CN106486586A - Light emitting device and method for manufacturing the same - Google Patents
Light emitting device and method for manufacturing the same Download PDFInfo
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- CN106486586A CN106486586A CN201510532841.1A CN201510532841A CN106486586A CN 106486586 A CN106486586 A CN 106486586A CN 201510532841 A CN201510532841 A CN 201510532841A CN 106486586 A CN106486586 A CN 106486586A
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- light
- solvent
- emitting devices
- fluorescent material
- emitting device
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- 238000000034 method Methods 0.000 title description 15
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 140
- 239000011241 protective layer Substances 0.000 claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical group [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims description 119
- 238000004020 luminiscence type Methods 0.000 claims description 56
- 239000000843 powder Substances 0.000 claims description 46
- 239000010408 film Substances 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 15
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- -1 mistake Oxide Substances 0.000 claims description 9
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- 229910052691 Erbium Inorganic materials 0.000 claims description 8
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
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- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001923 cyclic compounds Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N 4-penten-2-one Chemical compound CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910002420 LaOCl Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910003087 TiOx Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910007486 ZnGa2O4 Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005270 trialkylamine group Chemical group 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910052844 willemite Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 2
- 239000011707 mineral Substances 0.000 claims 2
- 239000012876 carrier material Substances 0.000 claims 1
- 210000004027 cell Anatomy 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241000276425 Xiphophorus maculatus Species 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002602 lanthanoids Chemical group 0.000 description 2
- 230000001795 light effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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Classifications
-
- 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
- H01L33/50—Wavelength conversion elements
- H01L33/505—Wavelength conversion elements characterised by the shape, e.g. plate or foil
-
- 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
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
Abstract
The invention discloses a light-emitting device and a preparation method thereof, wherein the light-emitting device comprises: a first light emitting unit; the second light-emitting unit covers the first light-emitting unit and comprises a fluorescent material film and a protective layer; the protective layer is located on the fluorescent material film, the protective layer is a silicon nitrogen material layer, and the tolerance temperature of the light-emitting device exceeds 320 ℃.
Description
Technical field
The present invention is with regard to a kind of light-emitting device, and it is prepared from by novel fluorescent material coating method,
Espespecially a kind of have excellent durability, the light-emitting device of weatherability, resistance to scraping and firm photoluminescent property.
Background technology
In recent years, because light emitting diode (LED) has, luminous efficiency is high, power consumption is few, service life
The advantages of length and component size are little, is widely used in various light-emitting devices.However, luminous two
Pole pipe has the problems such as radiating, luminance shortage and descending luminance, and cannot directly inspire white light, because
This, existing many research attempts develop efficient white light LEDs, to replace existing luminaire.
The white light LEDs of main flow at present, coordinate the YAG of gold-tinted glimmering using blue LED chip
Light powder body, with as white light source.Although with this produced white light of complementary color principle, its spectral wavelength
The seriality of distribution is not so good as sunlight, and the uneven situation of colored, therefore color saturation is relatively low.According to
This, the white light source producing in this way can only be used to simply illuminate, and cannot be widely applied to the people
Raw illumination market.Additionally, also can be utilized ultraviolet light-emitting diodes chip cooperation HONGGUANG, green glow, with
And blue light three-color phosphor, by red bluish-green trichromatic light mixing mechanism, white light can be mixed into.
At present, formed and can send the light emitting diode of white light and be packaged using following methods.First,
Weigh more than one fluorescent material of a proper proportion according to predetermined colour temperature.Then, by fluorescent material add to
Resin is (such as：Silica resin or epoxy resin) and stir, so that fluorescent material can be dispersed in resin.
Then, the resin being dispersed with fluorescent material is mixed with firming agent, fluorescent material will be dispersed with point gum machine
High viscosity colloid 102 is covered on LED chip 101, drying and encapsulation procedure, can be obtained one
It is stamped the white light LEDs element 10 of solid state fluorescence colloid, as shown in Figure 1.However, obtained is white
Light LED element, because the external form proportion of fluorescent material and size are irregular, therefore solid state fluorescence colloid holds
Easily because of fluorescent material material property disunity, and the problems such as lead to colour temperature to be forbidden uneven with mixed light.
In order to strengthen fixing fluorescence blob of viscose and prevent from causing LED element impaired because of aqueous vapor infiltration,
Typically transparent organic silicon glue will be covered once again or epoxide-resin glue will be sprayed on solid state fluorescence colloid.However,
Under long-time operation, organic silica gel or epoxide-resin glue often have the phenomenons such as yellow or fragmentation and occur,
Aqueous vapor or impurity still cannot be stoped to penetrate into LED element, cause luminous efficiency to reduce even integral member
Lost efficacy.And, organosilicon glue-line or epoxy glue layer be not high to the toleration of temperature (only to be can be suitably used for
Less than about 150 DEG C), therefore must take into ambient temperature during using LED element, it is greatly lowered LED's
Using value.Therefore, need badly at present and develop one kind there is excellent durability, weatherability, resistance to scraping
Light-emitting device, this light-emitting device simultaneously has the characteristics such as even light mixing, refractive index be good, to energy simultaneously
The using value of white light emitting device is significantly increased.
Content of the invention
The main object of the present invention provide a kind of have excellent durability, weatherability, resistance to scraping
Light-emitting device, it is combined by the first luminescence unit and the second luminescence unit, and wherein fluorescent material is tight
Closely connected cover the first luminescence unit, and the light-emitting device of the present invention have even light mixing, refractive index good,
Go out the medium characteristic of light intensity collection.
For reaching above-mentioned purpose, the light-emitting device of the present invention is via a kind of novel fluorescent material coating side
Method is completed, and comprises the following steps：(A) fluorescent material is scattered in one second solvent, with shape
Become a fluorescent material solution；(B) one first luminescence unit is placed in a container, and it is molten to inject one the 3rd
Agent, and the 3rd solvent covers the surface of this first luminescence unit；(C) should by one the 4th solvent injection
3rd solvent, to form one the 5th solvent；(D) this fluorescent material solution is added to the 5th solvent,
To form a fluorescent material film in the 5th solvent surface；(E) remove the 5th molten in this container
Agent, makes this fluorescent material film be formed at this first luminescence unit surface；(F) thin in this fluorescent material
One protective layer is formed on film；And (G) heat treatment is formed with this first luminescence unit of this protective layer；
Wherein, this protective layer is a silicon nitride material layer, and the tolerable temperature of this light-emitting device being obtained is 320
More than DEG C.
In step (D), the 5th solvent is the 3rd solvent and the combining of the 4th solvent, in step (C)
The middle rear standing 0～30 minute forming the 5th solvent, preferably 5～20 minutes, be more preferably 5～10 points
Clock, the fluorescent material solution being formed is inserted in the 5th solvent, and then can make phosphor in step (A)
Material thin film is well formed at the first luminescence unit surface.
In step (E) afterwards and before step (F), a step (E1) can be further included：It is glimmering that drying is formed with this
This substrate of luminescent material thin film, to remove the second solvent remaining on this first luminescence unit.And,
After step (G), a step (G1) can be further included：Repeat this step (A) to step (G), many to be formed
Individual fluorescent material film and multiple protective layer, accordingly, can form this fluorescent material film being arranged alternately
With this protective layer.In the art the usually intellectual of having can according to actually required light mixing mechanism,
And determine the fluorescent material film quantity arranging.
In the fluorescent material coating method of the present invention, the second solvent, the 3rd solvent and the 4th solvent are simultaneously
No particular restriction, as long as meet following conditions：3rd solvent proportion is more than the second solvent and the 4th solvent.
It is described in detail in detail, when the 4th solvent add the 3rd solvent formed five solvents when, second with the 4th solvent understand shape
Become temporary interface, and after time of repose exceedes about 30 minutes, this interface can disappear, that is,
Four solvents are thoroughly mixed with the 3rd solvent.It is preferred that this second solvent, the 3rd solvent and this
Four solvents can be each independently selected from by：Water, methanol, ethanol, propanol, butanol, isopropanol, third
Ketone, butanone, normal butane, pentane, normal hexane, normal heptane, ethyl acetate, butyl acetate, second
Ether, glycol dimethyl ether (DME), dichloromethane (DCM), dimethylformamide (DMF), four
Hydrogen furan (THF), METHYLPYRROLIDONE (NMP), 3- methoxy propyl fine (MPN) and its mixing
The set that thing is formed；So the invention is not restricted to this.This second preferred solvents is normal butane or isopropanol,
3rd preferred solvents are ethyl acetate, and the 4th preferred solvents are ether or 3- methoxy propyl is fine
(MPN).
The present invention separately provides a kind of light-emitting device, is made up of said method, this light-emitting device includes：One
First luminescence unit；And one second luminescence unit, be covered on this first luminescence unit, and this
Two luminescence units include a fluorescent material film and a protective layer, and wherein, this protective layer is located at this fluorescence
On material film, this protective layer is a silicon nitride material layer, and the tolerable temperature of this light-emitting device exceedes
320℃.
In the light-emitting device of the present invention, the thickness of this first luminescence unit and this second luminescence unit is simultaneously
It is not particularly limited, and the gross thickness of this first luminescence unit and this second luminescence unit is between 105 μm extremely
Between 225 μm, preferably between 120 μm to 210 μm.Additionally, the light-emitting device tool of the present invention
There is a uneven surface, therefore the outward appearance of light-emitting device is irregular platy structure.
In light-emitting device in the present invention and preparation method thereof, this silicon nitride material layer can comprise：At least one
Plant the silicon-nitrogen compound shown in Formulas I, one first solvent and a catalyst,
Wherein n is positive integer, preferably between 4 to 3000, more preferably between 4 to 300
Between；And the number-average molecular weight of this silicon-nitrogen compound is 150 to 150,000 gram/mole, preferably
Between 10,000 to 15,000 grams/mole.
Wherein, have after this silicon-nitrogen compound heat treatment high rigidity, substrate is had high-adhesiveness and
High temperature resistant, even if under conditions of about 300 DEG C of temperatures above, by silicon-nitrogen compound, the first solvent
And the silicon nitride material layer that catalyst is formed still consolidates and do not have the phenomenons such as yellow, cracking to occur, protection is glimmering
Luminescent material thin film and avoid fluorescent material peel off situation.Additionally, this silicon-nitrogen compound can mix one nanometer
Level material, it is at least one selected from TiO2、SiO2、ZnO、ZrO、Y2O3、Al2O3、CoO、
MnO2, the set that formed of PbO, NiO, CuO and its complex, the grain of this nanometer materials
Footpath can between 5nm to 500nm, can modulation Refractive Index of Material and light transmittance, promote mixed light
Effect and light extraction efficiency.
Wherein, this first solvent is the solvent of anhydrous state, and it is at least one selected from dimethylbenzene, first
Benzene, ethanol, methanol, isopropanol, ethylene glycol, butyl acetate, ethyl acetate, dibasic ester (Dibasic
) and the set that formed of petroleum ether ester；Preferably dibasic ester and methanol mixture.In addition, should
Catalyst is the miscellaneous cyclic compound of N-, one-alkylamine, di-alkyl amine, trialkylamine, organic acid, no
Machine acid, peroxide, metal carboxylate, vinyl acetone acid misfit thing, metal or organometallic
Compound；The preferably miscellaneous cyclic compound of N- or metal carboxylate.There is usual knowledge in the art
Person can according to the silicon-nitrogen compound selected it is considered to the property such as hardness needed for protective layer, mobility and select
Select appropriate solvent and catalyst.The silicon nitride material layer being formed by silicon-nitrogen compound, the first solvent and catalyst is relatively
The hole between fluorescent material film and substrate, the luminescent properties of firm fluorescent material penetrate in Canon.
In light-emitting device in the present invention and preparation method thereof, this fluorescent material may include a fluorescent powder,
A ball-type carrier preferably can be further included；Include this fluorescent powder and this ball-type carrier in this fluorescent material
In the case of, fluorescent powder can cover ball-type carrier surface；Fluorescent powder may be included in ball-type carrier inside；
Or part fluorescent powder covers ball-type carrier surface, and part fluorescent powder is contained in ball-type carrier inside.
Meanwhile, the material of ball-type carrier can be SiOx, TiOx, PS, PMMA or melmac.
The material of fluorescent powder can be typically known fluorescent material, such as：Selected from ZnO, ZrO2、PbO、
Y2O3、Y2O2、Zn2SiO4、Y3Al5O12、Y3(AlGa)5O12Y2SiO5、LaOCl、InBO3、
ZnGa2O4、ZnS、PbS、CdS、CaS、SrS、ZnxCd1-xS、Y2O2S, AlN and Gd2O2S
The compound of the set being formed, and can more adulterate as the compound of fluorescent powder and at least one be selected from
Cu, Ag, Eu, Yb, La, Cl, Tb, Al, Ce, Er, Zn, Mn and other group of the lanthanides unit
The set element that plain (Pr, Pm, Sm, Ho, Er) is formed.Furthermore, the particle diameter of ball-type carrier is relatively
Good between 10 μm to 100 μm, more preferably between 25 μm to 50 μm；And fluorescent material
The particle diameter of body preferably between 5 μm to 50 μm, more preferably between 10 μm to 25 μm.
Therefore, because fluorescent material particle diameter and property are homogeneous, and uniform phosphor can be formed in substrate surface
Material thin film.
In light-emitting device in the present invention and preparation method thereof, the first luminescence unit can be any LED
Chip or LED element semi-finished product, preferably one is formed with the blue light epi-wafer of epitaxial layer, a formal dress
LED chip (face-up chip), a vertical LED chip (vertical chip) or flip LED
Chip.
In light-emitting device in the present invention and preparation method thereof, this protective layer can be utilized in the art
Common coating process is formed on this fluorescent material film, such as spin-coating method, stick coating method, scrapes cutter painting
Method, rolling method, spraying coating, bristle coating, dipping coating etc..Therefore, fluorescent material film can
It is stable on substrate and is difficult to be stripped, adjustment simultaneously is coated with the refractive index of the substrate of fluorescent material.
Accordingly, through the fluorescent material coating method of the present invention, can be equal by property with easy processing procedure
One fluorescent material film is formed on substrate, and silicon nitrogen protective layer is formed at fluorescent material film
On, and then produce that even light mixing, refractive index be good, light-emitting device that is simultaneously having excellent durability,
There will not be the phenomenons such as yellow or deterioration even across long-time operation to occur, effectively prevent aqueous vapor or miscellaneous
Matter penetrates into light-emitting device, stably maintains the luminous efficiency of device.
Brief description
Fig. 1 is the schematic diagram of existing light emitting diode.
Fig. 2A to 2H is the fluorescent material flow chart of coating substrate surface of the embodiment of the present invention 1.
Specific embodiment
Below by way of particular specific embodiment, embodiments of the present invention are described, are familiar with the people of this skill
Scholar can be understood other advantages and effect of the present invention easily by content disclosed in this specification.This
Bright also can be implemented or be applied by other different specific embodiments, every thin in this specification
Section also can be directed to different viewpoints and application, carries out various modification and change under without departing from the spirit
More.
The invention provides a kind of have excellent durability, weatherability, resistance to scraping light-emitting device,
It is combined by the first luminescence unit and the second luminescence unit, and wherein fluorescent material closely pastes first
Luminescence unit, and the light-emitting device of the present invention has even light mixing, refractive index is good, go out light intensity collection
Medium characteristic.
The light-emitting device of the present invention is completed via a kind of novel fluorescent material coating method, including under
Row step：(A) fluorescent material is scattered in one second solvent, to form a fluorescent material solution；
(B) one first luminescence unit is placed in a container, and injects one the 3rd solvent, and the 3rd solvent covers
Cover the surface of this first luminescence unit；(C) one the 4th solvent is injected the 3rd solvent, to form one
5th solvent；(D) this fluorescent material solution is added to the 5th solvent, with the 5th solvent table
Face forms a fluorescent material film；(E) remove the 5th solvent in this container, make this fluorescent material
Thin film is formed at this first luminescence unit surface；(F) protective layer is formed on this fluorescent material film；
And (G) heat treatment is formed with this first luminescence unit of this protective layer；Wherein, this protective layer is one
Silicon nitride material layer, and the tolerable temperature of this light-emitting device being obtained is more than 320 DEG C.
In step (D), the 5th solvent is the 3rd solvent and the combining of the 4th solvent, in step (C)
The middle rear standing 0～30 minute forming the 5th solvent, preferably 5～20 minutes, be more preferably 5～10 points
Clock, the fluorescent material solution being formed is inserted in the 5th solvent, and then can make phosphor in step (A)
Material thin film is well formed at the first luminescence unit surface.
In step (E) afterwards and before step (F), a step (E1) can be further included：It is glimmering that drying is formed with this
This substrate of luminescent material thin film, to remove the second solvent remaining on this first luminescence unit.And,
After step (G), a step (G1) can be further included：Repeat this step (A) to step (G), many to be formed
Individual fluorescent material film and multiple protective layer, accordingly, can form this fluorescent material film being arranged alternately
With this protective layer.In the art the usually intellectual of having can according to actually required light mixing mechanism,
And determine the fluorescent material film quantity arranging.
In the fluorescent material coating method of the present invention, the second solvent, the 3rd solvent and the 4th solvent are simultaneously
No particular restriction, as long as meet following conditions：3rd solvent proportion is more than the second solvent and the 4th solvent.
It is described in detail in detail, when the 4th solvent add the 3rd solvent formed five solvents when, second with the 4th solvent understand shape
Become temporary interface, and after time of repose exceedes about 30 minutes, this interface can disappear, that is,
Four solvents are thoroughly mixed with the 3rd solvent.It is preferred that this second solvent, the 3rd solvent and this
Four solvents can be each independently selected from by：Water, methanol, ethanol, propanol, butanol, isopropanol, third
Ketone, butanone, normal butane, pentane, normal hexane, normal heptane, ethyl acetate, butyl acetate, second
Ether, glycol dimethyl ether (DME), dichloromethane (DCM), dimethylformamide (DMF), four
Hydrogen furan (THF), METHYLPYRROLIDONE (NMP), 3- methoxy propyl fine (MPN) and its mixing
The set that thing is formed；So the invention is not restricted to this.This second preferred solvents is normal butane or isopropanol,
3rd preferred solvents are ethyl acetate, and the 4th preferred solvents are ether or 3- methoxy propyl is fine
(MPN).
The present invention separately provides a kind of light-emitting device, is made up of said method, this light-emitting device includes：One
First luminescence unit；And one second luminescence unit, be covered on this first luminescence unit, and this
Two luminescence units include a fluorescent material film and a protective layer, and wherein, this protective layer is located at this fluorescence
On material film, this protective layer is a silicon nitride material layer, and the tolerable temperature of this light-emitting device exceedes
320℃.
In the light-emitting device of the present invention, the thickness of this first luminescence unit and this second luminescence unit is simultaneously
It is not particularly limited, and the gross thickness of this first luminescence unit and this second luminescence unit is between 105 μm extremely
Between 225 μm, preferably between 120 μm to 210 μm.Additionally, the light-emitting device tool of the present invention
There is a uneven surface, therefore the outward appearance of light-emitting device is irregular platy structure.
In light-emitting device in the present invention and preparation method thereof, this silicon nitride material layer can comprise：At least one
Plant the silicon-nitrogen compound shown in Formulas I, one first solvent and a catalyst,
Wherein n is positive integer, preferably between 4 to 3000, more preferably between 4 to 300
Between；And the number-average molecular weight of this silicon-nitrogen compound is 150 to 150,000 gram/mole, preferably
Between 10,000 to 15,000 grams/mole.
Wherein, have after this silicon-nitrogen compound heat treatment high rigidity, substrate is had high-adhesiveness and
High temperature resistant, even if under conditions of about 300 DEG C of temperatures above, by silicon-nitrogen compound, the first solvent
And the silicon nitride material layer that catalyst is formed still consolidates and do not have the phenomenons such as yellow, cracking to occur, protection is glimmering
Luminescent material thin film and avoid fluorescent material peel off situation.Additionally, this silicon-nitrogen compound can mix one nanometer
Level material, it is at least one selected from TiO2、SiO2、ZnO、ZrO、Y2O3、Al2O3、CoO、
MnO2, the set that formed of PbO, NiO, CuO and its complex, the grain of this nanometer materials
Footpath can between 5nm to 500nm, can modulation Refractive Index of Material and light transmittance, promote mixed light
Effect and light extraction efficiency.
Wherein, this first solvent is the solvent of anhydrous state, and it is at least one selected from dimethylbenzene, first
Benzene, ethanol, methanol, isopropanol, ethylene glycol, butyl acetate, ethyl acetate, dibasic ester (Dibasic
) and the set that formed of petroleum ether ester；Preferably dibasic ester and methanol mixture.In addition, should
Catalyst is the miscellaneous cyclic compound of N-, one-alkylamine, di-alkyl amine, trialkylamine, organic acid, no
Machine acid, peroxide, metal carboxylate, vinyl acetone acid misfit thing, metal or organometallic
Compound；The preferably miscellaneous cyclic compound of N- or metal carboxylate.There is usual knowledge in the art
Person can according to the silicon-nitrogen compound selected it is considered to the property such as hardness needed for protective layer, mobility and select
Select appropriate solvent and catalyst.The silicon nitride material layer being formed by silicon-nitrogen compound, the first solvent and catalyst is relatively
The hole between fluorescent material film and substrate, the luminescent properties of firm fluorescent material penetrate in Canon.
In light-emitting device in the present invention and preparation method thereof, this fluorescent material may include a fluorescent powder,
A ball-type carrier preferably can be further included；Include this fluorescent powder and this ball-type carrier in this fluorescent material
In the case of, fluorescent powder can cover ball-type carrier surface；Fluorescent powder may be included in ball-type carrier inside；
Or part fluorescent powder covers ball-type carrier surface, and part fluorescent powder is contained in ball-type carrier inside.
Meanwhile, the material of ball-type carrier can be SiOx, TiOx, PS, PMMA or melmac.
The material of fluorescent powder can be typically known fluorescent material, such as：Selected from ZnO, ZrO2、PbO、
Y2O3、Y2O2、Zn2SiO4、Y3Al5O12、Y3(AlGa)5O12Y2SiO5、LaOCl、InBO3、
ZnGa2O4、ZnS、PbS、CdS、CaS、SrS、ZnxCd1-xS、Y2O2S, AlN and Gd2O2S
The compound of the set being formed, and can more adulterate as the compound of fluorescent powder and at least one be selected from
Cu, Ag, Eu, Yb, La, Cl, Tb, Al, Ce, Er, Zn, Mn and other group of the lanthanides unit
The set element that plain (Pr, Pm, Sm, Ho, Er) is formed.Furthermore, the particle diameter of ball-type carrier is relatively
Good between 10 μm to 100 μm, more preferably between 25 μm to 50 μm；And fluorescent material
The particle diameter of body preferably between 5 μm to 50 μm, more preferably between 10 μm to 25 μm.
Therefore, because fluorescent material particle diameter and property are homogeneous, and uniform phosphor can be formed in substrate surface
Material thin film.
In light-emitting device in the present invention and preparation method thereof, the first luminescence unit can be any LED
Chip or LED element semi-finished product, preferably one is formed with the blue light epi-wafer of epitaxial layer, a formal dress
LED chip (face-up chip), a vertical LED chip (vertical chip) or flip LED
Chip.
In light-emitting device in the present invention and preparation method thereof, this protective layer can be utilized in the art
Common coating process is formed on this fluorescent material film, such as spin-coating method, stick coating method, scrapes cutter painting
Method, rolling method, spraying coating, bristle coating, dipping coating etc..Therefore, fluorescent material film can
It is stable on substrate and is difficult to be stripped, adjustment simultaneously is coated with the refractive index of the substrate of fluorescent material.
Embodiment 1
Fig. 2A to Fig. 2 H is the fluorescent material step of coating substrate surface of the embodiment of the present invention 1
Schematic diagram.
[preparing fluorescent material solution]
First, take fluorescent material as a fluorescent material, using about 15 μm of Y of particle diameter2O3:La3+、
YAG:La3+, and CdSe:The mixture of ZnS.By adjusting the ratio of various fluorescent powders, warp
After blue light-emitting diode excites, this fluorescent material can carry out mixed light in its surface and send white light.
Then, fluorescent material 210 is mixed in second solvent 211 with polymolecularity, obtains one
Fluorescent material mixed solution, wherein fluorescent material percentage by weight in the second solvent is 20wt%, such as schemes
Shown in 2A.Here, using normal butane as the second solvent.
[formation fluorescent powder film]
As shown in Figure 2 B, take one first luminescence unit 20, and be placed on a container 24 bottom,
Wherein, this first luminescence unit is a flip LED chip, then, injects the 3rd in container 24
Solvent 23, here, using pure water as the 3rd solvent.Then, as shown in Figure 2 C, in container 24
In reinject the 4th solvent 25, and the 4th solvent adding amount is the 1wt% of the 3rd solvent.When the 4th is molten
When agent 25 adds three solvents 23, form one between the 3rd solvent 23 and the 4th solvent 25 temporary
Interface 27, the 3rd solvent 23 and the 4th solvent 25 form the 5th solvent 26, here, adopting ether
As the 4th solvent.Then, form the 5th solvent 26 and stand 5 minutes, in the 5th solvent 26 surface
Insert the fluorescent material mixed solution shown in Fig. 2A, due to the ratio of the ethyl acetate as the 3rd solvent 23
It is higher than the normal butane as the second solvent 211 again, therefore the fluorescent material 210 in fluorescent material solution can be arranged
Row in its surface, and form one first fluorescent powder film 21, as shown in Figure 2 D.
Then, the 5th solvent 26 is removed from container 24, make the first fluorescent powder film 21 in send out
Electro-optical device 20 surface forming, as shown in Figure 2 E.Then, container 24 is placed in equipment for drying (figure
In do not show) in, to evaporate removing residual solvent.To be dried completely after, then can get one be formed at luminous
First fluorescent powder film 21 on device 20 surface, as shown in Figure 2 F.
[formation protective layer]
Prepare a silicon nitrogen material solution, the silicon-nitrogen compound structure such as Formula Il of use, with dibasic ester,
Methanol mixing solvent (solvent anharmonic ratio 1: 1), Metal Palladium catalyst (weight is than 0.5wt%) and nanoscale TiO2
(particle diameter 20nm, weight is than 1wt%) mixes.
After mix homogeneously, with method of spin coating by silicon nitrogen material solution coating in the first fluorescent powder film 21
On, and form one first protective layer 22, as shown in Figure 2 G.After standing, will have the first fluorescent material
First luminescence unit 20 of thin film 21 and the first protective layer 22 carries out heat treatment 10 seconds to 1 hour,
Made annealing treatment again, then completed the light emitting devices surface of the present embodiment, inorganic silica, silicon can be formed
The material layer such as nitrogen oxygen or silicon nitrogen, and this apparatus surface is uneven surface.In Fig. 2 G, first
Fluorescent powder film 21 and the first protective layer 22 be combined as the second luminescence unit 30.In this, first
The gross thickness of light unit 20 and the second luminescence unit 30 is 115 μm.Have in the art generally
Skill can select suitable curing mode according to the silicon nitrogen material SOLUTION PROPERTIES prepared.
Therefore, above-mentioned formation firm and have water oxygen resistant silicon nitride material layer, fixed fluorescent powder can be strengthened
Layer, through working long hours down does not have the phenomenons such as yellow or deterioration occur, can prevent aqueous vapor penetrate into and
Cause LED chip impaired, it is to avoid substrate luminous efficiency deteriorate, and can high temperature resistant more than 320
More than degree DEG C.By the above-mentioned prepared flip LED chip being coated with fluorescent powder film, through pilot
After bright, the color temperature of mixed light being sent is 5400K.
And, more repeatable above-mentioned steps as shown in Fig. 2 B to Fig. 2 G etc., form and have multilamellar
Fluorescent powder film interacts the composite construction of setting with multilayer resist, as illustrated in figure 2h, in the first guarantor
Second fluorescent powder film 21 ', the second protective layer 22 ', the 3rd fluorescence can be sequentially formed on sheath 22 again
Powder thin film 21 " and the 3rd protective layer 22 ", consequently, it is possible to the fluorescent powder film light mixing effect being formed
Can reach expected colour temperature and color rendering.In Fig. 2 H, the first protective layer 22, the second fluorescent material
The combination of thin film 21 ', the second protective layer 22 ', the 3rd fluorescent powder film 21 " and the 3rd protective layer 22 "
For the second luminescence unit 30 '.In this, the total thickness of the first luminescence unit 20 and the second luminescence unit 30 '
Spend for 145 μm.And, protective layer is arranged alternately with fluorescent powder film, can effective district glimmering every those
Light powder thin film, if the thin film that different phosphor material powders are made need to be arranged, is separated by with protective layer and can avoid respectively
Fluorescent powder film mutually mixes/interference, the required light mixing effect of impact.
[embodiment 2]
The manufacture method of the present embodiment is as described in Example 1.Except fluorescent material used in the present embodiment
Using particle diameter be nanosphere that 25 μm and material are PMMA as ball-type carrier, and fluorescent powder
Using about 5 μm of Y of particle diameter2O3:La3+、YAG:La3+, and CdSe:The mixture of ZnS, and
The mixture of fluorescent powder is contained in ball-type carrier inside.Additionally, using isopropanol as the second solvent,
And using 3- methoxy propyl fine (MPN) as the 4th solvent.Therefore, coating is obtained in the present embodiment
Have the flip LED chip of fluorescent powder film, through pilot bright after, the color temperature of mixed light that sent is 5700K.
Above-described embodiment is illustrated only for convenient explanation, and the interest field that the present invention is advocated is certainly
Being defined described in claim, rather than above-described embodiment should be only limitted to.
Claims (35)
1. a kind of light-emitting device, including：
One first luminescence unit；And
One second luminescence unit, it is covered on this first luminescence unit, and this second luminescence unit bag
Include a fluorescent material film and a protective layer；
Wherein, this protective layer is located on this fluorescent material film, and this protective layer is a silicon nitride material layer,
And the tolerable temperature of this light-emitting device is more than 320 DEG C.
2. light-emitting device as claimed in claim 1, wherein, this first luminescence unit and this second
The gross thickness of luminescence unit is between 105 μm to 225 μm.
3. light-emitting device as claimed in claim 1, it has a uneven surface.
4. light-emitting device as claimed in claim 1, wherein, this silicon nitride material layer comprises：At least
A kind of silicon-nitrogen compound shown in Formulas I, one first solvent and a catalyst,
Wherein n is positive integer, and the number-average molecular weight of this silicon-nitrogen compound be 150 to 150,000 gram/
Mole.
5. light-emitting device as claimed in claim 4, wherein, this silicon-nitrogen compound is to mix to receive
Meter level material, it is at least one selected from TiO2、SiO2、ZnO、ZrO、Y2O3、Al2O3、CoO、
MnO2, the set that formed of PbO, NiO, CuO and its complex.
6. light-emitting device as claimed in claim 4, wherein, the particle diameter of this nanometer materials is between 5
Between nm to 500nm.
7. light-emitting device as claimed in claim 4, wherein, this first solvent is at least one to be selected from
By dimethylbenzene, toluene, ethanol, methanol, isopropanol, ethylene glycol, butyl acetate, ethyl acetate,
The set that dibasic ester (Dibasic ester) and petroleum ether are formed.
8. light-emitting device as claimed in claim 4, wherein, this catalyst be the miscellaneous cyclic compound of N-,
One-alkylamine, di-alkyl amine, trialkylamine, organic acid, mineral acid, peroxide, metal carboxylic
Hydrochlorate, vinyl acetone acid misfit thing, metal or organo-metallic compound.
9. light-emitting device as claimed in claim 1, wherein, this first luminescence unit is a formation
There are the blue light epi-wafer of epitaxial layer, a packed LED chip (face-up chip), a vertical LED core
Piece (vertical chip) or a flip LED chip (flip chip).
10. light-emitting device as claimed in claim 1, wherein this fluorescent material include a ball-type carrier,
And a fluorescent powder.
11. light-emitting devices as claimed in claim 10, wherein this fluorescent powder cover this ball-type and carry
Body surface face or be contained in this ball-type carrier inside.
12. light-emitting devices as claimed in claim 10, the wherein material of this ball-type carrier be SiOx,
TiOx, PS, PMMA or melmac, and the scope of X is between 0.5～2.
13. light-emitting devices as claimed in claim 10, wherein this fluorescent powder are at least one to be selected from
By ZnO, ZrO2、PbO、Y2O3、Y2O2、Zn2SiO4、Y3Al5O12、Y3(AlGa)5O12Y2SiO5、
LaOCl、InBO3、ZnGa2O4、ZnS、PbS、CdS、CaS、SrS、ZnxCd1-xS、Y2O2S、
AlN、Gd2O2The compound of the set that S is formed, and X is between 0.5 to 2.
14. light-emitting devices as claimed in claim 13, wherein this compound doped at least one is selected from
By Cu, Ag, Eu, Yb, La, Cl, Tb, Al, Ce, Er, Zn, Mn, Pr, Pm, Sm,
The element of the set that Ho and Er is formed.
15. light-emitting devices as claimed in claim 10, the wherein particle diameter of this ball-type carrier are between 10
μm between 100 μm.
16. light-emitting devices as claimed in claim 10, the wherein particle diameter of this fluorescent powder are between 5 μm
To between 50 μm.
17. light-emitting devices as claimed in claim 1, wherein this second luminescence unit include multiple glimmering
Luminescent material thin film and multiple protective layer, wherein this fluorescent material film and this protective layer are arranged alternately.
A kind of 18. preparation methoies of light-emitting device, comprise the following steps：
(A) fluorescent material is scattered in one second solvent, to form a fluorescent material solution；
(B) one first luminescence unit is placed in a container, and injects one the 3rd solvent, and the 3rd solvent
Cover the surface of this first luminescence unit；
(C) one the 4th solvent is injected the 3rd solvent, to form one the 5th solvent；
(D) this fluorescent material solution is added to the 5th solvent, to be formed in the 5th solvent surface
One fluorescent material film；
(E) remove the 5th solvent in this container, make this fluorescent material film be formed at this first light
Cell surface；
(F) protective layer is formed on this fluorescent material film；And
(G) heat treatment is formed with this first luminescence unit of this protective layer；
Wherein, this protective layer is a silicon nitride material layer, and the tolerable temperature of this light-emitting device being obtained exists
More than 320 DEG C.
The preparation method of 19. light-emitting devices as claimed in claim 18, wherein, this silicon nitrogen material
Layer comprises：Silicon-nitrogen compound shown at least one Formulas I, one first solvent and a catalyst,
Wherein n is positive integer, and the number-average molecular weight of this silicon-nitrogen compound be 150 to 150,000 gram/
Mole.
The preparation method of 20. light-emitting devices as claimed in claim 19, wherein, this silicon nitrification
Thing is to mix nanometer materials, and it is at least one selected from TiO2、SiO2、ZnO、ZrO、Y2O3、
Al2O3、CoO、MnO2, the set that formed of PbO, NiO, CuO and its complex.
21. light-emitting devices as claimed in claim 20, wherein, the particle diameter of this nanometer materials is situated between
Between 5nm to 500nm.
The preparation method of 22. light-emitting devices as claimed in claim 19, wherein, this first solvent
Be at least one be selected from dimethylbenzene, toluene, ethanol, methanol, isopropanol, ethylene glycol, butyl acetate,
The set that ethyl acetate, dibasic ester and petroleum ether are formed.
The preparation method of 23. light-emitting devices as claimed in claim 19, wherein, this catalyst is N-
Miscellaneous cyclic compound, one-alkylamine, di-alkyl amine, trialkylamine, organic acid, mineral acid, mistake
Oxide, metal carboxylate, vinyl acetone acid misfit thing, metal or organo-metallic compound.
The preparation method of 24. light-emitting devices as claimed in claim 18, wherein, in step (E) afterwards,
And before step (F), further include a step (E1)：Drying be formed with this fluorescent material film this first
Luminescence unit.
The preparation method of 25. light-emitting devices as claimed in claim 18, after step (G), more wraps
Include a step (G1)：Repeat this step (A) to step (G), to form multiple fluorescent material films and many
Individual protective layer.
The preparation method of 26. light-emitting devices as claimed in claim 18, the wherein the 3rd solvent
Proportion is more than the proportion of this second solvent and the 4th solvent.
The preparation method of 27. light-emitting devices as claimed in claim 18, wherein this fluorescent material bag
Include a ball-type carrier and a fluorescent powder.
The preparation method of 28. light-emitting devices as claimed in claim 26, wherein this fluorescent powder are covered
Cover this ball-type carrier surface or be contained in this ball-type carrier inside.
The preparation method of 29. light-emitting devices as claimed in claim 26, wherein this ball-type carrier
Material is SiOx, TiOx, PS, PMMA or melmac.
The preparation method of 30. light-emitting devices as claimed in claim 26, wherein this fluorescent powder are
At least one is selected from ZnO, ZrO2、PbO、Y2O3、Y2O2、Zn2SiO4、Y3Al5O12、
Y3(AlGa)5O12Y2SiO5、LaOCl、InBO3、ZnGa2O4、ZnS、PbS、CdS、CaS、
SrS、ZnxCd1-xS、Y2O2S、AlN、Gd2O2The compound of the set that S is formed, and X Jie
Between 0.5 to 2.
The preparation method of 31. light-emitting devices as claimed in claim 29, wherein this compound are to mix
Miscellaneous at least one be selected from Cu, Ag, Eu, Yb, La, Cl, Tb, Al, Ce, Er, Zn, Mn,
The element of the set that Pr, Pm, Sm, Ho and Er are formed.
The preparation method of 32. light-emitting devices as claimed in claim 26, wherein this ball-type carrier
Particle diameter is between 10 μm to 100 μm.
The preparation method of 33. light-emitting devices as claimed in claim 26, wherein this fluorescent powder
Particle diameter is between 5 μm to 50 μm.
The preparation method of 34. light-emitting devices as claimed in claim 18, wherein this second solvent,
3rd solvent and the 4th solvent be each independently selected from by：Water, methanol, ethanol, propanol,
Butanol, isopropanol, acetone, butanone, normal butane, pentane, normal hexane, normal heptane, acetic acid second
Ester, butyl acetate, ether, glycol dimethyl ether (DME), dichloromethane (DCM), dimethyl
Methanamide (DMF), oxolane (THF), METHYLPYRROLIDONE (NMP), 3- methoxyl group
The set that third fine (MPN) and its mixture are formed.
The preparation method of 35. light-emitting devices as claimed in claim 18, wherein this first luminous list
Blue light epi-wafer that unit is formed with epitaxial layer for one, a packed LED chip (face-up chip), one vertical
Straight LED chip (vertical chip) or a flip LED chip (flip chip).
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| US20080128730A1 (en) * | 2006-11-15 | 2008-06-05 | The Regents Of The University Of California | Textured phosphor conversion layer light emitting diode |
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| CN109669300A (en) * | 2019-02-19 | 2019-04-23 | 江西轩宜之家智能技术有限公司 | A kind of luminous ito glass substrate and preparation method thereof |
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| CN106486586B (en) | 2019-10-01 |
| TWI591864B (en) | 2017-07-11 |
| TW201709566A (en) | 2017-03-01 |
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