CN117374198A - White light LED packaging structure and preparation method thereof - Google Patents
White light LED packaging structure and preparation method thereof Download PDFInfo
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- CN117374198A CN117374198A CN202311522292.0A CN202311522292A CN117374198A CN 117374198 A CN117374198 A CN 117374198A CN 202311522292 A CN202311522292 A CN 202311522292A CN 117374198 A CN117374198 A CN 117374198A
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- 238000004806 packaging method and process Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title description 7
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000011521 glass Substances 0.000 claims abstract description 60
- 239000002861 polymer material Substances 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 50
- 230000005284 excitation Effects 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 238000002834 transmittance Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 239000003292 glue Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- -1 rare earth ion Chemical class 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 238000009877 rendering Methods 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 19
- 239000004205 dimethyl polysiloxane Substances 0.000 description 9
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 9
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 9
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
Abstract
The white light LED packaging structure consists of an excitation layer and a fluorescence conversion layer, wherein the excitation layer consists of an LED chip; the fluorescent conversion layer consists of a fluorescent material layer and a polymer material layer, wherein the fluorescent material layer comprises a glass or ceramic matrix and a fluorescent substance, and the fluorescent substance comprises a first fluorescent substance, a second fluorescent substance and a third fluorescent substance; the polymer material layer is a high polymer material with higher light transmittance in the visible light band, and the surface of the polymer material layer is provided with a concave microstructure. The white light LED packaging structure can improve the luminous efficiency and the color rendering index of the device so as to meet the application requirements of high-performance white light LED devices.
Description
Technical Field
The invention relates to the technical field of white light LED devices, in particular to a white light LED packaging structure and a preparation method thereof.
Background
The luminous efficiency of a white light LED device is an important index for measuring the performance of the device, and besides factors such as the light transmittance of a packaging material, the chip efficiency, the quantum efficiency of a fluorescent material and the like, the structure of the device also has important influence on the luminous efficiency. Light emitted by the LED chip can be emitted into the air after being conducted by the packaging material and the fluorescent material, and when the light is transmitted from the medium with high refractive index to the medium with low refractive index, the larger the refractive index difference between the two mediums is, the larger the probability of total reflection of the light is; in addition, as the exit angle of light is larger, total reflection is more likely to occur. The total reflection effect enables only a small part of light emitted by the device to directly escape, and most of light can only be limited to be dissipated in the device in a thermal mode after being reflected, so that the luminous efficiency of the device is reduced.
The structural design is an effective method for improving the luminous efficiency of the white light LED device, and can reduce the probability of total reflection of light emitted from the device, thereby improving the performance of the device. The CN104037276a patent proposes a white LED device with a package structure having a gradient refractive index, in which the refractive index of the light conversion layer from the LED chip to the outside is reduced layer by packaging the light conversion layer uniformly mixed with fluorescent powder and nano scattering agents with different contents layer by layer on the chip. Through the gradient refractive index multilayer structure, the probability of total reflection during light emergence is reduced, and the extraction capacity of the white light device for emitted light is improved. However, the multilayer packaging structure of the scheme contains fluorescent powder, and as the refractive index of the fluorescent powder is larger than that of the packaging material, the probability of scattering light emitted by the chip by the fluorescent powder is increased, and the performance of the device is affected to a certain extent.
The gradient refractive index fluorescent glass LED packaging structure provided by the CN106517816A patent comprises a glass substrate and a plurality of layers of fluorescent glass coatings on the surface of the glass substrate, wherein each layer of fluorescent glass coating is prepared by taking modified glass powder and fluorescent powder as raw materials and adopting a plurality of layers of screen printing and low-temperature sintering technologies. The adoption of the gradient refractive index structure can reduce the phenomena of total reflection and Fresnel reflection of light emitted from the chip on the packaging interface due to large refractive index change, thereby improving the light-emitting efficiency and effectively solving the problem of poor stability of the device. However, the preparation process in the method is complicated, the industrial production is not facilitated, and the fluorescent glass slurry for screen printing also has the problem of poor fluorescent powder dispersibility.
Disclosure of Invention
In order to solve the problems in the prior art and improve the optical performance and reliability of a white light LED packaging device, the invention provides a white light LED packaging structure and a packaging method thereof, and the luminous efficiency and stability of the device can be obviously improved through the design of the packaging structure, so that the application requirements of the white light LED packaging device are met.
A white light LED packaging structure comprises an excitation layer composed of LED chips and a fluorescence conversion layer positioned above the excitation layer;
the fluorescent conversion layer consists of a fluorescent material layer and a polymer material layer, wherein the fluorescent material layer comprises packaging glue, a glass or ceramic matrix, a first fluorescent substance, a second fluorescent substance and a third fluorescent substance;
the packaging glue is epoxy resin or organic silica gel;
the glass or ceramic matrix is at least one of borate, silicate, phosphate and tellurate;
the mass ratio of the first fluorescent substance to the second fluorescent substance to the third fluorescent substance is as follows: (10% -40%): (10% -40%): (40% -90%);
the polymer material layer is at least one of high molecular polymers with the light transmittance of more than 90% in the visible light wave band.
A preparation method of a white light LED packaging structure comprises the following steps:
preparing a fluorescent material layer in the fluorescent conversion layer: fully grinding glass or ceramic matrix raw materials in an agate mortar, adding a first fluorescent substance, a second fluorescent substance and a third fluorescent substance, fully mixing the materials, sintering the materials at the temperature ranging from 300 ℃ to 1500 ℃, and cooling the materials to room temperature to obtain a fluorescent material layer;
preparing a polymer material layer in the fluorescent conversion layer: a method of directly coating or dissolving a polymer material in toluene and N, N-dimethylformamide and then coating the polymer material, and forming a polymer material layer on the surface of the fluorescent material layer; the relative humidity in the weather-proof box is 50-85%, the temperature is 5-20 ℃, the whole fluorescent material layer is put into the weather-proof box after the whole fluorescent material layer is lower than the temperature of the weather-proof box, and water drops are condensed on the surface of the polymer in a high humidity environment to form a concave microstructure array; taking out the fluorescent material layer from the weather-proof box, solidifying the polymer material layer on the surface and evaporating water drops to obtain the polymer material layer with the concave microstructure array on the surface;
and (3) packaging: and coating packaging glue on the periphery of the excitation layer, and then adhering the fluorescent conversion layer on the excitation layer in the order that the fluorescent material layer is close to the excitation layer and the polymer material layer is far away from the excitation layer.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through the refractive index difference between the polymer material layer and the fluorescent material layer and the concave microstructure array, the probability of total reflection during the emission of internal light is reduced, so that the interface incidence angle of the light is reduced, the light is easier to emit from the fluorescent conversion layer, and the luminous efficiency and the color rendering index of the device are improved.
Drawings
Fig. 1 is a schematic structural diagram of the present invention: numbering in the figures: 1. an LED chip; 2. a glass substrate; 3. a first fluorescent substance; 4. a second fluorescent substance; 5. a third fluorescent substance; 6. a layer of polymeric material;
FIG. 2 is an electroluminescence spectrum of a white light LED device in which PDMS is selected as a polymer material layer in example 1 of the present invention and a white light LED device without a polymer layer in comparative example 1;
FIG. 3 is a graph showing the change of the luminous intensity with current for the white LED device of example 1 of the present invention when PDMS was selected as the polymer material layer and the white LED device of comparative example 1 without the polymer layer;
FIG. 4 is a graph showing the change in luminous efficiency with current for a white LED device of example 1 of the present invention when PDMS is selected as the polymer material layer and a white LED device of comparative example 1 without the polymer layer;
fig. 5 is a graph showing the color rendering index versus current for the white LED device of example 1 of the present invention when PDMS is selected as the polymer material layer and the white LED device of comparative example 1 without the polymer layer.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments so that those skilled in the art can fully understand the technical contents of the present invention. The scope of the present invention includes all other embodiments that can be made by those skilled in the art without the need for inventive faculty on the basis of the embodiments of the present invention described.
The white light LED packaging structure provided by the invention consists of an excitation layer and a fluorescence conversion layer, wherein the fluorescence conversion layer is positioned above the excitation layer.
The excitation layer consists of an LED chip, the fluorescence conversion layer consists of a fluorescent material layer and a polymer material layer, and the fluorescent material layer comprises packaging glue, a glass or ceramic matrix, a first fluorescent substance, a second fluorescent substance and a third fluorescent substance;
the packaging glue is epoxy resin, organic silica gel and the like;
the glass or ceramic matrix is borate, silicate, phosphate, tellurate and the like;
the first fluorescent material emits light with peak wavelength of 420 to 500nm under the excitation of ultraviolet light or blue light wavelength; the first fluorescent material comprises Eu doped 2+ 、Ce 3+ 、Bi 3+ Silicate, aluminate, nitride, phosphate of at least one rare earth ion;
the second fluorescent material emits light with peak wavelength of 500-590 nm under the excitation of ultraviolet light or blue light wavelength; the second fluorescent material comprises Dy doped 3+ 、Bi 3+ 、Ce 3+ 、Tb 3+ 、Eu 2+ At least one rare earth ion or Mn 2+ Silicate, aluminate, nitride, phosphate of transition metal ions;
the third fluorescent material emits light with peak wavelength of 590 to 700nm under the excitation of ultraviolet light or blue light wavelength; the third fluorescent material comprises Sm 3+ 、Pr 3+ 、Eu 2+ 、Eu 3+ 、Ce 3+ At least one rare earth ion or Mn 4+ 、Mn 2+ Silicate, germanate, nitride, phosphate, fluoride of at least one transition metal ionA chemical compound;
the mass ratio of the first fluorescent substance to the second fluorescent substance to the third fluorescent substance is as follows: (10% -40%): (10% -40%): (40% -90%);
the polymer material layer comprises at least one polymer with light transmittance of more than 90% in the visible light band, such as Polycarbonate (PC), polymethyl methacrylate (PMMA), styrene block copolymer (SEBS), polyvinyl chloride (PVC), polyurethane elastomer (TPU), polyethylene (PE), fluorinated Ethylene Propylene (FEP), styrene Methyl Methacrylate (SMMA) and the like.
The refractive index of the selected polymer material layer is smaller than or equal to that of the fluorescent material layer;
the packaging structure of the white light LED and the packaging method thereof are characterized in that the packaging position of a fluorescent material layer in the fluorescent conversion layer is close to the LED chip, and the packaging position of a polymer material layer is far away from the LED chip;
the packaging structure of the white light LED and the packaging method thereof are characterized in that an excitation light source of the excitation layer is an LED ultraviolet light or purple light or blue light chip, and the emission wavelength of the excitation light source is between 200nm and 480nm;
a preparation method of a white light LED packaging structure comprises the following steps:
preparing a fluorescent material layer in the fluorescent conversion layer: fully grinding glass or ceramic matrix raw materials in an agate mortar, adding a first fluorescent substance, a second fluorescent substance and a third fluorescent substance, fully mixing the materials, sintering the materials at the temperature ranging from 300 ℃ to 1500 ℃, and cooling the materials to room temperature to obtain a fluorescent material layer;
preparing a polymer material layer in the fluorescent conversion layer: a method of directly coating or dissolving a polymer material in toluene and N, N-dimethylformamide and then coating the polymer material, and forming a polymer material layer on the surface of the fluorescent material layer; the relative humidity in the weather-proof box is 50-85%, the temperature is 5-20 ℃, the whole fluorescent material layer is put into the weather-proof box after the whole fluorescent material layer is lower than the temperature of the weather-proof box, and water drops are condensed on the surface of the polymer in a high humidity environment to form a concave microstructure array; taking out the fluorescent material layer from the weather-proof box, solidifying the polymer material layer on the surface and evaporating water drops to obtain the polymer material layer with the concave microstructure array on the surface;
and (3) packaging: and coating packaging glue on the periphery of the excitation layer, and then adhering the fluorescent conversion layer on the excitation layer in the order that the fluorescent material layer is close to the excitation layer and the polymer material layer is far away from the excitation layer.
The present invention will be described in detail with reference to the accompanying drawings, tables and examples.
As shown in fig. 1, the present invention is a package structure of a white LED, which includes an excitation layer and a fluorescent conversion layer. The excitation layer is composed of an LED chip 1, the fluorescent material layer in the fluorescent conversion layer comprises a glass or ceramic matrix 2 and fluorescent substances, wherein the fluorescent substances comprise a first fluorescent substance 3, a second fluorescent substance 4 and a third fluorescent substance 5, and the mass ratio of the first fluorescent substance to the second fluorescent substance to the third fluorescent substance is as follows: (10% -40%): (10% -40%): (40% -90%); the polymer material layer 6 is a polymer material with a light transmittance of 90% or more in the visible light range, and has a concave microstructure on its surface.
In the following examples and comparative examples, the excitation light source was an LED chip having an emission peak wavelength of 400nm, and the chip operating power was 0.5W. SiO (SiO) 2 The refractive index of the glass is between 1.45 and 1.47, the refractive index of the PMDS is between 1.38 and 1.42, the refractive index of the SEBS is between 1.40 and 1.45, and the refractive index of the TPU is between 1.40 and 1.44.
Example 1: white light LED packaging structure with PDMS as polymer material layer
The chemical formulas of the first, second and third fluorescent substances in the fluorescent material layer are respectively K 1.55 Al 11 O 17 :0.05Eu 2+ 、Ca 1.9 YHf 2 Al 3 O 12 :0.05Ce 3+ ,0.05Tb 3+ 、K 2 Ca 0.95 PO 4 F:0.05Eu 2+ The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the three components is 15 percent to 70 percent; the glass matrix comprises SiO 2 . Fluorescent material and SiO 2 Weighing 0.5g of mixed powder according to the mass ratio of 1:5, fully grinding for 30min, putting into a graphite grinding tool with the diameter of 10mm, and then putting into a discharge plasma sintering furnace for sintering. Sintering temperature of 1050The sintering pressure is 50MPa, and the heat preservation time is 2min. And (3) polishing the cooled sample by double-sided grinding to obtain the fluorescent glass wafer with the diameter of 10mm and the thickness of 1 mm.
After weighing 0.25g of PDMS main agent and 0.025g of PDMS curing agent, the mixture is fully mixed for 10min, and then the mixture is kept stand for 30min to remove internal bubbles. Uniformly coating the glass on the upper surface of fluorescent glass, transferring the glass into an oven at 50 ℃ for about 30min for pre-curing, taking out the glass, putting the glass into a refrigerator freezing layer at about minus 10 ℃ for 2h, taking out the glass, rapidly putting the glass into a weather-proof box with the environmental condition of 15 ℃ and 75% relative humidity in the box, condensing water drops on the surface of the polymer under the condition of high humidity, taking out the glass after 10min, transferring the glass into the oven for drying at 50 ℃ for 4h for curing the polymer film and evaporating the water drops, and finally obtaining the fluorescent glass with the concave microstructure array polymer layer on the surface.
According to the relative position that the polymer layer is far away from the LED chip and the fluorescent glass layer is close to the LED chip, placing fluorescent glass on the chip, filling gaps between the glass and the chip by using epoxy resin as packaging glue, and naturally curing in air for 6 hours to obtain the white light LED.
Example 2: white light LED packaging structure with SEBS as polymer material layer
The chemical formulas of the first, second and third fluorescent substances in the fluorescent material layer are respectively K 1.55 Al 11 O 17 :0.05Eu 2+ 、Ca 1.9 YHf 2 Al 3 O 12 :0.05Ce 3+ ,0.05Tb 3+ 、K 2 Ca 0.95 PO 4 F:0.05Eu 2+ The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the three components is 15 percent to 70 percent; the glass matrix comprises SiO 2 . Fluorescent material and SiO 2 Weighing 0.5g of mixed powder according to the mass ratio of 1:5, fully grinding for 30min, putting into a graphite grinding tool with the diameter of 10mm, and then putting into a discharge plasma sintering furnace for sintering. The sintering temperature is 1050 ℃, the sintering pressure is 50MPa, and the heat preservation time is 2min. And (3) polishing the cooled sample by double-sided grinding to obtain the fluorescent glass wafer with the diameter of 10mm and the thickness of 1 mm.
After weighing 0.1g of SEBS, dissolving the SEBS in 1ml of toluene solvent, fully mixing for 10min, standing for 30min to remove internal bubbles, and uniformly coating the SEBS on the upper surface of fluorescent glass. After the coating was completed, the fluorescent glass was left in air at room temperature for 15min to partially evaporate toluene, and the polymer layer was pre-cured. And (3) placing the fluorescent glass in a refrigerator freezing layer with the temperature of about minus 10 ℃ for 2 hours, taking out, rapidly placing the fluorescent glass in a weather-resistant box with the environmental condition of 15 ℃ and 75% relative humidity in the box, condensing water drops on the surface of the polymer under the condition of high humidity, taking out after 10 minutes, transferring the fluorescent glass into an oven, drying the fluorescent glass at 30 ℃ for 1 hour to solidify the polymer film and evaporate the water drops, and finally obtaining the fluorescent glass with the concave microstructure array polymer layer on the surface.
According to the relative position that the polymer layer is far away from the LED chip and the fluorescent glass layer is close to the LED chip, placing fluorescent glass on the chip, filling gaps between the glass and the chip by using epoxy resin as packaging glue, and naturally curing in air for 6 hours to obtain the white light LED.
Example 3: white light LED packaging structure with TPU as polymer material layer
The chemical formulas of the first, second and third fluorescent substances in the fluorescent material layer are respectively K 1.55 Al 11 O 17 :0.05Eu 2+ 、Ca 1.9 YHf 2 Al 3 O 12 :0.05Ce 3+ ,0.05Tb 3+ 、K 2 Ca 0.95 PO 4 F:0.05Eu 2+ The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the three components is 15 percent to 70 percent; the glass matrix comprises SiO 2 . Phosphor material and SiO 2 Weighing 0.5g of powder according to the mass ratio of 1:5, fully grinding for 30min, loading into a graphite grinding tool with the diameter of 10mm, and then placing into a discharge plasma sintering furnace for sintering. The sintering temperature is 1050 ℃, the sintering pressure is 50MPa, and the heat preservation time is 2min. And (3) polishing the cooled sample by double-sided grinding to obtain the fluorescent glass wafer with the diameter of 10mm and the thickness of 1 mm.
After weighing 0.15g of TPU, dissolving the TPU in 1ml of toluene solvent, fully mixing for 10min, standing for 30min to remove internal bubbles, and uniformly coating the TPU on the upper surface of fluorescent glass. After the coating was completed, the fluorescent glass was left in air at room temperature for 15min to partially evaporate toluene, and the polymer layer was pre-cured. And (3) placing the fluorescent glass in a refrigerator freezing layer with the temperature of about minus 10 ℃ for 2 hours, taking out, rapidly placing the fluorescent glass in a weather-resistant box with the environmental condition of 15 ℃ and 75% relative humidity in the box, condensing water drops on the surface of the polymer under the condition of high humidity, taking out after 10 minutes, transferring the fluorescent glass into an oven, drying the fluorescent glass at 30 ℃ for 1 hour to solidify the polymer film and evaporate the water drops, and finally obtaining the fluorescent glass with the concave microstructure array polymer layer on the surface.
According to the relative position that the polymer layer is far away from the LED chip and the fluorescent glass layer is close to the LED chip, placing fluorescent glass on the chip, filling gaps between the glass and the chip by using epoxy resin as packaging glue, and naturally curing in air for 6 hours to obtain the white light LED.
Comparative example 1
The preparation conditions of comparative example 1 were set based on example 1, except that the fluorescent conversion layer in comparative example 1 did not have a polymer material layer, which is also the main method of currently using fluorescent glass or ceramic in white LEDs, otherwise the same as in example 1.
Fig. 2 is an electroluminescence spectrum of example 1 and comparative example 1, in which the power of the test device was 0.5W, and it can be seen from the graph that example 1 is partially improved compared to the spectrum intensity of comparative example 1, and no new luminescence peak position is shown, indicating that the luminescence intensity of the device can be improved without causing a change in the luminescence peak position when PDMS is contained in the fluorescent conversion layer as a polymer material layer for example 1 and comparative example 1.
Fig. 3 is a graph showing that the addition of the polymer material layer makes the device exhibit a relatively higher light emission intensity compared with the light emission intensity of comparative example 1 at a different driving current when the voltage is fixed at 30V, and this trend is maintained with an increase in driving current, so that the addition of the PDMS polymer layer does not result in a decrease in the stability of the device for example 1 and comparative example 1.
Fig. 4 and 5 are changes in color rendering index and luminous efficiency at different driving currents when the voltage is fixed at 30V in example 1 and comparative example 1, respectively. By the low differential refractive index characteristic of the polymer material layer and the roughened surface characteristic with the concave structure, the probability of total reflection during light emergence is reduced, and therefore the luminous efficiency and the color rendering index of the white light LED device are improved. As can be seen from fig. 4, example 1 shows a higher color rendering index as a whole than comparative example 1 at different driving currents. The luminous efficiency of example 1 in fig. 5 is higher than that of comparative example 1 at each driving current, indicating that the polymer material layer is advantageous for improving the luminous efficiency of the white LED device.
| Luminous efficiency (lm/W) | Color rendering index | Color temperature (K) | |
| Example 1 | 23.27 | 52.3 | 6803 |
| Example 2 | 20.85 | 51.4 | 6854 |
| Example 3 | 21.76 | 51.8 | 6829 |
| Comparative example 1 | 20.09 | 50.9 | 6897 |
The above table lists the color rendering index, luminous efficiency, and color temperature of examples 1-3 and comparative example 1 at a device power fixed at 0.5W. As can be seen from the table, compared with comparative example 1, the performance parameters corresponding to the 3 embodiments are improved to a certain extent, which means that for the white LED device structure, a polymer material layer with refractive index smaller than that of the fluorescent material layer and similar in value is added to the light-emitting surface, and surface roughening treatment is performed on the polymer material layer under a certain condition, so that the performance of the device can be effectively improved.
Claims (7)
1. The white light LED packaging structure is characterized by comprising an excitation layer formed by LED chips and a fluorescence conversion layer positioned above the excitation layer;
the fluorescent conversion layer consists of a fluorescent material layer and a polymer material layer, wherein the fluorescent material layer comprises packaging glue, a glass or ceramic matrix, a first fluorescent substance, a second fluorescent substance and a third fluorescent substance;
the packaging glue is epoxy resin or organic silica gel;
the glass or ceramic matrix is at least one of borate, silicate, phosphate and tellurate;
the mass ratio of the first fluorescent substance to the second fluorescent substance to the third fluorescent substance is as follows: (10% -40%): (10% -40%): (40% -90%);
the polymer material layer is at least one of high molecular polymers with the light transmittance of more than 90% in the visible light wave band.
2. The white light LED packaging structure according to claim 1, wherein the first fluorescent substance emits light with a peak wavelength of 420 to 500nm under the excitation of ultraviolet light, purple light or blue light; first oneThe fluorescent material comprises Eu doped 2+ 、Ce 3+ 、Bi 3+ Silicate, aluminate, nitride, phosphate of at least one rare earth ion;
the second fluorescent material emits light with peak wavelength of 500-590 nm under the excitation of ultraviolet light or blue light wavelength; the second fluorescent material comprises Dy doped 3+ 、Bi 3+ 、Ce 3+ 、Tb 3+ 、Eu 2+ At least one rare earth ion or Mn 2+ Silicate, aluminate, nitride, phosphate of transition metal ions;
the third fluorescent material emits light with peak wavelength of 590 to 700nm under the excitation of ultraviolet light or blue light wavelength; the third fluorescent material comprises Sm 3+ 、Pr 3+ 、Eu 2+ 、Eu 3+ 、Ce 3+ At least one rare earth ion or Mn 4+ 、Mn 2+ Silicate, germanate, nitride, phosphate, fluoride of at least one transition metal ion.
3. The white LED package structure of claim 1, wherein the phosphor layer is encapsulated in a position near the excitation layer and the polymer layer is encapsulated in a position far from the excitation layer.
4. The white light LED package structure according to claim 1, wherein the excitation light source of the excitation layer is an LED ultraviolet light or purple light or blue light chip, and the emission peak wavelength range is 200nm-480nm.
5. The white LED package structure of claim 1, wherein the refractive index of the selected polymer material layer is less than or equal to the refractive index of the phosphor material layer.
6. The white light LED package structure according to claim 1, wherein the polymer material layer is one or more of polycarbonate, polymethyl methacrylate, styrene block copolymer, polyvinyl chloride, polyurethane elastomer, polyethylene, fluorinated ethylene propylene, and styrene methyl methacrylate.
7. A method of making the white LED package structure of claim 1, comprising the steps of:
preparing a fluorescent material layer in the fluorescent conversion layer: fully grinding glass or ceramic matrix raw materials in an agate mortar, adding a first fluorescent substance, a second fluorescent substance and a third fluorescent substance, fully mixing the materials, sintering the materials at the temperature ranging from 300 ℃ to 1500 ℃, and cooling the materials to room temperature to obtain a fluorescent material layer;
preparing a polymer material layer in the fluorescent conversion layer: a method of directly coating or dissolving a polymer material in toluene and N, N-dimethylformamide and then coating the polymer material, and forming a polymer material layer on the surface of the fluorescent material layer; the relative humidity in the weather-proof box is 50-85%, the temperature is 5-20 ℃, the whole fluorescent material layer is put into the weather-proof box after the whole fluorescent material layer is lower than the temperature of the weather-proof box, and water drops are condensed on the surface of the polymer in a high humidity environment to form a concave microstructure array; taking out the fluorescent material layer from the weather-proof box, solidifying the polymer material layer on the surface and evaporating water drops to obtain the polymer material layer with the concave microstructure array on the surface;
and (3) packaging: and coating packaging glue on the periphery of the excitation layer, and then adhering the fluorescent conversion layer on the excitation layer in the order that the fluorescent material layer is close to the excitation layer and the polymer material layer is far away from the excitation layer.
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| CN202311522292.0A CN117374198A (en) | 2023-11-15 | 2023-11-15 | White light LED packaging structure and preparation method thereof |
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