TWI566426B - A method of preparing a film of an organic solar cell using a continuous reel method - Google Patents
A method of preparing a film of an organic solar cell using a continuous reel method Download PDFInfo
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- TWI566426B TWI566426B TW102129746A TW102129746A TWI566426B TW I566426 B TWI566426 B TW I566426B TW 102129746 A TW102129746 A TW 102129746A TW 102129746 A TW102129746 A TW 102129746A TW I566426 B TWI566426 B TW I566426B
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- 238000000034 method Methods 0.000 title claims description 51
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 230000009975 flexible effect Effects 0.000 claims description 20
- 239000011787 zinc oxide Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 150000002466 imines Chemical class 0.000 claims 2
- 229920000573 polyethylene Polymers 0.000 claims 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 230000005525 hole transport Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007764 slot die coating Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- AZSFNTBGCTUQFX-UHFFFAOYSA-N C12=C3C(C4=C5C=6C7=C8C9=C(C%10=6)C6=C%11C=%12C%13=C%14C%11=C9C9=C8C8=C%11C%15=C%16C=%17C(C=%18C%19=C4C7=C8C%15=%18)=C4C7=C8C%15=C%18C%20=C(C=%178)C%16=C8C%11=C9C%14=C8C%20=C%13C%18=C8C9=%12)=C%19C4=C2C7=C2C%15=C8C=4C2=C1C12C3=C5C%10=C3C6=C9C=4C32C1(CCCC(=O)OC)C1=CC=CC=C1 Chemical compound C12=C3C(C4=C5C=6C7=C8C9=C(C%10=6)C6=C%11C=%12C%13=C%14C%11=C9C9=C8C8=C%11C%15=C%16C=%17C(C=%18C%19=C4C7=C8C%15=%18)=C4C7=C8C%15=C%18C%20=C(C=%178)C%16=C8C%11=C9C%14=C8C%20=C%13C%18=C8C9=%12)=C%19C4=C2C7=C2C%15=C8C=4C2=C1C12C3=C5C%10=C3C6=C9C=4C32C1(CCCC(=O)OC)C1=CC=CC=C1 AZSFNTBGCTUQFX-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 235000015096 spirit Nutrition 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
- B05D1/265—Extrusion coatings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/546—No clear coat specified each layer being cured, at least partially, separately
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/586—No clear coat specified each layer being cured, at least partially, separately
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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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
- Y02E10/549—Organic PV cells
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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
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Description
本發明係關於一種製備有機太陽能電池之膜層之方法，尤指一種使用連續捲軸法(roll to roll,R2R)進行有機太陽能電池之主動層及電子傳輸層之製備，並結合了狹縫(slot-die)塗佈之技術，以在生產效能和降低成本方面取得絕對優勢之製備方法。
太陽能電池的研究是再生能源中受眾人期待的一個方向。雖然現今已商業化的多數產品是以矽為其主要材料，不過使用高分子材料所開發之有機太陽能電池因其製程簡單、造價便宜、材質輕盈、可撓曲等特性而受到業界與學術界的矚目。
目前在製備有機太陽能電池時，其多是透過旋轉塗佈(Spin Coating)為製備太陽能電池薄膜之技術手段，其優點在於能夠使得該薄膜具有較佳之平整性與均勻性。然而，旋轉塗佈的一大限制在於無法用於製備大面積之太陽能電池薄膜，僅能用於小面積地製備產品，在未來商業化考量降低成本上有先天上的瓶頸存在，因此必須考慮以大面積方式來製備有機太陽能電池。
R2R製程即是一種具有潛力用以大面積製備有機太陽能電池的技術，其在產業界已有配合可撓性顯示器(flexible display)的製備，基於可撓性顯示器「軟」之特性，R2R製程即可良好地配合其運作，得以在較低成本之下生產這些具有可塑性、重量輕
、耐衝擊等優點之顯示器。
目前於太陽能電池領域的開發研究當中，也有嘗試引進R2R製程的潮流；然而，如何讓R2R製程能在太陽能電池的製備過程中發揮其特長，而讓製備成本得以降低之餘，其所形成之膜層亦能提供良好的工作效率，則仍有待技術能夠有進一步的改良。
本發明之主要目的，係提供一種使用連續捲軸法製備有機太陽能電池之膜層之方法，其透過R2R製程並利用狹縫塗佈技術快速且大面積地讓有機太陽能電池之電子傳輸層以及主動層成形，可降低有機太陽能電池的製作成本。
本發明之另一目的，係提供一種使用狹縫塗佈技術製備有機太陽能電池之膜層之方法，其藉由控制R2R製程中對電子傳輸層以及主動層的參數條件及特定溶劑之使用，而讓形成之膜層具有較佳的工作效率。
本發明之再一目的，係提供一種使用連續捲軸法製備有機太陽能電池之膜層之方法，其係配合使用狹縫塗佈之技術，使得用於製備電子傳輸層以及主動層的混摻材料得以被大面積、高均勻度、高材料利用率地塗佈，有助於提高膜層的品質。
故為了達到上述之目的，本發明揭示了一種使用連續捲軸法製備有機太陽能電池之膜層之方法，其係包含步驟：捲出(unwind)一軟性基板，該軟性基板之上係具有一陰極層；狹縫塗佈(slot die coating)一電子傳輸層於該陰極層之上，該電子傳輸層之材質係包含選自於氧化鋅(ZnO)以及氧化鋅摻鋁(Aluminum
doped ZnO,AZO)所組成之群組其中之一者，以及乙氧基聚乙烯亞胺(polyethylenimine ethoxylated,PEIE)；燒結該電子傳輸層；狹縫塗佈一主動層於該電子傳輸層之上，該主動層之材質係混摻鄰二甲苯(O-xylene)為溶劑，並同時烘乾該主動層；以及捲取(rewind)該軟性基板。在此些步驟的執行之下，有機太陽能電池之膜層即得以搭配R2R製程而順利成形。
1‧‧‧捲出部
2‧‧‧加工部
3‧‧‧捲取部
4‧‧‧塗佈頭
51‧‧‧軟性基板
52‧‧‧陰極層
53‧‧‧電子傳輸層
54‧‧‧主動層
55‧‧‧電洞傳輸層
56‧‧‧陽極層
S1~S5‧‧‧步驟
第一圖：其係為本發明一較佳實施例之步驟流程圖；第二圖：其係為本發明所使用之R2R製程架構示意圖；第三圖：其係為本發明所使用之R2R製程結合狹縫塗佈之架構示意圖；以及第四圖：其係為本發明之太陽電池之膜層之結構變化流程示意圖。
為使本發明之特徵及所達成之功效有更進一步之瞭解與認識，謹佐以較佳之實施例及配合詳細之說明，說明如後：首先，請參考第一圖，其係為本發明所揭示方法之步驟流程圖；如圖所示，其係包含了步驟：步驟S1：捲出一軟性基板，該軟性基板之上係具有一陰極層；步驟S2：狹縫塗佈一電子傳輸層於該陰極層之上，該電子傳輸層之材質係包含ZnO以及PEIE；步驟S3：燒結該電子傳輸層；步驟S4：狹縫塗佈一主動層於該電子傳輸層之上，該主動層之材質係混摻O-xylene為溶劑，並同時烘乾該主動層；以及
步驟S5：捲取該軟性基板。
本發明所揭示之方法係建立於R2R之機制下而得以運作，請參考第二圖以及第三圖，其係為R2R製程的簡單架構示意，其係包含了一捲出部1、一加工部2以及一捲取部3，其可讓軟板等軟性材料從圓筒狀的捲出部1捲出後，在加工部2之區段配合塗佈頭4於軟板的表面進行加工，因而賦予其特定用途之功能；最後再將之捲取為圓筒狀。其係為一種高效能、低成本之連續生產方式。
請配合第四圖所示之結構變化，本發明於步驟S1係捲出一軟性基板51，其具有可撓曲之性質而得以在R2R製程下使用。此軟性基板51之上係具有一陰極層52，其係做為有機太陽能電池之具有透明性質之陰極端，此陰極層52之材質係包含了具有導電性質之銦錫氧化物(Indium Tin Oxide,ITO)。其可透過沉積的方式而形成於軟性基板51之上。
在具有陰極層52的軟性基板51捲出後，接著於步驟S2，本發明利用狹縫塗佈(slot die coating)的方法，讓電子傳輸層53形成於陰極層52之上。此電子傳輸層53之功能係在於幫助主動層當中，經電子和電洞分離之後所產生的電子經由其而傳輸至陰極層52。
於此，本發明所選用的電子傳輸層之材質係包含作為主體之ZnO以及作為改質材料的PEIE，其中PEIE在進行混摻改質前已先行以重量百分比0.4%(體積百分比則為0.358%)稀釋於乙二醇甲醚(2-methoxyethanol)中，之後再以此稀釋溶液與ZnO混摻。ZnO會
在塗佈前先混摻佔其體積百分比20%之PEIE，之後再以不同溶劑稀釋以達到較佳之膜層結構。經實驗測試，較佳之溶劑係為異丙醇(IPA)，而其稀釋之比例則是(ZnO+PEIE)：IPA=1：10為佳。經IPA稀釋後的ZnO、PEIE混和物會透過狹縫塗佈的方法而分布於陰極層52之上，此種狹縫式塗佈的優點在於均勻度高、材料利用率高，可應用之塗佈材料黏度範圍大，並且可以良好控制其塗佈邊界。其運作之示意可參考第三圖。
在前述ZnO、PEIE以及IPA之混和物塗佈於陰極層52上後，步驟S3即係將此些材料經燒結而完成電子傳輸層53的製作。這階段的燒結條件係控制於150℃、維持時間對於電池效率的影響則如下表一所示，係以持續60分鐘為宜。燒結處理後的電子傳輸層53即在IPA的逸散之下而讓PEIE均勻地分布於ZnO結構當中。此經PEIE改質之ZnO的表面缺陷會有效地被PEIE包圍修飾而形成鈍化(passivation)，因而移除了表面缺陷的問題，讓電子電洞之結合不會於此處發生，提高了電子傳輸層53的工作效率。
本發明除了使用ZnO作為電子傳輸層53之材質之一以外，另也可使用AZO取代ZnO，此時AZO也會混摻佔其體積百分比20%之
PEIE，惟此實施例所使用之溶劑係為去離子水(Deionized water,DI)，稀釋之比例以(AZO+PEIE)：DI=1：1為佳。燒結條件則係控制於150℃、維持10分鐘為宜。下表二係為電子傳輸層53在使用ZnO、AZO為材質，以及分別使用體積百分比20%之PEIE進行混摻之下對於效率之影響比較。
待電子傳輸層53形成後，接著於步驟S4狹縫塗佈一主動層54於電子傳輸層53之上，該主動層54之材質並無特殊限定，例如使用較常見之P3HT(Poly(3-hexyl-thiophene-2,5-diyl))：PCBM([6,6]-phenyl-C61-butyric acid methyl ester)之混摻，或是PTQ1(poly[2,3-bis-(3-octyloxy-phenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl])：PC71BM([6,6]-phenyl-C71-butyric acid methyl ester)之組合，讓電子與電洞對於能夠於上述材料混摻之介面處拆解分離。
本發明於製備主動層54之步驟中，其技術特徵在於混摻「非毒化物」O-xylene為溶劑，並在塗佈的同時以R2R烘箱在90~150
℃的烘乾溫度下，使主動層54乾燥成膜。請參考下表三，本發明透過使用O-xylene為溶劑，其對於電池效率之提升較使用氯苯(chlorobenzene,CB)為主動層溶劑來得較佳。主動層54在此步驟中所受的烘乾溫度會造成高分子不同的結晶特性以致影響太陽電池的光電轉換效率，若烘乾溫度僅調控於30℃、70℃等低溫範圍，則太陽電池產品的主動層結晶品質及光電轉換效率就無此水準，較為不佳。另考量到軟性基板51的耐熱度，因此也不會以高於150℃之高溫進行烘乾。之後配合使用習知之主動層熱退火處理，即可大幅提升太陽電池之光電轉換效率。下表四係為使用O-xylene為主動層溶劑時，不同主動層烘乾溫度對於電池效率之影響對照，可證實本發明所選擇之溫度範圍能獲致成品具有較高的光電轉換效率。
最後，步驟S5就會將軟性基板51收捲於在R2R製程架構中的
捲取部3，此經捲取的軟性基板51除了在捲出時已具有的陰極層52以外，另已於前述該些步驟執行的過程中，經狹縫塗佈而快速且大面積地依次設置了電子傳輸層53以及主動層54位於其上。
所收捲的太陽電池半成品，可將之再以其他方法續行加工設置電洞傳輸層55以及陽極層56於主動層54之上，即完成太陽電池之製備。此電洞傳輸層55之材質係為多元，可為聚(3,4-乙烯二氧噻吩)(PEDOT)與聚苯乙烯磺酸(PSS)的混合物，或者是使用五氧化二釩(V2O5)、三氧化鉬(MoO3)等材料，用於輔助電洞的傳輸。而陽極層56則以較穩定的銀(Ag)為材質。
配合透過上述之步驟處理，本發明使用R2R製程進行有機太陽能電池之膜層的製備，並配合製程參數條件的準確控制，落實了在大面積化製備膜層之下可獲致之生產效率的提高，因而使得太陽能電池的製造成本降低，有利於進一步推動發展以及推廣應用。同時，藉由搭配特定溶劑的參與以及使用狹縫塗佈的技術，依序完成電子傳輸層之燒結及主動層之烘乾，並配合習知之主動層熱退火處理，以完成太陽電池之製備。本發明基於R2R製程所形成之電子傳輸層組成處理以降低表面缺陷以及主動層之結晶控制分別在傳遞電子及光電轉換效率的表現上也相當優異；故在兼具了降低成本和效率提升等太陽能電池重點發展要點之下，本發明無疑提供了一種極具產業價值之使用連續捲軸法製備有機太陽能電池之膜層之方法。
惟以上所述者，僅為本發明之較佳實施例而已，並非用來限定本發明實施之範圍，舉凡依本發明申請專利範圍所述之形狀、構造、特徵及精神所為之均等變化與修飾，均應包括於本發明之
申請專利範圍內。
S1~S5‧‧‧步驟
Claims (10)
- 一種使用連續捲軸法(roll to roll)製備有機太陽能電池之膜層之方法，其係包含步驟：捲出(unwind)一軟性基板，該軟性基板之上係具有一陰極層；狹縫塗佈(slot die coating)一電子傳輸層於該陰極層之上，該電子傳輸層之材質係包含具有氧化鋅以及乙氧基聚乙烯亞胺(polyethylenimine ethoxylated,PEIE)之混合物，乙氧基聚乙烯亞胺均勻分布於氧化鋅中；燒結該電子傳輸層；狹縫塗佈一主動層於該電子傳輸層之上，該主動層之材質係混摻鄰二甲苯(O-xylene)為溶劑，並同時烘乾該主動層，烘乾溫度係為90~150℃；以及捲取(rewind)該軟性基板。
- 如申請專利範圍第1項所述之方法，其中該陰極層之材質係為銦錫氧化物。
- 如申請專利範圍第1項所述之方法，其中於狹縫塗佈該電子傳輸層於該陰極層之上之步驟中，所使用之氧化鋅係混摻體積百分比20%之乙氧基聚乙烯亞胺，且此乙氧基聚乙烯亞胺已先行以重量百分比0.4%稀釋於乙二醇甲醚(2-methoxyethanol)中。
- 如申請專利範圍第3項所述之方法，其係使用異丙醇為溶劑。
- 如申請專利範圍第4項所述之方法，其中氧化鋅於混摻乙氧基聚乙烯亞胺後，其與異丙醇之體積比例係為1：10。
- 如申請專利範圍第1項所述之方法，其中於燒結該電子傳輸層之步驟中，燒結溫度係為150℃，燒結時間係為60分鐘。
- 一種使用連續捲軸法(roll to roll)製備有機太陽能電池之膜層之方法，其係包含步驟：捲出(unwind)一軟性基板，該軟性基板之上係具有一陰極層；狹縫塗佈(slot die coating)一電子傳輸層於該陰極層之上，該電子傳輸層之材質係包含具有氧化鋅摻鋁以及乙氧基聚乙烯亞胺(polyethylenimine ethoxylated,PEIE)之混合物，乙氧基聚乙烯亞胺均勻分布於氧化鋅摻鋁中；燒結該電子傳輸層；狹縫塗佈一主動層於該電子傳輸層之上，該主動層之材質係混摻鄰二甲苯(O-xylene)為溶劑；烘乾該主動層，烘乾溫度係為90~150℃；以及捲取(rewind)該軟性基板。
- 如申請專利範圍第7項所述之方法，其中於狹縫塗佈該電子傳輸層於該陰極層之上之步驟中，係使用去離子水為溶劑。
- 如申請專利範圍第8項所述之方法，其中氧化鋅摻鋁於混摻乙氧基聚乙烯亞胺後，其與去離子水之體積比例係為1：1。
- 如申請專利範圍第7項所述之方法，其中於燒結該電子傳輸層之步驟中，燒結溫度係為150℃，燒結時間係為10分鐘。
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