CN102476482A - Packaging film, packaging structure and its formation method - Google Patents
Packaging film, packaging structure and its formation method Download PDFInfo
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- CN102476482A CN102476482A CN201010562736XA CN201010562736A CN102476482A CN 102476482 A CN102476482 A CN 102476482A CN 201010562736X A CN201010562736X A CN 201010562736XA CN 201010562736 A CN201010562736 A CN 201010562736A CN 102476482 A CN102476482 A CN 102476482A
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- hydrophilic group
- inorganic oxide
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- monomer
- organic layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a packaging film. By an atomic layer deposition method, an inorganic oxide layer is formed on an organic packaging layer formed by a polymer containing a hydrophilic group to obtain the packaging film, wherein a covalent bond is jointed between the inorganic oxide layer and the organic packaging layer. The above packaging film can be used to improve the water absorption problem of present organic packaging layers, and is applicable to be used to package photoelectric elements.
Description
[technical field]
The present invention relates to a kind of encapsulating structure, relate more specifically to the encapsulating film that this encapsulating structure adopts.
[background technology]
The commercial solar cell module uses the good ethylene-vinyl acetate copolymer of moisture-proof (EVA) as encapsulating material more at present.But carbonyl resin such as EVA is in the ultraviolet ray irradiation damage flavescence easily down of sunshine, and then influences the efficient that penetrates of sunshine.One of present replacement scheme penetrates the high vinyl butyral-vinyl alcohol of efficient-vinyl acetate co-polymer (poly (vinylbutryl-co-vinyl alcohol-co-vinyl acetate) for ultraviolet ray.Yet the hydroxyl of above-mentioned copolymer absorbs water easily, can't avoid the solar cell of its encapsulation of aqueous vapor infringement.In sum, need the water imbibition of the copolymer that reduces above-mentioned hydroxyl at present badly, it is applied in the photoelectric cell such as solar cell.
[summary of the invention]
The present invention provides a kind of encapsulating film, comprises the formed organic encapsulated layer of the polymer that contains hydrophilic group; And be formed at the inorganic oxide layer on this organic encapsulated layer; Wherein has the covalent bond knot between inorganic oxide layer and the organic encapsulated layer.
The present invention also provides a kind of encapsulating structure, comprises photoelectric cell; And above-mentioned encapsulating film coats photoelectric cell; Wherein organic encapsulated layer is located between photoelectric cell and the inorganic oxide layer.
The present invention further provides a kind of formation method of encapsulating structure, comprises photoelectric cell is provided; Coat photoelectric cell with the formed organic encapsulated layer of the polymer that contains hydrophilic group; And on organic encapsulated layer, form inorganic oxide layer with atomic layer deposition method, wherein have the covalent bond knot between inorganic oxide layer and the organic encapsulated layer.
[description of drawings]
Fig. 1 is the sketch map of the encapsulating structure of an embodiment of the present invention.
[main description of reference numerals]
10～substrate;
11～photoelectric cell;
13～organic encapsulated layer;
15～inorganic oxide layer.
[specific embodiment]
The present invention provides a kind of formation method of encapsulating structure.Shown in the encapsulating structure of Fig. 1, the photoelectric cell 11 on the substrate 10 is provided.Substrate 10 is flexible materials such as plastic cement.Photoelectric cell can be device such as light-emittingdiode (LED) or the LCD (LCD) that converts electrical energy into luminous energy, and also can be transform light energy is the device such as the solar cell of electric energy.The organic polymer that then forms with the monomer polymerization that contains hydrophilic group is as organic encapsulated layer 13; To coat photoelectric cell 11, wherein should organic encapsulated layer 13 formation after, its surperficial possess hydrophilic property functional group; This organic polymer for example is polyvinyl alcohol (Polyvinylalcohol; PVA), polyacrylate (Polyacrylate), polyvinyl butyral resin (Polyvinyl butyral, PVB), poly hydroxy ethyl acrylate (polyhydroxyethyl methacrylate, pHEMA).In an embodiment of the present invention, hydrophilic group is hydroxyl or carboxylic acid group, and organic encapsulated layer 13 can be polyvinyl alcohol (PVA).In another embodiment of the present invention; Can further adopt the monomer copolymerization of other monomer that does not contain hydrophilic group and above-mentioned hydrophilic group to form organic encapsulated layer 13, the molar ratio with monomer that contains hydrophilic group and the monomer that does not contain hydrophilic group was good greater than 50: 50 especially.If the molar ratio of monomer that contains hydrophilic group is less than the molar ratio of the monomer that does not contain hydrophilic group; Then can't help ald film nucleation to grow up, form the monomer for example vinyl alcohol (vinyl alcohol), vinyl butyral (vinyl butyral) or the hydroxyethyl methacrylate (HEMA) that still have hydrophilic group behind the polymer; And the monomer that does not have hydrophilic group behind the formation polymer for example ethene (ethylene), propylene (propylene), butylene (butene), vinyl chloride (vinyl chloride), isoprene (isoprene), styrene (styrene), acid imide (imide), methyl methacrylate (MMA), vinylacetate (vinyl acetate).For instance; Organic encapsulated layer 13 can be polyvinyl alcohol (PVA), vinyl butyral-vinyl alcohol-vinyl acetate co-polymer or hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) copolymer, and the monomer that contains hydrophilic group (HEMA) that wherein comprises in the copolymer with HEMA and MMA was good with the molar ratio of the monomer (MMA) that does not contain hydrophilic group greater than 50: 50.Method with organic encapsulated layer 13 packaged photoelectronic elements 11 can be rubbing method.In an embodiment of the present invention, the thickness of organic encapsulated layer 13 is between 1 μ m-20 μ m.If the thickness of organic encapsulated layer 13 is thin excessively, effective covered substrate, and influence the growth quality of follow-up organic encapsulated layer film.If the thickness of organic encapsulated layer 13 is blocked up, will cause light transmittance to descend.
Then on organic encapsulated layer 13, form inorganic oxide layer 15 with atomic layer deposition method.Above-mentioned atomic layer deposition method is a low temperature process, and its temperature is roughly between 50 to 120 ℃.If the temperature of atomic layer deposition method is low excessively, then the one-tenth of inorganic oxide layer is long-time of a specified duration excessively.If the temperature of atomic layer deposition method is too high, then possibly damages organic encapsulated layer 13, even damage the photoelectric cell 11 that organic encapsulated layer 13 coats.The principle of atomic layer deposition method is the pulsation that utilizes the steam after precursor gas or the heating to produce, at the substrate surface of the desire deposition film of successively growing up.For instance, can utilize the steam after argon gas heats trimethyl aluminium to send in the reaction chamber earlier.The hydroxyl reaction on trimethyl aluminium and organic encapsulated layer 13 surfaces is suc as formula 1 thus.In formula 1, n is the hydroxy number on organic encapsulated layer 13 surfaces.Organic encapsulated layer surface-(OH)
n+ nAl (CH
3)
3→ organic encapsulated layer surface-(O-Al (CH
3)
2 *)
n+ nCH
4(formula 1)
Then with Ar or N
2Purify reaction chamber etc. non-reactive gas, remove unnecessary trimethyl aluminium and byproduct of reaction methane.Then with oxidation source H
2O imports reaction chamber, carries out the reaction of formula 2.Organic encapsulated layer surface-(O-Al (CH
3)
2 *)
n+ 2nH
2O → organic encapsulated layer surface-(O-Al-(OH)
2 *)
n+ 2nCH
4(formula 2)
Then again with Ar or N
2Purify reaction chamber etc. non-reactive gas, remove unnecessary aqueous vapor and byproduct methane.The reaction of above-mentioned formula 1-2 and two cleanings are called an ALD circulation, and its surface will be covered with hydroxyl once more.Above-mentioned circulation can constantly repeat, up to the inorganic oxide layer 15 of growth adequate thickness.Can know to have the covalent bond knot between the surface of organic encapsulated layer 13 and the inorganic oxide layer 15 by above-mentioned explanation.Above-mentioned inorganic oxide layer 15 can be monolayer material such as aluminium oxide, zinc oxide, zirconia, silica or hafnium oxide, also can be multilayer material such as the alumina-zirconia alternately arranged.In an embodiment of the present invention, the thickness of inorganic oxide layer 15 is between between the 5nm to 100nm.If the thickness of inorganic oxide layer 15 is thin excessively, then can't effectively stop aqueous vapor or other pollutant infringement photoelectric cell 11.If the thickness of inorganic oxide layer is blocked up, then can reduce the light transmission and the pliability of encapsulating structure.Because inorganic oxide layer 15 is fine and close nanoscale structures, can't influence the flexible character of organic encapsulated layer 13.In other words, the encapsulating film of being made up of inorganic oxide layer 15 and organic encapsulated layer 13 is a pliability.If substrate 10 also has pliability with photoelectric cell 11, the above-mentioned bendable encapsulating film of arranging in pairs or groups again can be accomplished the encapsulating structure of flexible.
In order to let above and other objects of the present invention, characteristic and the advantage can be more obviously understandable, hereinafter is special to be lifted a plurality of embodiment and also combines accompanying drawing to elaborate as follows:
[embodiment]
The experiment of aqueous vapor penetrance
The MOCON Aquatran that uses MOCON company to produce measures.
The helium breakthrough experiment
Use helium leakage detector (Helium Leakage detector) to measure.
The oxygen penetration experiment
The MOCON Oxtran that uses MOCON company to produce measures.
Embodiment 1
Get commercially available vinyl butyral-vinyl alcohol-vinyl acetate co-polymer film (Polyvinylbutyral-vinyl alcohol-vinyl acetate; Available from the Changchun chemical industry); Under 50 ℃, carry out atomic layer deposition method with aluminum oxide layer on copolymer film, step is following:
A. in apparatus for atomic layer deposition (available from Cambridge NanoTech company), aforesaid copolymer film is inserted in the reaction chamber, feed trimethyl aluminium gas, under 120 ℃, carry out deposition reaction, gas pulses (pulse) time was 0.03 second;
B. feed Ar gas, bleed 5 seconds of time;
C. feed the water vapour of heating-up temperature to 25 ℃, 0.02 second burst length;
D. feed Ar gas, bleed 5 seconds of time;
A. to d. step 70 time is carried out in circulation repeatedly;
Obtain alumina layer, its thickness is about 35nm.
Embodiment 2
Get commercially available polyvinyl alcohol (PVA) film (available from the Changchun chemical industry), its structure is as shown in the formula shown in 1.Then with embodiment 1, under 120 ℃, carry out atomic layer deposition method, on polyvinyl alcohol film, its aluminium oxide thickness is about 35nm with aluminum oxide layer.
Embodiment 3
Get commercially available polyvinyl alcohol (PVA) film (available from the Changchun chemical industry).Then under 120 ℃, carry out atomic layer deposition method; And alternating deposit alumina layer
/on polyvinyl alcohol film, step is following for hafnium oxide layer
:
A. in apparatus for atomic layer deposition (available from Cambridge NanoTech company), aforesaid polyvinyl alcohol film is inserted in the reaction chamber, feed trimethyl aluminium gas, under 120 ℃ of temperature, carry out deposition reaction, 0.03 second of burst length;
B. feed Ar gas, bleed 5 seconds of time;
C. feed the water vapour of heating-up temperature to 25 ℃, the burst length was 0.02 second;
D. feed Ar gas, bleed 5 seconds of time;
E. repeat a. step, but only trimethyl aluminium is changed with four (dimethyl amine) hafnium, and proceed b. to d. step;
Carry out a. to e. step 70 time repeatedly;
The multilevel oxide thickness that obtains is about 35nm.
Embodiment 4
Get hydroxyethyl methacrylate (2-Hydroxyethyl 2-methylprop-2-enoate; Be called for short HEMA, its structure is as shown in the formula shown in 2) (methyl 2-methylpropenoate is called for short MMA with methyl methacrylate; Its structure is as shown in the formula shown in 3) the formed copolymer film of copolymerization; The synthetic method of this film is for example following: the MMA monomer of 6 moles HEMA monomers and 4 moles is dissolved in the methyl alcohol jointly, places under the nitrogen atmosphere, add 80 milligrams of free radical starting agent azodiisobutyronitrile AIBN (Azobisisobutyronitrile); Be heated to 65 ℃ and maintenance level concussion speed 400rpm with water-bath, reacted 24 hours.The feeding manner of monomer can directly get in the reactive tank simultaneously, and charge proportion is to carry out with the mode of control monomer molar ratio, and with regard to present embodiment, the molar ratio of its HEMA monomer and MMA monomer was greater than 50: 50.Then, under 120 ℃, carry out atomic layer deposition method with embodiment 1, aluminum oxide layer on the HEMA copolymer film, its aluminium oxide thickness is about 35nm.
Comparative example 5
Get polyimides (its structure is as shown in the formula shown in 4 for Polyimide, PI) film, do not have hydroxyl in the monomer whose.Then, under 120 ℃, carry out atomic layer deposition method with embodiment 1, aluminum oxide layer on the PI film, its aluminium oxide thickness is about 35nm.
The inorganic oxide thickness of fixing these five kinds of experimental examples, its aqueous vapor penetrance, oxygen penetration rate, and the result of helium penetrance more as shown in table 1.
Table 1
Can know that by table 1 alumina layer that ALD grows up can significantly reduce the aqueous vapor penetrance of the copolymer of hydroxyl monomer.And the aqueous vapor penetrance with more polyhydric PVA can be greater than vinyl butyral-vinyl alcohol-vinyl acetate co-polymer.In addition; Can know by embodiment 1,2,4 and comparative example 5 contrasts; Along with the molar ratio of the monomer that has hydrophilic group in the copolymerized macromolecule with the monomer that does not contain hydrophilic group increases, its helium penetrance reduces thereupon, that is the choke ability improves; This is because more hydroxyl can make the aluminium oxide of ald and the covalent bond density between the film surface higher, can further reduce the aqueous vapor penetrance of composite membrane.In sum, it is generally acknowledged that the high-hydroscopicity PVA that is inappropriate for packaged photoelectronic element behind the aluminium oxide of collocation ALD deposition, is more suitable for as encapsulating film than the copolymer that contains small amount of hydroxyl groups on the contrary.In addition, when adopting the sandwich construction of aluminium oxide/hafnium oxide alternately, the penetrance of its aqueous vapor, oxygen and nitrogen can be lower than the single alumina layer of similar thickness.
Though the present invention discloses as above with a plurality of preferred embodiments, so it is not that those skilled in the art under any the present invention are not breaking away from the spirit and scope of the present invention in order to qualification the present invention, and Ying Kezuo changes arbitrarily and retouches.Therefore, protection scope of the present invention should be as the criterion with the appended claims restricted portion.
Claims (14)
1. encapsulating film comprises:
Organic layer, it is formed by the polymer that contains hydrophilic group; And
Inorganic oxide layer, it is formed on this organic layer;
Wherein has the covalent bond knot between this inorganic oxide layer and this organic layer.
2. encapsulating film as claimed in claim 1, wherein this hydrophilic group is hydroxyl or carboxylic acid group.
3. encapsulating film as claimed in claim 1, wherein this organic layer comprises polyvinyl alcohol.
4. encapsulating film as claimed in claim 1; The polymer that contains hydrophilic group that wherein forms this organic layer further comprises the material that is formed by monomer that does not contain hydrophilic group and the monomer copolymerization that contains hydrophilic group, and this molar ratio of monomer and this monomer that does not contain hydrophilic group that contains hydrophilic group was greater than 50: 50.
5. encapsulating film as claimed in claim 1, wherein this inorganic oxide layer comprises aluminium oxide, zinc oxide, zirconia, silica, hafnium oxide or above-mentioned combination.
6. encapsulating film as claimed in claim 1, wherein the thickness of this inorganic oxide layer is 5nm to 100nm.
7. encapsulating structure comprises:
Photoelectric cell; And
Encapsulating film as claimed in claim 1 coats this photoelectric cell;
Wherein this organic layer is located between this photoelectric cell and this inorganic oxide layer.
8. the formation method of an encapsulating structure comprises:
Photoelectric cell is provided;
Coat this photoelectric cell with the formed organic layer of the polymer that contains hydrophilic group; And
On this organic layer, form inorganic oxide layer with atomic layer deposition method;
Wherein has the covalent bond knot between this inorganic oxide layer and this organic layer.
9. the formation method of encapsulating structure as claimed in claim 8, wherein this hydrophilic group is hydroxyl or carboxylic acid group.
10. the formation method of encapsulating structure as claimed in claim 8, wherein this organic layer comprises polyvinyl alcohol.
11. the formation method of encapsulating structure as claimed in claim 8; Wherein, This polymer that contains hydrophilic group forms this organic layer with monomer that does not contain hydrophilic group and the monomer copolymerization that contains hydrophilic group, and this molar ratio of monomer and this monomer that does not contain hydrophilic group that contains hydrophilic group was greater than 50: 50.
12. the formation method of encapsulating structure as claimed in claim 8, wherein this inorganic oxide layer comprises aluminium oxide, zinc oxide, zirconia, silica, hafnium oxide or above-mentioned combination.
13. the formation method of encapsulating structure as claimed in claim 8, wherein the thickness of this inorganic oxide layer is 5nm to 100nm.
14. the formation method of encapsulating structure as claimed in claim 8 is 25 to 120 ℃ with the temperature that on this organic layer, forms this inorganic oxide layer wherein.
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| CN201010562736XA CN102476482A (en) | 2010-11-25 | 2010-11-25 | Packaging film, packaging structure and its formation method |
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| CN201010562736XA CN102476482A (en) | 2010-11-25 | 2010-11-25 | Packaging film, packaging structure and its formation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103441203A (en) * | 2013-07-24 | 2013-12-11 | 重庆四联光电科技有限公司 | Packaging method and packaging structure for semiconductor device |
| CN106960891A (en) * | 2017-03-09 | 2017-07-18 | 杭州福斯特应用材料股份有限公司 | A kind of photovoltaic transparent composite membrane and preparation method and application |
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| CN106960891A (en) * | 2017-03-09 | 2017-07-18 | 杭州福斯特应用材料股份有限公司 | A kind of photovoltaic transparent composite membrane and preparation method and application |
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Application publication date: 20120530 |