CN101714583A - Flexible thin film solar cell and preparation method thereof - Google Patents
Flexible thin film solar cell and preparation method thereof Download PDFInfo
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- CN101714583A CN101714583A CN200910206697A CN200910206697A CN101714583A CN 101714583 A CN101714583 A CN 101714583A CN 200910206697 A CN200910206697 A CN 200910206697A CN 200910206697 A CN200910206697 A CN 200910206697A CN 101714583 A CN101714583 A CN 101714583A
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- 239000010409 thin film Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 60
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 18
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920006254 polymer film Polymers 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 33
- 238000005516 engineering process Methods 0.000 claims description 22
- 239000010408 film Substances 0.000 claims description 20
- 229920005570 flexible polymer Polymers 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 7
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 7
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 6
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims description 6
- 238000001947 vapour-phase growth Methods 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
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- 230000015572 biosynthetic process Effects 0.000 claims description 3
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- 229920000307 polymer substrate Polymers 0.000 abstract description 4
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- 239000000047 product Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 1
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- 239000004411 aluminium Substances 0.000 description 1
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- 238000013082 photovoltaic technology Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
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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
- Y02E10/548—Amorphous silicon PV cells
-
- 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
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Abstract
The invention provides a flexible thin film solar cell, wherein the cell comprises the following structures: a light inlet substrate (21) which is formed from a flexible thin polymer film; a first electrode layer (22) which is formed by depositing zinc oxide on the light inlet substrate (21); a photoelectric conversion layer (23) which consists of p-type, i-type and n-type amorphous silicon layers formed in turn on the first electrode layer (22); and a second electrode layer (24) which is formed by depositing zinc oxide on the photoelectric conversion layer (23). The preparation method forms front and back electrode layers of the thin film solar cell by adopting a zinc oxide low-temperature deposition process, enables the thin polymer film to be taken as a flexible substrate, and can transplant the process for manufacturing the thin film solar cell with a glass substrate to the process for manufacturing the flexible thin film solar cell with a polymer substrate.
Description
Technical field
The present invention relates to solar cell fabrication process, particularly be used for a kind of flexible thin-film solar cell and preparation method thereof.
Background technology
Along with high speed development, the technology of modern industry updates and to the demand of the energy, the change of essence is taking place energy resource structure now fast.Traditional energy: the use amount of coal, oil, natural gas will arrive the peak in the year two thousand twenty-the year two thousand forty, and will peter out after the year two thousand fifty.Regenerative resource alternative energy sources such as (mainly being solar energy) is since fast development in 2000, to the year two thousand fifty use amount will peak.Conventional solar cell is to use monocrystalline silicon or polysilicon thin slice, and wherein the silicon materials application is more, and waste is serious, and element silicon purifying technique complexity and cost are too high.Thin-film solar cells is used amorphous silicon or other materials, the element silicon amount is used and seldom or is not used silicon materials, so there is not the raw material bottleneck substantially, especially amorphous silicon thin-film solar cell, low and the technical maturity of cost, so develop very soon, become one of the most ripe product of current thin film solar cell.
The amorphous microcrystalline silicon film solar batteries is the handsome person in the hull cell industrialization technology of new generation, it is good at conversion efficiency height, good stability, main feature such as with low cost, becomes the mainstream technology that at first realizes the electrical network equivalent point in the photovoltaic technology probably.The conventional films battery is that the basis makes with the glass substrate, and glass is a kind of good protective material, has good light transmittance again, is a kind of excellent backing material.But glass also has its limitation, and is heavier as the inflexibility and the weight of glass, influences its application in some special dimension.Relatively more direct as the curved face type product, as the sunlight window of roof of the vehicle, or the solar power system that the subsides wing is installed on the drone etc.; Portable for another example, can roll up folding charging system etc.; In addition, the requirement of a lot of general character was that the weight of system is low weight during these were used, and this is even more important concerning aerospace applications.The backing material of existing flexible thin-film solar cell adopts stainless steel film and polymer film usually.Because therefore stainless steel film cost height, heavy and have conductivity will satisfy the needs of above these application, the light-weight polymer film is a kind of more satisfactory backing material.Therefore it is non-conductive, can make assembly with ready-made laser cutting parameter, and cuts after not needing hull cell made again, and connects again then.Polymer substrate such as polyimides (Kapton) film has high-low temperature resistant, acidproof alkali, anti-solvent, electric insulation (H level), radiation proof, is fit to the vacuum filming technology, and performance such as thin thickness and pulling force be good, is a kind of good selection of flexible solar battery.
As shown in Figure 1, a kind of layer structure of traditional unijunction amorphous silicon thin-film solar cell shown in it.This amorphous silicon thin-film solar cell is a deposition, sputter sensitive surface electrode 2, photoelectric conversion layer 3, rear surface electrode 4 and form successively on transparency carrier 1 (mainly being glass).As transparency carrier 1, can adopt glass plate, transparent resin film etc.Sensitive surface electrode 2 is made of for example ITO transparent conductive oxides such as (pluging with molten metal tin-oxide).From sensitive surface electrode 2 sides, photoelectric conversion layer 3 has the laminated structure of p type amorphous silicon layer, i type amorphous silicon layer and n type amorphous silicon layer.Rear surface electrode 4 is made of the laminated film of metal materials such as for example silver, aluminium, titanium, copper and metal oxides such as ITO, SnO.
Yet traditional in the past hull cell technology no matter be p-i-n structure or n-i-p structure, all has at least one procedure to adopt higher temperature, promptly surpasses the highest bearing temperature (about 400 ℃) of polymer film.Is to prepare on the temperature about 500 ℃ as adopting aumospheric pressure cvd method (APCVD) formation with tin oxide in the p-i-n structure as the electrically conducting transparent membrane material of electrode; Then will form the silver layer that possesses good suede structure in the n-i-p structure also is to prepare under quite high underlayer temperature.Therefore traditional technology is difficult, and even change technology and reduce coating temperature, the conversion efficiency of the solar cell of made is lower to be applied to flexible polymer substrate, and generally below 5%, it is too high to influence effect and cost.
Therefore this tradition thin-film solar cells manufacturing process that is used for glass substrate is difficult to directly transplanting and is applied to make with the manufacturing of polymeric material as the flexible thin-film solar cell of substrate.
Summary of the invention
In order to be applied to make the thin-film solar cells of flexible substrate after realizing the thin-film solar cells manufacturing process of traditional glass substrate revised a little, a kind of novel flexible thin-film solar cell and manufacture method thereof are proposed at this.
According to an aspect of the present invention, provide a kind of flexible thin-film solar cell, comprising following structure: advance light face substrate with what flexible polymer film constituted at this; Advancing first electrode layer that deposit zinc oxide forms on the light face substrate; The photoelectric conversion layer that on first electrode layer, constitutes by the p type that forms successively, i type and n type amorphous silicon layer; And the second electrode lay that deposit zinc oxide forms on described photoelectric conversion layer.
According to another aspect of the present invention, provide a kind of flexible thin-film solar cell, comprising following structure: the shady face substrate that constitutes with flexible polymer film at this; The third electrode layer that deposit zinc oxide forms on the shady face substrate; The photoelectric conversion layer that on the third electrode layer, constitutes by the n type that forms successively, i type and p type amorphous silicon layer; And the 4th electrode layer that deposit zinc oxide forms on described photoelectric conversion layer.
According to another aspect of the present invention, wherein said advance light face substrate by light transmission greater than 80% and the thin polymer film that can bear greater than 200 ℃ temperature constitute; Described shady face substrate is made of the thin polymer film that can bear greater than 200 ℃ temperature.
According to another aspect of the present invention, the wherein said material that advances light face substrate adopts PEN (PEN) or polyether sulfone (PES); The material of described shady face substrate adopts PEN (PEN), polyether sulfone (PES) or polyimides (Kapton) material.
According to another aspect of the present invention, wherein said first to fourth electrode layer is to adopt low-pressure chemical vapor phase deposition (LPCVD) technology deposit zinc oxide under 150 ℃-250 ℃ temperature to form.
The present invention also provides a kind of method of making flexible thin-film solar cell, comprising following steps: form into light face substrate with flexible polymer film; Advancing on the light face substrate deposit zinc oxide as first electrode layer; On first electrode layer by the p type that forms successively, i type and n type amorphous silicon layer as photoelectric conversion layer; And on described photoelectric conversion layer deposit zinc oxide as the second electrode lay.
The present invention also provides the another kind of method of making flexible thin-film solar cell, comprising following steps: form the shady face substrate with flexible polymer film; Deposit zinc oxide is as the third electrode layer on the shady face substrate; On the third electrode layer by the n type that forms successively, i type and p type amorphous silicon layer as photoelectric conversion layer; And on described photoelectric conversion layer deposit zinc oxide as the 4th electrode layer.
Description of drawings
Fig. 1 illustrates the layer structure of general thin solar cell;
Fig. 2 illustrates the layer structure according to p-i-n flexible thin-film solar cell of the present invention;
Fig. 3 illustrates the layer structure according to n-i-p flexible thin-film solar cell of the present invention; And
Describe the preferred embodiments of the present invention in detail below in conjunction with accompanying drawing.
Embodiment
Because being used for the thin-film solar cells manufacturing process of glass substrate, the tradition of above being mentioned to directly apply to the high efficiency flexible thin-film solar cell of manufacturing, changing into manufacturing for the thin-film solar cells manufacturing process that realizes making glass substrate is the flexible thin-film solar cell of substrate with the polymer film, and reduces the equipment input cost and improve product efficiency.The present invention proposes a kind of novel flexible thin-film solar cell and manufacture method thereof.
Because tradition is used for the thin-film solar cells manufacturing process of glass substrate, generally adopt aumospheric pressure cvd method (APCVD) to form nesa coating when making the p-i-n thin-film solar cells as electrode with tin oxide, and when making the n-i-p thin-film solar cells general employing need at high temperature make have good suede structure silver layer as back electrode.Therefore need to revise the high-temperature technology that these form electrode film, reduce the temperature that forms electrode film.For this reason, the present invention adopts with the zinc oxide material of low-pressure chemical vapor phase deposition (LPCVD) technology preparation and makes thin-film solar cells as the front and back electrode, because its preparation temperature is no more than 250 ℃, so can be easy to adopt the flexible polymer substrate material.Owing to do not need to change the basic technology condition, thus the conversion efficiency of battery can be accomplished and on glass substrate basically identical, promptly at present about 9%.
Specifically, for p-i-n type structure, only glass substrate is replaced as flexible polymer substrate.The transparent polymer substrate can be attached on the glass substrate in manufacturing process, technology need not done big change when making like this.Take off from glass plate after completing, final product is made in row encapsulation more as required then again.
Except that being attached on, polymer substrate carries out on the glass substrate can also using reel-to-reel (roll-to-roll) method and directly using flexible polymer substrate to process the various technology production processes.This method may all will be done bigger change to all machines.
As the encapsulating material of sunlight incident one side, the used backing material of this p-i-n structure must satisfy several conditions simultaneously, that is:
Light transmission＞80%
Temperature tolerance, the withstand temperature palpus of substrate＞200 ℃
As encapsulating material, then need to have performances such as stronger permeability resistance and uvioresistant ray as directly
Other physics and chemical property are as stretching resistance, hot coefficient of dilatation, corrosion resistance or the like
In order all to satisfy above terms and conditions, the present invention adopts the backing material of following two kinds of polymeric materials as flexible thin-film solar cell:
A) through heat treated PEN (PEN): this material can bear and surpass 200 ℃ treatment temperature, and is because its anti-ultraviolet performance is bad, aging easily.Therefore, need in addition with glass or ethylene-tetrafluoroethylene copolymer (Tefzel), perhaps will be attached to the glass of building inner surface with the glass shielding of ultraviolet as the thin-film solar cells of substrate, prevent that film-substrate is aging with PEN as the front encapsulating material.
B) PES (polyether sulfone): this material is a kind of possible PEN substitution material, and not only temperature tolerance is good, and anti-ultraviolet property is also preferable.
For the n-i-p structure, be about to flexible substrate and be placed on shady face, on n, i, the order of p is plated film successively.The alternative backing material kind of this kind structure is some more relatively, because the high light transmittance condition can be relaxed slightly.Except that above PEN and PES material, Kapton is a kind of available flexible substrate material.Because its light transmission is relatively poor, whole solar cell there is application product than the high light transmittance requirement, as sun roof etc., then not too suitable.
This constructed products useable glass or Tefzel be as the front encapsulating material, and back of the body encapsulating material can be glass or polymeric material, as thermoplastic's polyester (TPT) etc., perhaps not adds back of the body encapsulation.
The structure and the manufacturing process of flexible thin-film solar cell of the present invention are described with reference to the accompanying drawings.
Fig. 2 illustrates the layer structure according to p-i-n flexible thin-film solar cell of the present invention.Wherein flexible substrate 21 is for advancing light face substrate, its adopt light transmission greater than 80%, withstand temperature is greater than 200 ℃ thin polymer film.The preferred film that adopts PEN (PEN) or PES (polyether sulfone) material.On the flexible substrate 21 by LPCVD technology under about 150 ℃-250 ℃ temperature deposit zinc oxide (ZnO) as preceding electrode 22, the laminated structure that forms p type, i type and n type amorphous silicon layer successively on preceding electrode is as photoelectric conversion layer 23 then, and this photoelectric conversion layer 23 can be the laminated construction that many group p-i-n layers are arranged.At last on the photoelectric conversion layer 23 by LPCVD technology under about 150 ℃-250 ℃ temperature deposit zinc oxide (ZnO) as back electrode 24.
Fig. 3 illustrates the layer structure according to n-i-p flexible thin-film solar cell of the present invention.Wherein flexible substrate 34 is the shady face substrate, and it adopts withstand temperature greater than 200 ℃ thin polymer film.The preferred film that adopts PEN (PEN), PES (polyether sulfone) or Kapton (polyimides) material.On the flexible substrate 34 by LPCVD technology under about 150 ℃-250 ℃ temperature deposit zinc oxide (ZnO) as back electrode 33, the laminated structure that forms n type, i type and p type amorphous silicon layer successively on preceding electrode is as photoelectric conversion layer 32 then, and this photoelectric conversion layer 32 can be the laminated construction that many group n-i-p layers are arranged.At last on the photoelectric conversion layer 32 by LPCVD technology under about 150 ℃-250 ℃ temperature deposit zinc oxide (ZnO) as preceding electrode 31.
Though described embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art can make various distortion or modification within the scope of the appended claims.
Claims (16)
1. flexible thin-film solar cell, comprising following structure:
Advance light face substrate (21) with what flexible polymer film constituted;
Advancing upward first electrode layer (22) of deposit zinc oxide formation of light face substrate (21);
Go up the photoelectric conversion layer (23) that constitutes by the p type that forms successively, i type and n type amorphous silicon layer at first electrode layer (22); And
Go up the second electrode lay (24) that deposit zinc oxide forms at described photoelectric conversion layer (23).
2. flexible thin-film solar cell according to claim 1, wherein:
Advance light face substrate (21) by light transmission greater than 80% and the thin polymer film that can bear greater than 200 ℃ temperature constitute.
3. flexible thin-film solar cell according to claim 1 and 2, wherein:
The material that advances light face substrate (21) adopts PEN (PEN) or polyether sulfone (PES).
4. flexible thin-film solar cell according to claim 1, wherein:
First electrode layer (22) and the second electrode lay (24) are to adopt low-pressure chemical vapor phase deposition (LPCVD) technology deposit zinc oxide under 150 ℃-250 ℃ temperature to form.
5. flexible thin-film solar cell, comprising following structure:
Shady face substrate (34) with the flexible polymer film formation;
Go up the third electrode layer (33) that deposit zinc oxide forms at shady face substrate (34);
Go up the photoelectric conversion layer (32) that constitutes by the n type that forms successively, i type and p type amorphous silicon layer at third electrode layer (33); And
Go up the 4th electrode layer (31) that deposit zinc oxide forms at described photoelectric conversion layer (32).
6. flexible thin-film solar cell according to claim 5, wherein:
Shady face substrate (34) is made of the thin polymer film that can bear greater than 200 ℃ temperature.
7. according to claim 5 or 6 described flexible thin-film solar cells, wherein:
The material of shady face substrate (34) adopts PEN (PEN), polyether sulfone (PES) or polyimides (Kapton) material.
8. flexible thin-film solar cell according to claim 5, wherein:
Third electrode layer (33) and the 4th electrode layer (31) are to adopt low-pressure chemical vapor phase deposition (LPCVD) technology deposit zinc oxide under 150 ℃-250 ℃ temperature to form.
9. method of making flexible thin-film solar cell, comprising following steps:
Form into light face substrate (21) with flexible polymer film;
Advancing the last deposit zinc oxide of light face substrate (21) as first electrode layer (22);
Go up by the p type that forms successively, i type and n type amorphous silicon layer as photoelectric conversion layer (23) at first electrode layer (22); And
Go up deposit zinc oxide as the second electrode lay (24) at described photoelectric conversion layer (23).
10. the method for manufacturing flexible thin-film solar cell according to claim 9, wherein:
Adopt light transmission greater than 80% and the thin polymer film that can bear greater than 200 ℃ temperature constitute into light face substrate (21).
11. according to the method for claim 9 or 10 described manufacturing flexible thin-film solar cells, wherein:
Adopt PEN (PEN) or polyether sulfone (PES) to constitute and advance light face substrate (21).
12. the method for manufacturing flexible thin-film solar cell according to claim 9, wherein:
Adopt low-pressure chemical vapor phase deposition (LPCVD) technology deposit zinc oxide under 150 ℃-250 ℃ temperature to form described first electrode layer (22) and described the second electrode lay (24).
13. a method of making flexible thin-film solar cell, comprising following steps:
Form shady face substrate (34) with flexible polymer film;
Go up deposit zinc oxide as third electrode layer (33) at shady face substrate (34);
Go up by the n type that forms successively, i type and p type amorphous silicon layer as photoelectric conversion layer (32) at third electrode layer (33); And
Go up deposit zinc oxide as the 4th electrode layer (31) at described photoelectric conversion layer (32).
14. flexible thin-film solar cell according to claim 13, wherein:
Shady face substrate (34) is made of the thin polymer film that can bear greater than 200 ℃ temperature.
15. according to the method for claim 13 or 14 described manufacturing flexible thin-film solar cells, wherein:
Adopt PEN (PEN), polyether sulfone (PES) or polyimides (Kapton) material to constitute shady face substrate (34).
16. according to the method for claim 13 or 14 described manufacturing flexible thin-film solar cells, wherein:
Adopt low-pressure chemical vapor phase deposition (LPCVD) technology deposit zinc oxide under 150 ℃-250 ℃ temperature to constitute described third electrode layer (33) and described the 4th electrode layer (31).
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| WO2014180281A1 (en) * | 2013-05-07 | 2014-11-13 | 上海硕拉投资管理合伙企业（有限合伙） | Thin-film solar cell panel and manufacturing method therefor |
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| CN103296114A (en) * | 2013-05-07 | 2013-09-11 | 杨立友 | Solar automobile skylight and manufacturing method thereof |
| WO2014180281A1 (en) * | 2013-05-07 | 2014-11-13 | 上海硕拉投资管理合伙企业（有限合伙） | Thin-film solar cell panel and manufacturing method therefor |
| CN103296114B (en) * | 2013-05-07 | 2015-09-23 | 宁波山迪光能技术有限公司 | Solar telephone skylight and preparation method thereof |
| EP2996160A4 (en) * | 2013-05-07 | 2017-01-11 | Shanghai Solar Investment Management Partnerships | Thin-film solar cell panel and manufacturing method therefor |
| CN103465385A (en) * | 2013-09-18 | 2013-12-25 | 北京汉能创昱科技有限公司 | Flexible thin-film solar cell and segmentation, connection and preparation methods thereof |
| CN103465385B (en) * | 2013-09-18 | 2015-09-16 | 北京汉能创昱科技有限公司 | A kind of flexible thin-film solar cell and burst, connection and preparation method |
| CN113878979A (en) * | 2021-12-06 | 2022-01-04 | 杭州晶宝新能源科技有限公司 | Manufacturing method of precision template, precision template and application |
| CN113878979B (en) * | 2021-12-06 | 2022-03-15 | 杭州晶宝新能源科技有限公司 | Manufacturing method of precision template, precision template and application |
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