 400, 0.05g of 2,4, 6-trimethylbenzoylphosphonic acid ethyl ester and 5g of ethylene glycol are mixed and ground under a dark condition to prepare slurry; then, dropwise adding the slurry into 17g of dimethyl silicone oil to form spherical liquid drops; and then irradiating by ultraviolet light to perform photocuring, centrifuging, washing and drying to obtain the blank.
The photocuring time was 10 minutes.
In the step (1), the specific method of the nitriding sintering treatment comprises the following steps: spreading the blank at the bottom of a crucible, covering a graphite plate above the crucible, continuously introducing argon at the flow rate of 50mL/min, heating to 800 ℃, continuously introducing nitrogen at the flow rate of 200mL/min, continuously heating to 1500 ℃, preserving heat for 4 hours, and naturally cooling to room temperature.
The heating rate is 10 ℃/min, and the nitrogen gas is stopped to be introduced when the temperature is naturally cooled to 300 ℃.
The specific method of the step (2) comprises the following steps: adding 1g of composite microspheres and 3g of antimony oxide into 12g of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
In the step (3), the specific method for depositing the barium strontium titanate film on the back surface of the glass substrate is as follows: preparing corresponding solutions of 0.05g of barium nitrate, 0.18g of strontium nitrate, 0.2g of ammonium fluotitanate and 0.21g of boric acid by using 100g of water respectively, mixing and stirring the solutions uniformly, adjusting the pH value to be 3, and vacuumizing until no bubbles are discharged to obtain a premixed solution; then completely immersing the glass substrate into a Piranha solution, soaking for 2 hours, cleaning with ethanol, drying with nitrogen, then completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, soaking for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 20 hours at 55 ℃, taking out and drying to deposit the barium strontium titanate film on the back surface of the glass substrate.
In the step (3), the spin coating process conditions are as follows: the rotation speed is 7000r/min, and the spin coating time is 40 s.
In the step (3), the post-treatment process conditions are as follows: the treatment was carried out at 700 ℃ for 3 hours.
Example 3
A glass packaging method for improving LED light-emitting rate, as shown in figure 2, sequentially stacking a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8 and a glass substrate 10 from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1; the light reflecting layer 12 is processed on the back surface of the glass substrate 10 by the following specific method:
(1) firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material, then mixing zirconyl nitrate hydrate and the porous silicon dioxide microspheres to prepare slurry, forming a blank body through photocuring, and performing nitridation sintering treatment to obtain composite microspheres;
(2) then, preparing a premix by taking the composite microspheres and antimony oxide as raw materials for later use;
(3) then, a barium strontium titanate film is deposited on the back surface of the glass substrate 10, and then a premix is spin-coated on the surface of the barium strontium titanate film, and post-treatment is performed to form the light reflection layer 12.
The metal conductive layer 8 is divided into a region N and a region P which are respectively bonded to the glass substrate 10 through the metal adhesion layer 9; welding corresponding metal electrodes 6, namely a metal electrode N and a metal electrode P on the region N and the region P respectively through conductive welding materials 7, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and is in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is applied to the periphery of the gallium nitride layer, wherein the side of the metal electrode N that passes through the gallium nitride layer portion is also coated with the inorganic insulating medium.
The metal adhesion layer 9 is made of titanium nitride, and the inorganic insulating medium 5 is aluminum nitride.
In the step (1), the preparation method of the porous silica microspheres comprises the following steps: firstly, adding 1g of polystyrene seeds into 13g of ammonia water ethanol solution, and uniformly stirring and dispersing to obtain a seed suspension; then adding 2.5g of tetraethoxysilane into 7g of absolute ethyl alcohol, and stirring and dispersing uniformly to obtain tetraethoxysilane solution; then simultaneously adding the ethyl orthosilicate solution and 6g of ammonia water ethanol solution into the seed suspension, stirring and reacting for 3.5 hours, standing for 1.5 hours, centrifuging, washing and calcining to obtain the porous silicon dioxide microspheres; wherein the ammonia water ethanol solution is prepared by mixing 25% mass concentration ammonia water solution and absolute ethyl alcohol in a volume ratio of 1: 5 stirring and mixing evenly.
The polystyrene seed had a particle size of 1.5 μm and CV of 3%.
The adding speed of the ethyl orthosilicate solution and the ammonia water ethanol solution to the seed suspension is 3.5mL/min and 2mL/min respectively.
In the step (1), the preparation method of the blank body comprises the following steps: under the condition of keeping out of the sun, 1g of zirconyl nitrate hydrate, 0.4g of porous silica microspheres, 0.25g of polyethylene glycol 400, 0.04g of 2,4, 6-trimethyl benzoyl ethyl phosphonate and 6g of ethylene glycol are mixed and ground to prepare slurry; then, dropwise adding the slurry into 16g of dimethyl silicone oil to form spherical liquid drops; and then irradiating by ultraviolet light to perform photocuring, centrifuging, washing and drying to obtain the blank.
The photocuring time was 12 minutes.
In the step (1), the specific method of the nitriding sintering treatment comprises the following steps: spreading the blank at the bottom of a crucible, covering a graphite plate above the crucible, continuously introducing argon at the flow rate of 50mL/min, heating to 800 ℃, continuously introducing nitrogen at the flow rate of 200mL/min, continuously heating to 1500 ℃, preserving heat for 3.5 hours, and naturally cooling to room temperature.
The heating rate is 10 ℃/min, and the nitrogen gas is stopped to be introduced when the temperature is naturally cooled to 300 ℃.
The specific method of the step (2) is as follows: and adding 1g of composite microspheres and 4g of antimony oxide into 11g of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
In the step (3), the specific method for depositing the barium strontium titanate film on the back surface of the glass substrate is as follows: preparing 0.055g of barium nitrate, 0.175g of strontium nitrate, 0.22g of ammonium fluotitanate and 0.2g of boric acid into corresponding solutions by using 100g of water respectively, mixing and stirring the solutions uniformly, adjusting the pH value to 3.1, and vacuumizing until no air bubbles are discharged to obtain a premixed solution; then completely immersing the glass substrate into a Piranha solution, soaking for 2 hours, cleaning with ethanol, drying with nitrogen, then completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, soaking for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 22 hours at 53 ℃, taking out and drying to deposit the barium strontium titanate film on the back surface of the glass substrate.
In the step (3), the spin coating process conditions are as follows: the rotation speed is 7000r/min, and the spin coating time is 45 s.
In the step (3), the post-treatment process conditions are as follows: the treatment was carried out at 650 ℃ for 4 hours.
Comparative example 1
A glass packaging method for improving LED light-emitting rate, as shown in figure 2, sequentially stacking a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8 and a glass substrate 10 from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1; the light reflecting layer 12 is processed on the back surface of the glass substrate 10 by the following specific method:
(1) firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material;
(2) then preparing a premix by taking the porous silicon dioxide microspheres and antimony oxide as raw materials for later use;
(3) then, a barium strontium titanate film is deposited on the back surface of the glass substrate 10, and then a premix is spin-coated on the surface of the barium strontium titanate film, and post-treatment is performed to form the light reflection layer 12.
The metal conductive layer 8 is divided into a region N and a region P which are respectively bonded to the glass substrate 10 through the metal adhesion layer 9; welding corresponding metal electrodes 6, namely a metal electrode N and a metal electrode P on the region N and the region P respectively through conductive welding materials 7, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and is in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is applied to the periphery of the gallium nitride layer, wherein the side of the metal electrode N that passes through the gallium nitride layer portion is also coated with the inorganic insulating medium.
The metal adhesion layer 9 is made of titanium nitride, and the inorganic insulating medium 5 is aluminum nitride.
In the step (1), the preparation method of the porous silica microspheres comprises the following steps: firstly, adding 1g of polystyrene seeds into 12g of ammonia water ethanol solution, and uniformly stirring and dispersing to obtain a seed suspension; adding 3g of tetraethoxysilane into 6g of absolute ethyl alcohol, and uniformly stirring and dispersing to obtain a tetraethoxysilane solution; then simultaneously adding the ethyl orthosilicate solution and 7g of ammonia water ethanol solution into the seed suspension, stirring and reacting for 3 hours, standing for 2 hours, centrifuging, washing and calcining to obtain the porous silicon dioxide microspheres; wherein the ammonia water ethanol solution is prepared by mixing 25% mass concentration ammonia water solution and absolute ethyl alcohol in a volume ratio of 1: 5 stirring and mixing evenly.
The polystyrene seed had a particle size of 1.5 μm and CV of 3%.
The adding speed of the ethyl orthosilicate solution and the ammonia water ethanol solution to the seed suspension is 3.5mL/min and 2mL/min respectively.
The specific method of the step (2) is as follows: and adding 1g of porous silicon dioxide microspheres and 5g of antimony oxide into 10g of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
In the step (3), the specific method for depositing the barium strontium titanate film on the back surface of the glass substrate is as follows: preparing corresponding solutions of 0.06g of barium nitrate, 0.17g of strontium nitrate, 0.25g of ammonium fluotitanate and 0.19g of boric acid by respectively using 100g of water, mixing and stirring the solutions uniformly, adjusting the pH value to be 3.2, and vacuumizing until no bubbles are discharged to obtain a premixed solution; then completely immersing the glass substrate into a Piranha solution, soaking for 2 hours, cleaning with ethanol, drying with nitrogen, then completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, soaking for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 25 hours at 52 ℃, taking out and drying to deposit the barium strontium titanate film on the back surface of the glass substrate.
In the step (3), the spin coating process conditions are as follows: the rotating speed is 6000r/min, and the spin coating time is 50 s.
In the step (3), the post-treatment process conditions are as follows: the treatment was carried out at 600 ℃ for 5 hours.
Comparative example 2
A glass packaging method for improving LED light-emitting rate, as shown in figure 2, sequentially stacking a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8 and a glass substrate 10 from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1; the light reflecting layer 12 is processed on the back surface of the glass substrate 10 by the following specific method:
(1) firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material, then mixing zirconyl nitrate hydrate and the porous silicon dioxide microspheres to prepare slurry, forming a blank body through photocuring, and performing nitridation sintering treatment to obtain composite microspheres;
(2) then, preparing a premix compound by taking the composite microspheres as a raw material for later use;
(3) then, a barium strontium titanate film is deposited on the back surface of the glass substrate 10, and then a premix is spin-coated on the surface of the barium strontium titanate film, and post-treatment is performed to form the light reflection layer 12.
The metal conductive layer 8 is divided into a region N and a region P which are respectively bonded to the glass substrate 10 through the metal adhesion layer 9; welding corresponding metal electrodes 6, namely a metal electrode N and a metal electrode P on the region N and the region P respectively through conductive welding materials 7, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and is in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is applied to the periphery of the gallium nitride layer, wherein the side of the metal electrode N that passes through the gallium nitride layer portion is also coated with the inorganic insulating medium.
The metal adhesion layer 9 is made of titanium nitride, and the inorganic insulating medium 5 is aluminum nitride.
In the step (1), the preparation method of the porous silica microspheres comprises the following steps: firstly, adding 1g of polystyrene seeds into 12g of ammonia water ethanol solution, and uniformly stirring and dispersing to obtain a seed suspension; adding 3g of tetraethoxysilane into 6g of absolute ethyl alcohol, and uniformly stirring and dispersing to obtain tetraethoxysilane solution; then simultaneously adding the ethyl orthosilicate solution and 7g of ammonia water ethanol solution into the seed suspension, stirring and reacting for 3 hours, standing for 2 hours, centrifuging, washing and calcining to obtain the porous silicon dioxide microspheres; wherein the ammonia water ethanol solution is prepared by mixing 25% mass concentration ammonia water solution and absolute ethyl alcohol in a volume ratio of 1: 5 stirring and mixing evenly.
The polystyrene seed had a particle size of 1.5 μm with CV of 3%.
The adding speed of the ethyl orthosilicate solution and the ammonia water ethanol solution to the seed suspension is 3.5mL/min and 2mL/min respectively.
In the step (1), the preparation method of the blank body comprises the following steps: 1g of zirconyl nitrate hydrate, 0.3g of porous silica microspheres, 0.3g of polyethylene glycol 400, 0.03g of 2,4, 6-trimethylbenzoylphosphonic acid ethyl ester and 7g of ethylene glycol are mixed and ground under a dark condition to prepare slurry; then, the slurry is dripped into 15g of dimethyl silicone oil drop by drop to form spherical liquid drops; and then irradiating by ultraviolet light, carrying out photocuring, centrifuging, washing and drying to obtain the blank.
The photocuring time was 15 minutes.
In the step (1), the specific method of the nitriding sintering treatment comprises the following steps: spreading the blank at the bottom of a crucible, covering a graphite plate above the crucible, continuously introducing argon at the flow rate of 50mL/min, heating to 800 ℃, continuously introducing nitrogen at the flow rate of 200mL/min, continuously heating to 1500 ℃, preserving heat for 3 hours, and naturally cooling to room temperature.
The heating rate is 10 ℃/min, and the nitrogen gas is stopped to be introduced when the temperature is naturally cooled to 300 ℃.
The specific method of the step (2) is as follows: and adding 1g of the composite microspheres into 10g of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
In the step (3), the specific method for depositing the barium strontium titanate film on the back surface of the glass substrate is as follows: preparing corresponding solutions of 0.06g of barium nitrate, 0.17g of strontium nitrate, 0.25g of ammonium fluotitanate and 0.19g of boric acid by respectively using 100g of water, mixing and stirring the solutions uniformly, adjusting the pH value to be 3.2, and vacuumizing until no bubbles are discharged to obtain a premixed solution; then completely immersing the glass substrate into a Piranha solution, performing immersion treatment for 2 hours, cleaning with ethanol, drying with nitrogen, completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, performing immersion treatment for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 25 hours at 52 ℃, taking out and drying to deposit the barium strontium titanate film on the back surface of the glass substrate.
In the step (3), the spin coating process conditions are as follows: the rotating speed is 6000r/min, and the spin coating time is 50 s.
In the step (3), the post-treatment process conditions are as follows: treated at 600 ℃ for 5 hours.
Comparative example 3
A glass packaging method for improving LED light-emitting rate, as shown in figure 2, sequentially stacking a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8 and a glass substrate 10 from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1; the light reflecting layer 12 is processed on the back surface of the glass substrate 10 by the following specific method:
(1) firstly, antimony oxide is used as a raw material to prepare a premix for later use;
(2) then, a barium strontium titanate film is deposited on the back surface of the glass substrate 10, and then a premix is spin-coated on the surface of the barium strontium titanate film, and post-treatment is performed to form the light reflection layer 12.
The metal conductive layer 8 is divided into a region N and a region P which are respectively bonded to the glass substrate 10 through the metal adhesion layer 9; welding corresponding metal electrodes 6, namely a metal electrode N and a metal electrode P on the region N and the region P respectively through conductive welding materials 7, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and is in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is coated on the periphery of the gallium nitride layer, wherein the side surface of the metal electrode N penetrating through the gallium nitride layer part is also coated with the inorganic insulating medium.
The metal adhesion layer 9 is made of titanium nitride, and the inorganic insulating medium 5 is aluminum nitride.
The specific method of the step (1) is as follows: and adding 5g of antimony oxide into 10g of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
In the step (2), the specific method for depositing the barium strontium titanate film on the back surface of the glass substrate is as follows: preparing corresponding solutions of 0.06g of barium nitrate, 0.17g of strontium nitrate, 0.25g of ammonium fluotitanate and 0.19g of boric acid by respectively using 100g of water, mixing and stirring the solutions uniformly, adjusting the pH value to be 3.2, and vacuumizing until no bubbles are discharged to obtain a premixed solution; then completely immersing the glass substrate into a Piranha solution, soaking for 2 hours, cleaning with ethanol, drying with nitrogen, then completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, soaking for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 25 hours at 52 ℃, taking out and drying to deposit the barium strontium titanate film on the back surface of the glass substrate.
In the step (2), the spin coating process conditions are as follows: the rotating speed is 6000r/min, and the spin coating time is 50 s.
In the step (2), the process conditions of the post-treatment are as follows: the treatment was carried out at 600 ℃ for 5 hours.
Comparative example 4
A glass packaging method for improving LED light-emitting rate, as shown in figure 2, sequentially stacking a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8 and a glass substrate 10 from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1; the light reflecting layer 12 is processed on the back surface of the glass substrate 10 by the following specific method: a barium strontium titanate thin film is deposited on the back surface of the glass substrate 10 to form the light reflecting layer 12.
The metal conductive layer 8 is divided into a region N and a region P which are respectively bonded to the glass substrate 10 through the metal adhesion layer 9; welding corresponding metal electrodes 6, namely a metal electrode N and a metal electrode P on the region N and the region P respectively through conductive welding materials 7, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and is in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is applied to the periphery of the gallium nitride layer, wherein the side of the metal electrode N that passes through the gallium nitride layer portion is also coated with the inorganic insulating medium.
The metal adhesion layer 9 is made of titanium nitride, and the inorganic insulating medium 5 is aluminum nitride.
The specific method for depositing the barium strontium titanate film on the back surface of the glass substrate is as follows: preparing corresponding solutions of 0.06g of barium nitrate, 0.17g of strontium nitrate, 0.25g of ammonium fluotitanate and 0.19g of boric acid by respectively using 100g of water, mixing and stirring the solutions uniformly, adjusting the pH value to be 3.2, and vacuumizing until no bubbles are discharged to obtain a premixed solution; then completely immersing the glass substrate into a Piranha solution, soaking for 2 hours, cleaning with ethanol, drying with nitrogen, then completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, soaking for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 25 hours at 52 ℃, taking out and drying to deposit the barium strontium titanate film on the back surface of the glass substrate.
Comparative example 5
A glass packaging method for improving LED light-emitting rate, as shown in figure 2, sequentially stacking a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8 and a glass substrate 10 from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1; the light reflecting layer 12 is processed on the back surface of the glass substrate 10 by the following specific method:
(1) firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material, then mixing zirconyl nitrate hydrate and the porous silicon dioxide microspheres to prepare slurry, forming a blank body through photocuring, and performing nitridation sintering treatment to obtain composite microspheres;
(2) then, preparing a premix by taking the composite microspheres and antimony oxide as raw materials for later use;
(3) then, the light reflecting layer 12 is formed by spin-coating a premix on the back surface of the glass substrate 10 and post-processing.
The metal conductive layer 8 is divided into a region N and a region P which are respectively bonded to the glass substrate 10 through the metal adhesion layer 9; welding corresponding metal electrodes 6, namely a metal electrode N and a metal electrode P on the region N and the region P respectively through conductive welding materials 7, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and is in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is applied to the periphery of the gallium nitride layer, wherein the side of the metal electrode N that passes through the gallium nitride layer portion is also coated with the inorganic insulating medium.
The metal adhesion layer 9 is made of titanium nitride, and the inorganic insulating medium 5 is aluminum nitride.
In the step (1), the preparation method of the porous silica microspheres comprises the following steps: firstly, adding 1g of polystyrene seeds into 12g of ammonia water ethanol solution, and uniformly stirring and dispersing to obtain a seed suspension; adding 3g of tetraethoxysilane into 6g of absolute ethyl alcohol, and uniformly stirring and dispersing to obtain a tetraethoxysilane solution; then simultaneously adding the ethyl orthosilicate solution and 7g of ammonia water ethanol solution into the seed suspension, stirring and reacting for 3 hours, standing for 2 hours, centrifuging, washing and calcining to obtain the porous silicon dioxide microspheres; wherein the ammonia-water ethanol solution is prepared by mixing an ammonia-water solution with the mass concentration of 25% and absolute ethyl alcohol according to the volume ratio of 1: 5 stirring and mixing evenly.
The polystyrene seed had a particle size of 1.5 μm and CV of 3%.
The adding speed of the tetraethoxysilane solution and the ammonia water ethanol solution to the seed suspension is 3.5mL/min and 2mL/min respectively.
In the step (1), the preparation method of the blank body comprises the following steps: 1g of zirconyl nitrate hydrate, 0.3g of porous silica microspheres, 0.3g of polyethylene glycol 400, 0.03g of 2,4, 6-trimethylbenzoylphosphonic acid ethyl ester and 7g of ethylene glycol are mixed and ground under a dark condition to prepare slurry; then, dropwise adding the slurry into 15g of dimethyl silicone oil to form spherical liquid drops; and then irradiating by ultraviolet light, carrying out photocuring, centrifuging, washing and drying to obtain the blank.
The photocuring time was 15 minutes.
In the step (1), the specific method of the nitriding sintering treatment comprises the following steps: spreading the blank at the bottom of a crucible, covering a graphite plate above the crucible, continuously introducing argon at the flow rate of 50mL/min, heating to 800 ℃, continuously introducing nitrogen at the flow rate of 200mL/min, continuously heating to 1500 ℃, preserving heat for 3 hours, and naturally cooling to room temperature.
The heating rate is 10 ℃/min, and the nitrogen is stopped to be introduced when the temperature is naturally cooled to 300 ℃.
The specific method of the step (2) is as follows: and adding 1g of composite microspheres and 5g of antimony oxide into 10g of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
In the step (3), the spin coating process conditions are as follows: the rotating speed is 6000r/min, and the spin coating time is 50 s.
In the step (3), the post-treatment process conditions are as follows: the treatment was carried out at 600 ℃ for 5 hours.
Comparative example 6
Fig. 1 is a longitudinal sectional view of a conventional glass substrate package structure, in which a sapphire substrate 1, a gallium nitride layer, a metal conductive layer 8, and a glass substrate 10 are sequentially stacked from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer 2, a gallium nitride epitaxial light-emitting layer 3 and a gallium nitride epitaxial P-type layer 4 along the direction far away from the sapphire substrate 1, and the metal conducting layer 8 is divided into a region N and a region P and is respectively bonded to the glass substrate 10 through a metal adhesion layer 9; silver-plated reflecting layers 11 are respectively arranged on the surfaces of the region N and the region P, and corresponding metal electrodes 6, namely the metal electrodes N and the metal electrodes P are respectively welded through conductive welding materials 7, wherein the metal electrodes N sequentially penetrate through the gallium nitride epitaxial P-type layer 4 and the gallium nitride epitaxial light-emitting layer 3 and are in contact with the gallium nitride epitaxial N-type layer 2, and the metal electrodes P are in contact with the gallium nitride epitaxial P-type layer 4; an inorganic insulating medium 5 is applied to the periphery of the gallium nitride layer, wherein the side of the metal electrode N that passes through the gallium nitride layer portion is also coated with the inorganic insulating medium. The metal adhesion layer is made of titanium nitride, and the inorganic insulating medium is aluminum nitride.
Test examples
The same LED period is packaged by adopting the methods of examples 1-3 or comparative examples 1-6 respectively, and then the light-emitting rate of the LED is tested, wherein the specific method refers to patent CN102252829B, and the result is shown in Table 1.
TABLE 1 test results of light extraction
| Light emission (%) | |
| Example 1 | 89.5 |
| Example 2 | 85.8 |
| Example 3 | 87.6 |
| Comparative example 1 | 75.2 |
| Comparative example 2 | 68.1 |
| Comparative example 3 | 72.3 |
| Comparative example 4 | 63.6 |
| Comparative example 5 | 69.7 |
| Comparative example 6 | 49.2 |
As can be seen from table 1, the encapsulation methods of examples 1 to 3 greatly improved the light extraction rate compared to comparative example 6 (conventional silver plating method).
In the comparative example 1, zirconyl nitrate hydrate is omitted during preparation of the premix, in the comparative example 2, antimony oxide is omitted during preparation of the premix, in the comparative example 3, the composite microspheres are omitted during preparation of the premix, in the comparative example 4, the premix spin coating is omitted, in the comparative example 5, the barium strontium titanate film is omitted, in the comparative example 6, the traditional silver plating method is adopted, the LED light-emitting rate is obviously reduced, and the synergistic effect of the barium strontium titanate film deposited on the back surface of the glass substrate and the subsequent spin-coating premix is demonstrated to improve the LED light-emitting rate together.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A glass packaging method for improving the light-emitting rate of an LED is characterized in that a sapphire substrate, a gallium nitride layer, a metal conducting layer and a glass substrate are sequentially stacked from top to bottom; the gallium nitride layer comprises a gallium nitride epitaxial N-type layer, a gallium nitride epitaxial light-emitting layer and a gallium nitride epitaxial P-type layer along the direction far away from the sapphire substrate; the method for processing the light reflecting layer on the back surface of the glass substrate comprises the following steps:
(1) firstly, preparing porous silicon dioxide microspheres by taking polystyrene as a template and tetraethoxysilane as a raw material, then mixing zirconyl nitrate hydrate and the porous silicon dioxide microspheres to prepare slurry, forming a blank body through photocuring, and performing nitridation sintering treatment to obtain composite microspheres;
(2) then, preparing a premix by taking the composite microspheres and antimony oxide as raw materials for later use;
(3) then depositing a barium strontium titanate film on the back surface of the glass substrate, then spin-coating premix on the surface of the barium strontium titanate film, and performing post-treatment to form the light reflection layer.
2. The glass packaging method for improving the light extraction rate of the LED according to claim 1, wherein the metal conductive layer is divided into a region N and a region P, and the regions N and P are respectively bonded to the glass substrate through metal adhesion layers; respectively welding a metal electrode N and a metal electrode P on the region N and the region P through conductive welding materials, wherein the metal electrode N sequentially penetrates through the gallium nitride epitaxial P-type layer and the gallium nitride epitaxial light-emitting layer and is in contact with the gallium nitride epitaxial N-type layer, and the metal electrode P is in contact with the gallium nitride epitaxial P-type layer; and coating an inorganic insulating medium on the periphery of the gallium nitride layer, wherein the side surface of the metal electrode N penetrating through the gallium nitride layer part is also coated with the inorganic insulating medium.
3. The glass packaging method for improving the light-emitting efficiency of the LED according to claim 1, wherein in the step (1), the preparation method of the porous silica microspheres comprises the following steps in parts by weight: firstly, adding 1 part of polystyrene seeds into 12-15 parts of ammonia water ethanol solution, and uniformly stirring and dispersing to obtain a seed suspension; adding 2-3 parts of tetraethoxysilane into 6-8 parts of absolute ethyl alcohol, and uniformly stirring and dispersing to obtain tetraethoxysilane solution; then simultaneously adding an ethyl orthosilicate solution and 5-7 parts of an ammonia water ethanol solution into the seed suspension, stirring and reacting for 3-4 hours, standing for 1-2 hours, centrifuging, washing, calcining, and recording to obtain the porous silicon dioxide microspheres; wherein the ammonia water ethanol solution is prepared by mixing 25% mass concentration ammonia water solution and absolute ethyl alcohol in a volume ratio of 1: 5 stirring and mixing evenly.
4. The glass packaging method for improving the light-emitting efficiency of the LED according to claim 1, wherein in the step (1), the preparation method of the green body comprises the following steps in parts by weight: firstly, under the condition of keeping out of the sun, mixing and grinding 1 part of zirconyl nitrate hydrate, 0.3-0.5 part of porous silica microspheres, 0.2-0.3 part of polyethylene glycol 400, 0.03-0.05 part of ethyl 2,4, 6-trimethylbenzoylphosphonate and 5-7 parts of ethylene glycol to prepare slurry; then, dropwise adding the slurry into 15-17 parts of dimethyl silicone oil to form spherical liquid drops; and then irradiating by ultraviolet light, carrying out photocuring, centrifuging, washing and drying to obtain the blank.
5. The glass packaging method for improving the light-emitting efficiency of the LED according to claim 1, wherein in the step (1), the specific method of the nitridation sintering treatment is as follows: the method comprises the steps of firstly, flatly paving a blank at the bottom of a crucible, covering a graphite plate above the crucible, continuously introducing argon at the flow rate of 50mL/min, heating to 800 ℃, continuously introducing nitrogen at the flow rate of 200mL/min, continuously heating to 1500 ℃, preserving heat for 3-4 hours, and naturally cooling to room temperature.
6. The glass packaging method for improving the light-emitting efficiency of the LED according to claim 1, wherein the specific method in the step (2) comprises the following steps in parts by weight: adding 1 part of composite microspheres and 3-5 parts of antimony oxide into 10-12 parts of polyethylene glycol 200, and grinding and uniformly mixing to obtain the premix.
7. The glass packaging method for improving the light extraction efficiency of the LED according to claim 1, wherein in the step (3), the specific method for depositing the barium strontium titanate film on the back surface of the glass substrate in parts by weight is as follows: respectively preparing 0.05-0.06 part of barium nitrate, 0.17-0.18 part of strontium nitrate, 0.2-0.25 part of ammonium fluotitanate and 0.19-0.21 part of boric acid into corresponding solutions by using 100 parts of water, mixing and stirring the solutions uniformly, adjusting the pH = 3-3.2, vacuumizing until no air bubbles are discharged, and obtaining a premixed solution; then completely immersing the glass substrate into a Piranha solution, soaking for 2 hours, cleaning with ethanol, drying with nitrogen, then completely immersing the glass substrate into an octadecyl trichlorosilane toluene solution with the mass concentration of 1%, soaking for 35 minutes, taking out, cleaning with ethyl acetate, and drying with nitrogen to obtain a pretreated glass substrate; and finally, completely immersing the glass substrate into the premixed solution, standing for 20-25 hours at 52-55 ℃, taking out and drying to deposit the barium strontium titanate film on the back surface of the glass substrate.
8. The glass packaging method for improving the light extraction rate of the LED according to claim 1, wherein in the step (3), the spin coating process conditions are as follows: the rotation speed is 6000 to 7000r/min, and the spin coating time is 40 to 50 s.
9. The glass packaging method for improving the light extraction rate of the LED according to claim 1, wherein in the step (3), the post-treatment process conditions are as follows: treating at 600-700 deg.C for 3-5 hours.
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| CN86107671A (en) * | 1985-11-22 | 1987-07-15 | 明尼苏达州采矿制造公司 | Transparent non-vitreous zirconia microspheres and process for preparing thereof |
| JP2000113682A (en) * | 1998-09-30 | 2000-04-21 | Kyocera Corp | Optical recording device |
| JP2006227162A (en) * | 2005-02-16 | 2006-08-31 | Konica Minolta Opto Inc | Antireflection film, method of manufacturing antireflection film, polarizing plate, and display device |
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