CN109962150A - A kind of packaging film and preparation method thereof, photoelectric device - Google Patents
A kind of packaging film and preparation method thereof, photoelectric device Download PDFInfo
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- CN109962150A CN109962150A CN201711339298.9A CN201711339298A CN109962150A CN 109962150 A CN109962150 A CN 109962150A CN 201711339298 A CN201711339298 A CN 201711339298A CN 109962150 A CN109962150 A CN 109962150A
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- Prior art keywords
- film
- packaging film
- blend
- organic
- packaging
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- 229920006280 packaging film Polymers 0.000 title claims abstract description 72
- 239000012785 packaging film Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 239000012528 membrane Substances 0.000 claims abstract description 40
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 34
- 239000004626 polylactic acid Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 26
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical compound CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001301 oxygen Substances 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- 230000004888 barrier function Effects 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 160
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229920006381 polylactic acid film Polymers 0.000 description 12
- 238000005538 encapsulation Methods 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- 238000005266 casting Methods 0.000 description 9
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 235000013842 nitrous oxide Nutrition 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229960001296 zinc oxide Drugs 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram 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
- 230000002209 hydrophobic effect Effects 0.000 description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- APIDIPGVBRXKEJ-UHFFFAOYSA-N acetic acid titanium Chemical compound [Ti].CC(O)=O.CC(O)=O APIDIPGVBRXKEJ-UHFFFAOYSA-N 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/005—Processes relating to semiconductor body packages relating to encapsulations
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention discloses a kind of packaging film and preparation method thereof, photoelectric device, wherein, the packaging film includes the first organic film being stacked, the first blend film being made of polymer and ceramic material, the 1-4 layer ceramic membrane being made of ceramic material, the second blend film being made of polymer and ceramic material, the second organic film.The present invention is using the first organic film and the second organic film as aqueous vapor separation layer, using 1-4 layers of fine and close ceramic membrane as oxygen barrier layer, the blended layer being made of polymer and ceramic material is set between the ceramic membrane and organic film simultaneously, the blended layer can effectively promote the binding force between organic film and ceramic membrane, to enhance the water and oxygen barrier property of packaging film, and then meet requirement of the photoelectric device to steam permeability, improve the service life of photoelectric device.
Description
Technical field
The present invention relates to field of photoelectric devices more particularly to a kind of packaging film and preparation method thereof, photoelectric device.
Background technique
The service life of photoelectric device is that its very important parameter in order to improve the service life of photoelectric device makes it
Reach commercial horizontal, encapsulation is a vital link.For photoelectric device, encapsulation is not only to prevent scuffing etc.
Physical protection, it is often more important that prevent steam in external environment, the infiltration of oxygen, steam or oxygen in these environment penetrate into
Device inside can accelerate the aging of device.Therefore the encapsulating structure of photoelectric device must have good water, Oxygen permeation to stop function
Energy.
Currently, the encapsulation technology of commercial photoelectric device is just from traditional cover-plate type encapsulation to novel thin film integrative packaging
Development.It is encapsulated compared to traditional cover board, thin-film package can be substantially reduced the thickness and quality of device, about save 50%
Potential packaging cost, while thin-film package can be suitably used for flexible device.Thin film encapsulation technology will be the inexorable trend developed.
The prior art generallys use encapsulating film of the organic film with transparent hydrophobic performance as photoelectric device, however,
Existing organic film is generally configured with the performance of preferably barrier steam, but its barrier properties for gases is poor to limit it as encapsulation
The extensive use of thin-film material in the opto-electronic device.
For the barrier properties for gases for improving organic packages thin-film material, the means most often taken are introduced among organic film
One layer of inorganic ceramic film forms multilayer film encapsulating structure.But between simple inorganic ceramic film and organic film not
Compatibility causes composite property poor, to affect the water and oxygen barrier property of packaging film material.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of packaging film and preparation method thereof,
Photoelectric device, it is intended to solve the problems, such as that existing packaging film water and oxygen barrier property is poor.
Technical scheme is as follows:
A kind of packaging film, wherein including successively stack the first organic film, be made of polymer and ceramic material first
Blend film, the 1-4 layer ceramic membrane being made of ceramic material, the second blend film being made of polymer and ceramic material, second have
Machine film.
The packaging film, wherein the ceramic material is silica, aluminium oxide, zinc oxide, titanium oxide and tungsten oxide
One of or it is a variety of.
The packaging film, wherein first organic film material, the second organic film material, the first blend film
In polymer and the polymer in the second blend film be independently selected from polylactic acid, polytetrafluoroethylene (PTFE), polymethyl siloxane and poly-
One of propylene is a variety of.
The packaging film, wherein first organic film with a thickness of 1-3 μm；And/or it is described second organic thin
The thickness of film is 1-3 μm.
The packaging film, wherein first blend film with a thickness of 0.8-1.2 μm；And/or second blending
The thickness of film is 0.8-1.2 μm.
The packaging film, wherein the ceramic membrane with a thickness of 0.1-1 μm.
A kind of preparation method of packaging film, wherein include the following steps:
Device to be packaged is provided, deposits the first organic film in the device surface；
The first blend film is deposited on the first organic film, first blend film is made of polymer and ceramic material；
The N layer ceramic membrane of lamination setting, 1≤N≤4 are deposited in the first blend film；
The second blend film is deposited on n-th layer ceramic membrane, second blend film is made of polymer and ceramic material；
The second organic film is deposited in the second blend film.
The preparation method of the packaging film, wherein the system that the first hybrid films are deposited on the first organic film
It is standby to include the following steps:
Under alkaline condition, inorganic precursor and organic monomer are carried out under an inert atmosphere according to predetermined weight ratio anti-for the first time
It answers；
Catalyst is added, obtains intermingling material after carrying out the second secondary response under vacuum conditions；
It will be distributed in tetrahydrofuran solvent after intermingling material drying, obtain the blending being made of polymer and ceramic material
Liquid；
The blended liquid being made of polymer and ceramic material is deposited on the first organic film, obtains the first blend film.
The preparation method of the packaging film, wherein the inorganic precursor is ethyl orthosilicate, aluminum nitrate, acetic acid
Zinc, sodium tungstate or butyl titanate.
The preparation method of the packaging film, wherein the organic monomer is lactic acid, tetrafluoroethene, methylsiloxane
With one of propylene or a variety of.
The preparation method of the packaging film, wherein the catalyst is in stannous octoate, stannous acetate and hydrochloric acid
It is one or more.
The preparation method of the packaging film, wherein the temperature of the first set reaction is 50-100 DEG C and/or heating
Rate is 0.5-1 DEG C/min.
The preparation method of the packaging film, wherein the temperature of second secondary response is 150-200 DEG C.
A kind of photoelectric device, including first electrode, luminescent layer and second electrode, wherein be arranged in the second electrode
There is packaging film, the packaging film is packaging film described in any of the above embodiments or the packaging film is any of the above-described
The packaging film of the method preparation.
The utility model has the advantages that packaging film provided by the invention includes the first organic film being stacked, by polymer and pottery
First blend film of ceramic material composition, the 1-4 layer ceramic membrane being made of ceramic material, be made of polymer and ceramic material the
Two blend films, the second organic film.The present invention is using the first organic film and the second organic film as aqueous vapor separation layer, by 1-4
The fine and close ceramic membrane of layer is arranged as oxygen barrier layer, while between the ceramic membrane and organic film by polymer and ceramics
The blended layer of material composition, the blended layer can effectively promote the binding force between organic film and ceramic membrane, to enhance envelope
The water and oxygen barrier property of film is filled, and then meets requirement of the photoelectric device to steam permeability, that improves photoelectric device uses the longevity
Life.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of packaging film preferred embodiment of the present invention；
Fig. 2 is a kind of flow chart of the preparation method preferred embodiment of packaging film of the present invention.
Specific embodiment
The present invention provides a kind of packaging films and preparation method thereof, photoelectric device, to make the purpose of the present invention, technical side
Case and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific reality described herein
Example is applied only to explain the present invention, is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is a kind of structural schematic diagram of packaging film preferred embodiment provided by the invention, as schemed institute
Show, the packaging film include the first organic film 10 being stacked, by polymer and ceramic material form first be blended
Film 20, the 1-4 layer ceramic membrane 30 being made of ceramic material, the second blend film 40, second being made of polymer and ceramic material
Organic film 50.
Specifically, present embodiment, will be fine and close using the first organic film and the second organic film as aqueous vapor separation layer
Ceramic membrane as oxygen barrier layer, and by between ceramic membrane and organic film add by polymer and ceramic material group
At blend film, the blend film can not only enhance the compatibility between ceramic membrane and organic film, additionally it is possible to reduce film layer it
Between defect, to enhance the water and oxygen barrier property and optical property of packaging film.
Preferably, first organic film material, the second organic film material, the polymer in the first blend film and
Polymer in second blend film is transparent hydrophobic material, concretely polylactic acid, polytetrafluoroethylene (PTFE), polymethyl siloxane and
One of polypropylene is a variety of.As an example, the preferred polylactic acid of present embodiment (PLA) prepares organic film and blending
Film, because it not only has stronger water vapor rejection performance, but also PLA is a kind of renewable, degradable Novel environment-friendlymaterial material,
Many performances of PLA can be controlled by preparation process and modified method.
It preferably, in the present embodiment, will be described to guarantee that the packaging film has preferable water vapor rejection performance
First organic film is set as 1-3 μm.
It is highly preferred that the thickness of second organic film is also configured as 1-3 μm.
In order to make up the poor defect of organic film gas barrier property, present embodiment by the first organic film and
The 1-4 layers of dense ceramic membrane prepared by ceramic material are provided between second organic film.
In one embodiment, the ceramic material is in silica, aluminium oxide, zinc oxide, titanium oxide and tungsten oxide
It is one or more, but not limited to this.It is preferred that silica is as ceramic membrane materials because silicon oxide film not only transparency it is high,
Consistency is high, and stronger with the binding force of organic film, and oxygen resistance is best.
It is highly preferred that in the present embodiment, to guarantee that the packaging film has preferable oxygen resistance, the ceramics
Film is provided with layer 2-3, and the thickness of the ceramic membrane is set as 0.1-1 μm.
Further, present embodiment is provided with one layer by polymer and ceramics between the ceramic membrane and organic film
The blend film of material composition, the blend film can not only enhance the compatibility between ceramic membrane and organic film, additionally it is possible to reduce
Defect between film layer, to enhance the water and oxygen barrier property and optical property of packaging film.
Preferably, in the present embodiment, to enhance the binding force between the ceramic membrane and organic film, by described the
The thickness of one blend film is set as 0.8-1.2 μm.
It is highly preferred that the thickness of second blend film is also configured as 0.8-1.2 μm.
The multilayer encapsulation film that present embodiment provides is capable of forming good covering ladder, utilizes the common work of multilayer film
With, it can effectively completely cut off the infiltration of steam and oxygen, can satisfy requirement of the photoelectric device to steam permeability, thus
Improve the service life of photoelectric device；The packaging film belongs to transparent membrane simultaneously, can be used for the envelope of top illuminating device and screen
Assembling structure.
Further, the present invention also provides a kind of preparation methods of packaging film, wherein as shown in Fig. 2, comprising steps of
S1, device to be packaged is provided, deposits the first organic film in the device surface；
S2, the first blend film is deposited on the first organic film, first blend film is made of polymer and ceramic material；
S3, the N layer ceramic membrane that lamination setting is deposited in the first blend film, 1≤N≤4；
S4, the second blend film is deposited on n-th layer ceramic membrane, second blend film is made of polymer and ceramic material；
S5, the second organic film is deposited in the second blend film.
Further, the preparation that the first hybrid films are deposited on the first organic film includes the following steps:
Under alkaline condition, inorganic precursor and organic monomer are carried out under an inert atmosphere according to predetermined weight ratio anti-for the first time
It answers；
Catalyst is added, obtains intermingling material after carrying out the second secondary response under vacuum conditions；
It will be distributed in tetrahydrofuran solvent after intermingling material drying, obtain the blending being made of polymer and ceramic material
Liquid；
The blended liquid being made of polymer and ceramic material is deposited on the first organic film, obtains the first blend film.
Preferably, the inorganic precursor be ethyl orthosilicate, aluminum nitrate, zinc acetate, sodium tungstate or butyl titanate, but
It is without being limited thereto.
Preferably, the organic monomer be lactic acid, tetrafluoroethene, one of methylsiloxane and propylene or a variety of, but
It is without being limited thereto.
It is highly preferred that the inorganic precursor and organic monomer carry out first according to the weight ratio of 1:1 under an inert atmosphere
Secondary response.
Preferably, the catalyst is one of stannous octoate, stannous acetate and hydrochloric acid or a variety of, but not limited to this.
Preferably, the temperature of the first set reaction is 50-100 DEG C and/or heating rate is 0.5-1 DEG C/min.
Preferably, the temperature of second secondary response is 150-200 DEG C.
Preferably, the inert atmosphere is one of nitrogen, helium, neon and argon gas or a variety of, but not limited to this.
It is prepared in polylactic acid-silica blended liquid specific embodiment a kind of, first using 30% Strong oxdiative ammonium as urging
Agent is added in ethyl alcohol, is then stirred under the conditions of 50-80 DEG C, adds 10-20ml ethyl orthosilicate while stirring
(TEOS), continuing stirring 15-25 h can be obtained silica ethanol solution；
Under alkaline condition, by concentration be 10% silica ethanol solution and ammonium lacate according to weight ratio be 1:1 ratio in nitrogen
It is reacted under gas atmosphere, reaction temperature is 80 DEG C, and heating rate is 0.8 DEG C/min, and reaction time 1.5h is added later
For the stannous octoate of 0.05g as catalyst the reaction was continued in a vacuum 5h, reaction temperature is 180 DEG C；Wherein, reaction equation is such as
Shown in lower:
SiO2-OH+OH-CO(CH3)CH-OH=SiO2-O-CO(CH3)CH-OH
SiO2-O-CO(CH3)CH-OH+OH-CO(CH3)CH-OH=SiO2- O-(CO (CH3) CH-O)nH
The product drying that reaction obtains is dispersed in tetrahydrofuran solvent later, polylactic acid-silica blended liquid is made.
It is prepared in polymethyl siloxane-silica blended liquid specific embodiment a kind of, first by 30% Strong oxdiative ammonium
It is added in ethyl alcohol as catalyst, is then stirred under the conditions of 50-80 DEG C, adds the positive silicic acid of 10-20ml while stirring
Ethyl ester (TEOS), continuing stirring 15-25 h can be obtained silica ethanol solution；
By concentration be 15% silica ethanol solution and methyltrimethoxysilane weight ratio be 1:1 ratio in nitrogen gas
It is reacted under atmosphere, 10-20 min is stirred at a temperature of 50-60 DEG C, through salt acid for adjusting pH value between 2-3, and in salt
It allows precursor compound to hydrolyze to form semi-intercrossing network under the catalytic action of acid, allows hydrolysis and monomer polymerization while being prepared into
To silicon dioxide-poly methylsiloxane intermingling material；
It will be dispersed in tetrahydrofuran solvent after silicon dioxide-poly methylsiloxane intermingling material drying, poly- first be made
Radical siloxane-silica blended liquid.
It is prepared in polytetrafluoroethylene (PTFE)-titanium dioxide blending liquid specific embodiment a kind of, under alkaline condition, by titanium
After sour four butyl ester alcoholic solutions react 0.5-1h under an inert atmosphere according to a certain percentage with tetrafluoroethene, 0.01-1g salt is added
Acid, through salt acid for adjusting pH value between 2-3, and formation polytetrafluoroethylene (PTFE)-titanium dioxide is total under the catalytic action of hydrochloric acid
Mixed liquid.
Make blend film that there is good binding force by polymer-ceramic material blended liquid prepared by the above method, and
And inorganic ceramic material hydridization is increased in polymer network so that membrane stability is blended.
Preferably, in the present embodiment, the side of casting, spin coating or printing can be used in the organic film and blend film
It is prepared by formula.
The ceramic membrane preferably uses PECVD method to prepare: with PECVD(plasma enhanced chemical vapor deposition method) side
Method prepares SiO2For film, device to be packaged is placed on the substrate of PECVD device, is passed through silane (SiH4) and laughing gas
(N2O it) is reacted under plasmoid, technological temperature is lower than 150 DEG C, reaction equation are as follows:
SiH4+2N2O=SiO2+2N2+H2
Plated film specific process parameter is SiH4For 10-45 sccm, N2O is 100-364 sccm, N2For 300-800sccm；Wherein
For nitrogen as diluent gas, main function is to influence reaction chamber reaction gases partial pressure situation；It is preferred that the power of PECVD device is
Between 30W-200 W, wherein the smaller deposition rate of power is smaller, and uniformity of film is better, but need to take into account deposition rate and
Uniformity of film, so power selection is between 30W-200W.Film deposition rate is kept between 20 nm-50 nm.
Further, the present invention also provides a kind of photoelectric device, including first electrode, luminescent layer and second electrode,
In, packaging film is provided in the second electrode, the packaging film is packaging film described in any of the above embodiments or institute
State the packaging film that packaging film is the preparation of any of the above-described the method.The packaging film can be imitated guaranteeing that device shines
The infiltration for effectively completely cutting off steam and oxygen on the basis of rate and light emission luminance, to improve device lifetime.
It elaborates below by specific embodiment to a kind of photoelectric device of the present invention and its packaging method:
Embodiment 1
1, the structure of photoelectric device are as follows: ITO substrate/PEDOT:PSS (50 nm)/poly-TPD (30 nm)/quantum dot light emitting
Layer (20 nm)/ZnO (30nm)/silver (70 nm)/packaging film (4100 nm), wherein the material of the packaging film is
PLA/SiO2- PLA blend film/SiO2/ SiO2- PLA blend film/PLA laminated film, the SiO2Film thickness is 100 nm,
The thickness of two layers of PLA film is 1000 nm, two layers of SiO2The thickness of-PLA blend film is 1000nm.
2, photoelectric device packaging method comprising steps of
1), the PLA chloroformic solution of 10 mg/ml is cast using the method for casting on the silver electrode top surface of photoelectric device
Film forming, then 0.8 Pa is dried in vacuo 30 min and is prepared into PLA film under the conditions of 120 DEG C；
2) SiO for being, under alkaline condition, 5 wt% by mass fraction2Alcoholic solution and ammonium lacate according to 1:1 ratio in nitrogen gas
It is reacted under atmosphere, reaction temperature is 100 DEG C, reaction time 1h, and reaction is added pungent in above-mentioned reaction system after completing
For sour stannous 0.01g as catalyst the reaction was continued in a vacuum 5 h, reaction temperature is 150 DEG C.Reaction product is dissolved in four
In hydrogen tetrahydrofuran solution, solution concentration is 10 mg/ml, casting film is carried out in the PLA film surface, then in 120 DEG C of items
0.8 Pa is dried in vacuo 30 min and is prepared into SiO under part2- PLA blend film；
3) method for, then using PECVD, uses silane (SiH4) it is 16 sccm and laughing gas (N2O it is) 120 sccm, is waiting
It is reacted under ionic condition, technological temperature is 150 DEG C, and power is 40 W, and nitrogen flow is 300 sccm, and plated film rate is 25
Silica membrane is prepared under the conditions of nm/min；
4) one layer of SiO, is prepared on the silica membrane surface using the method for step 2 again2- PLA blend film；
5), using the method for step 1) SiO described in step 4)2- PLA blend film surface prepares PLA film, then 120
0.8 Pa is dried in vacuo 30 min under the conditions of DEG C, realizes the encapsulation to photoelectric device.
Embodiment 2
1, the structure of photoelectric device are as follows: ITO substrate/PEDOT:PSS (50 nm)/poly-TPD (30 nm)/quantum dot light emitting
Layer (20 nm)/ZnO (30nm)/silver (70 nm)/packaging film (9000 nm), wherein the material of the packaging film is
PLA/SiO2- PLA blend film/SiO2/ SiO2- PLA blend film/PLA laminated film, the SiO2Film thickness is 1000 nm,
The thickness of two layers of PLA film is 3000 nm, two layers of SiO2The thickness of-PLA blend film is 1000nm.
2, photoelectric device packaging method comprising steps of
1), the PLA chloroformic solution of 10 mg/ml is cast using the method for casting on the silver electrode top surface of photoelectric device
Film forming, then 0.8 Pa is dried in vacuo 30 min and is prepared into PLA film under the conditions of 120 DEG C；
2) SiO for being, under alkaline condition, 20 wt% by mass fraction2Alcoholic solution and ammonium lacate according to 1:1 ratio in nitrogen
It is reacted under atmosphere, reaction temperature is 100 DEG C, reaction time 1h, and reaction is added in above-mentioned reaction system after completing
For stannous octoate 0.01g as catalyst the reaction was continued in a vacuum 5 h, reaction temperature is 150 DEG C.Reaction product is dissolved in
In tetrahydrofuran solution, solution concentration is 10 mg/ml, casting film is carried out in the PLA film surface, then at 120 DEG C
Under the conditions of 0.8 Pa be dried in vacuo 30 min be prepared into SiO2- PLA blend film；
3) method for, then using PECVD, uses silane (SiH4) it is 40 sccm and laughing gas (N2O) be 300sccm, wait from
It is reacted under sub- state, technological temperature is 150 DEG C, and power is 190 W, and nitrogen flow is 600 sccm, and plated film rate is 40 nm/
Silica membrane is prepared under the conditions of min；
4) one layer of SiO, is prepared on the silica membrane surface using the method for step 2 again2- PLA blend film；
5), using the method for step 1) SiO described in step 4)2- PLA blend film surface prepares PLA film, then 120
0.8 Pa is dried in vacuo 30 min under the conditions of DEG C, realizes the encapsulation to photoelectric device.
Embodiment 3
1, the structure of photoelectric device are as follows: ITO substrate/PEDOT:PSS (50 nm)/poly-TPD (30 nm)/quantum dot light emitting
Layer (20 nm)/ZnO (30nm)/silver (70 nm)/packaging film (4100 nm), wherein the material of the packaging film is
PLA/ZnO-PLA blend film/ZnO/ ZnO-PLA blend film/PLA laminated film, the ZnO film is with a thickness of 100 nm, and two layers
The thickness of PLA film is 1000 nm, and the thickness of two layers of ZnO-PLA blend film is 1000nm.
2, photoelectric device packaging method comprising steps of
1), the PLA chloroformic solution of 10 mg/ml is cast using the method for casting on the silver electrode top surface of photoelectric device
Film forming, then 0.8 Pa is dried in vacuo 30 min and is prepared into PLA film under the conditions of 120 DEG C；
2), under alkaline condition, by mass fraction be 10 wt% ZnO alcoholic solution and ammonium lacate according to 1:1 ratio in nitrogen gas
It is reacted under atmosphere, reaction temperature is 100 DEG C, reaction time 1h, and reaction is added pungent in above-mentioned reaction system after completing
For sour stannous 0.01g as catalyst the reaction was continued in a vacuum 5 h, reaction temperature is 150 DEG C.Reaction product is dissolved in four
In hydrogen tetrahydrofuran solution, solution concentration is 10 mg/ml, casting film is carried out in the PLA film surface, then in 120 DEG C of items
0.8 Pa is dried in vacuo 30 min and is prepared into ZnO-PLA blend film under part；
3) method for, then using PECVD is 50 sccm and laughing gas (N using zinc acetate (DEZn)2It O) is 100 sccm,
It is reacted under plasmoid, technological temperature is 100 DEG C, power 150W, and nitrogen flow is 600 sccm, and plated film rate is 40
Zinc-oxide film is prepared under the conditions of nm/min；
4) layer of ZnO-PLA blend film, is prepared in the zinc oxide films film surface using the method for step 2 again；
5), using the method for step 1), the ZnO-PLA blend film surface described in step 4) prepares PLA film, then 120
0.8 Pa is dried in vacuo 30 min under the conditions of DEG C, realizes the encapsulation to photoelectric device.
Embodiment 4
1, the structure of photoelectric device are as follows: ITO substrate/PEDOT:PSS (50 nm)/poly-TPD (30 nm)/quantum dot light emitting
Layer (20 nm)/ZnO (30nm)/silver (70 nm)/packaging film (4100 nm), wherein the material of the packaging film is
PTFE/TiO2-PTFE blend film/TiO2/ TiO2-PTFE blend film/PTFE film, the TiO2 film thickness are 100 nm,
The thickness of two layers of polytetrafluoroethylene (PTFE) film is 1000 nm, and the thickness of two layers of TiO2-PTFE blend film is
1000nm。
2, photoelectric device packaging method comprising steps of
1), the PTFE chloroformic solution of 10 mg/ml is cast using the method for casting on the silver electrode top surface of photoelectric device
Film forming, then 0.8 Pa is dried in vacuo 30 min and is prepared into PTFE film under the conditions of 120 DEG C；
2), under alkaline condition, TiO2 alcoholic solution and tetrafluoroethene that mass fraction is 10 wt% are existed according to the ratio of 1:1
It is reacted under nitrogen atmosphere, reaction temperature is 100 DEG C, reaction time 1h, after reaction completion in above-mentioned reaction system
Hydrochloric acid 0.01g is added as catalyst the reaction was continued in a vacuum 5 h, reaction temperature is 150 DEG C.Reaction product is dissolved in
In tetrahydrofuran solution, solution concentration is 10 mg/ml, casting film is carried out in the PTFE film surface, then at 120 DEG C
Under the conditions of 0.8 Pa be dried in vacuo 30 min be prepared into TiO2-PTFE blend film；
3) method for, then using PECVD is 50 sccm and laughing gas (N using acetic acid titanium (DETi)2It O) is 100 sccm,
It is reacted under plasmoid, technological temperature is 100 DEG C, power 150W, and nitrogen flow is 600 sccm, and plated film rate is 40
Titanium deoxid film is prepared under the conditions of nm/min；
4) one layer of TiO2-PTFE blend film, is prepared on the titanium deoxid film surface using the method for step 2 again；
5), using the method for step 1), the TiO2-PTFE blend film surface described in step 4) prepares PTFE film, then exists
0.8 Pa is dried in vacuo 30 min under the conditions of 120 DEG C, realizes the encapsulation to photoelectric device.
In conclusion packaging film provided by the invention includes the first organic film being stacked, by polymer and pottery
First blend film of ceramic material composition, the ceramic membrane being made of ceramic material second are total to by polymer and ceramic material form
Mixed film, the second organic film.The present invention causes 1-4 layers using the first organic film and the second organic film as aqueous vapor separation layer
Close ceramic membrane is arranged as oxygen barrier layer, while between the ceramic membrane and organic film by polymer and ceramic material
The blended layer of composition, the blended layer can effectively promote the binding force between organic film and ceramic membrane, to enhance thinner package
The water and oxygen barrier property of film, and then meet requirement of the photoelectric device to steam permeability, improve the service life of photoelectric device.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (14)
1. a kind of packaging film, which is characterized in that including be stacked the first organic film, by polymer and ceramic material group
At the first blend film, be made of ceramic material 1-4 layer ceramic membrane, by polymer and ceramic material form second be blended
Film, the second organic film.
2. packaging film according to claim 1, which is characterized in that the ceramic material is silica, aluminium oxide, oxidation
One of zinc, titanium oxide and tungsten oxide are a variety of.
3. packaging film according to claim 1, which is characterized in that first organic film material, second organic thin
Membrane material, the polymer in the first blend film and the polymer in the second blend film are independently selected from polylactic acid, polytetrafluoroethylene (PTFE),
One of polymethyl siloxane and polypropylene are a variety of.
4. packaging film according to claim 1, which is characterized in that first organic film with a thickness of 1-3 μm；
And/or second organic film with a thickness of 1-3 μm.
5. packaging film according to claim 1, which is characterized in that first blend film with a thickness of 0.8-1.2 μm；
And/or second blend film with a thickness of 0.8-1.2 μm.
6. packaging film according to claim 1, which is characterized in that the ceramic membrane with a thickness of 0.1-1 μm.
7. a kind of preparation method of packaging film, which is characterized in that comprising steps of
Device to be packaged is provided, deposits the first organic film in the device surface；
The first blend film is deposited on the first organic film, first blend film is made of polymer and ceramic material；
The N layer ceramic membrane of lamination setting, 1≤N≤4 are deposited in the first blend film；
The second blend film is deposited on n-th layer ceramic membrane, second blend film is made of polymer and ceramic material；
The second organic film is deposited in the second blend film.
8. the preparation method of packaging film according to claim 7, which is characterized in that described to sink on the first organic film
The preparation of the first hybrid films of product includes the following steps:
Under alkaline condition, inorganic precursor and organic monomer are carried out under an inert atmosphere according to predetermined weight ratio anti-for the first time
It answers；
Catalyst is added, obtains intermingling material after carrying out the second secondary response under vacuum conditions；
It will be distributed in tetrahydrofuran solvent after intermingling material drying, obtain the blending being made of polymer and ceramic material
Liquid；
The blended liquid being made of polymer and ceramic material is deposited on the first organic film, obtains the first blend film.
9. the preparation method of packaging film according to claim 8, which is characterized in that the inorganic precursor is positive silicic acid
Ethyl ester, aluminum nitrate, zinc acetate, sodium tungstate or butyl titanate.
10. the preparation method of packaging film according to claim 8, which is characterized in that the organic monomer be lactic acid, four
Vinyl fluoride, one of methylsiloxane and propylene or a variety of.
11. the preparation method of packaging film according to claim 8, which is characterized in that the catalyst be stannous octoate,
One of stannous acetate and hydrochloric acid are a variety of.
12. the preparation method of packaging film according to claim 8, which is characterized in that the temperature of the first set reaction
It is 0.5-1 DEG C/min for 50-100 DEG C and/or heating rate.
13. the preparation method of packaging film according to claim 8, which is characterized in that the temperature of second secondary response
It is 150-200 DEG C.
14. a kind of photoelectric device, including first electrode, luminescent layer and second electrode, which is characterized in that in the second electrode
It is provided with packaging film, the packaging film is packaging film described in any one of claims 1-6 or the packaging film
For the packaging film of any one of claim 7-13 the method preparation.
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