TWI501997B - 芳香族聚醯亞胺膜、疊層體及太陽電池 - Google Patents
芳香族聚醯亞胺膜、疊層體及太陽電池 Download PDFInfo
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- TWI501997B TWI501997B TW099140100A TW99140100A TWI501997B TW I501997 B TWI501997 B TW I501997B TW 099140100 A TW099140100 A TW 099140100A TW 99140100 A TW99140100 A TW 99140100A TW I501997 B TWI501997 B TW I501997B
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- KRIXEEBVZRZHOS-UHFFFAOYSA-N tetradecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(O)=O KRIXEEBVZRZHOS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
- H01L31/03928—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
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Description
本發明係關於一種聚醯亞胺膜,尤其適用於CIS系太陽電池的基板,可承受450℃以上、甚至接近500℃以上之高溫的熱處理之具有極高耐熱性與尺寸安定性的聚醯亞胺膜。又,本發明係關於利用該聚醯亞胺膜之疊層體及具有高轉換效率之CIS系太陽電池。
近年來,在光電轉換效率高的太陽電池方面,使用CuInSe2
、或於其中固熔有Ga之Cu(In,Ga)Se2
等黃銅礦構造半導體層的太陽電池(CIS系太陽電池)正受到矚目。CIS系太陽電池,一般而言,於基板上具有:設置了背面電極層、於其上之作為光吸收層的黃銅礦構造半導體層、緩衝層、透明電極層、抽出電極的構成。
以往,CIS系太陽電池的基板係使用玻璃(鈉鈣玻璃),設置於基板上的背面電極係使用Mo。此外,也有人提出使用可撓性膜作為基板的CIS系太陽電池(專利文獻1等)。使用可撓性基板的太陽電池,因為其柔軟性與輕量性,相較於使用習知玻璃基板的太陽電池,具有擴大應用範圍的可能性。又,使用可撓性基板的另一優點為可利用在量產性上具優異性之捲對捲方式製造太陽電池。
然而,使用可撓性基板,例如使用聚醯亞胺基板之CIS系太陽電池,相較於使用玻璃基板者,有轉換效率變低的傾向。其原因係為了形成缺陷較少之高品質的CIS系半導體薄膜,需要以450℃以上、較佳為接近500℃以上的高溫進行熱處理,但即使是高耐熱性樹脂之聚醯亞胺,耐熱溫度約為450℃,加熱到更高溫度有其困難度。
就製造使用了聚醯亞胺基板之高轉換效率的CIS系太陽電池之方法而言,專利文獻2揭示一方法,係於聚醯亞胺基板上形成電極膜,其次於電極膜之上方(亦即,直接的或間接的於電極膜上)形成包含Cu、與In及/或Ga、與Se及/或S之薄膜後,將該薄膜急速升溫後,於450℃以上,更佳為於500℃~600℃保持10秒~300秒,藉此形成黃銅礦構造半導體膜之方法,及於聚醯亞胺基板上形成電極膜,接著於電極膜之上方形成包含Cu與In及/或Ga之薄膜後,將該薄膜於含有Se及/或S之氣體環境中急速升溫後,於450℃以上,更佳為於500℃~600℃保持10秒~300秒,藉此形成黃銅礦構造半導體膜。該製造方法中,將形成半導體膜之前趨物薄膜之步驟與將該前趨物薄膜熱處理之步驟分離,並藉由在加熱前趨物薄膜使結晶成長之階段急速升溫,短時間保持在500℃以上的高溫,可得適用於太陽電池之光吸收層之黃銅礦構造半導體薄膜。然而,雖然係短時間,但須於高溫進行熱處理,故該方法在習知聚醯亞胺膜有時會有以下情況:聚醯亞胺基板機械特性明顯劣化、翹曲、於電極膜或半導體膜產生裂紋。
專利文獻3揭示一種太陽電池,係於基板膜上形成至少具有電極層及黃銅礦構造半導體薄膜的疊層而構成,特徵在於:基板膜係將芳香族二元胺類與芳香族四羧酸酐類縮聚而成之聚醯亞胺膜,膜厚為3~200μm、至300℃為止之平均線膨脹係數為1~10ppm/℃、長邊方向之拉伸斷裂強度為300MPa以上,就較佳基板膜而言,記載將具有苯并唑構造之芳香族二元胺類與芳香族四羧酸酐類縮聚成之聚醯亞胺苯并唑膜。又,於實施例8也記載一種CIS系太陽電池,係將從3,3’,4,4’-聯苯四羧酸二酐及對苯二胺以熱醯亞胺化得到之聚醯亞胺膜作為基板使用。然而,專利文獻3記載之聚醯亞胺膜,雖然考慮到至300℃為止之升溫過程的尺寸變化,但有必要考慮更高溫範圍(~500℃以上)之尺寸變化及機械特性的劣化。
又,專利文獻4揭示一種聚醯亞胺絕緣膜的形成方法,係於基板上塗佈聚醯胺酸漆,將該塗膜硬化形成聚醯亞胺絕緣膜時,為降低絕緣膜之殘留應力(具體而言係降低線膨脹係數),在成膜步驟中於100℃~160℃的溫度範圍加熱維持至少30分鐘的方法。然而,即使在專利文獻4中,也有必要將更高溫度範圍(~500℃以上)之尺寸變化及機械特性的劣化列入考慮。
[專利文獻1]國際公開第98/50962號小冊子
[專利文獻2]日本特開2003-179238號公報
[專利文獻3]日本特開2007-317834號公報
[專利文獻4]日本特開平7-307114號公報
如上述,可耐高溫之熱處理,具有極高耐熱性與尺寸安定性之聚醯亞胺膜並非習知。尤其,習知之聚醯亞胺膜,若在與膜的兩面直接接觸而設置金屬層等不透氣性層的狀態以高溫進行熱處理,則耐彎曲性(相對於彎曲的折抗性)會顯著下降。
因此,本發明之目的在提供一種聚醯亞胺膜,係可耐高溫熱處理,具有極高耐熱性與尺寸安定性,更具體而言,係提供一種聚醯亞胺膜,具有極高耐熱性,即使在於膜的兩面直接設置有金屬層的狀態以高溫進行熱處理,仍具有優異的尺寸安定性,更具有耐彎曲性等優異的機械特性。又,本發明之目的尤其提供一種可實現高轉換效率之CIS系太陽電池的聚醯亞胺膜,更進一步提供一種疊層體,係於該聚醯亞胺膜上形成作為CIS系太陽電池之電極的導電層者。
本發明係關於以下事項。
1.一種聚醯亞胺膜,係使以3,3’,4,4’-聯苯四羧酸二酐為主成分之芳香族四羧酸成分,與以對苯二胺為主成分之芳香族二元胺成分反應而得者,其特徵為由25℃至500℃為止之升溫過程的尺寸變化率之最大值,以升溫前之25℃的尺寸為基準,係大於+0.6%且為+0.9%以下的範圍內。
2.如上述1.之聚醯亞胺膜,其中,以500℃熱處理20分鐘後之重量減少率為1質量%以下。
3.如上述1.或2.之聚醯亞胺膜,其中,25~500℃之線膨脹係數為大於10ppm/℃且為20ppm/℃以下。
4.如上述1.~3.中任一項之聚醯亞胺膜,其厚度為7.5~75μm。
5.一種於如上述1.~4.中任一項之聚醯亞胺膜上形成金屬層而得之疊層體。
6.如上述5.之疊層體,其中該金屬層包含鉬。
7.如上述5或6之疊層體,其中該金屬層係藉由濺鍍或蒸鍍形成者。
8.一種CIS系太陽電池,係於如上述1.~4.中任一項之聚醯亞胺膜所構成之基板上,至少包含具導電性的金屬層與黃銅礦構造半導體層。
9.一種聚醯亞胺膜的製造方法,係利用熱醯亞胺化的方法,包含以下步驟:聚醯亞胺前趨物溶液製造步驟,使以3,3’,4,4’-聯苯四羧酸二酐為主成分之芳香族四羧酸成分、與以對苯二胺為主成分之芳香族二元胺成分於溶媒中反應;澆鑄步驟,將所製造之聚醯亞胺前趨物溶液流延塗佈於支持體上並加熱以製造自撐膜;硬化步驟,將製得之自撐膜加熱並進行醯亞胺化反應;其特徵為該澆鑄步驟之自撐膜係以下式(A)表示之重量減少率為36~39%之範圍者:
重量減少率(%)=(W1-W2)/W1×100 (A)
(W1係自撐膜之質量,W2係硬化後之聚醯亞胺膜之質量);該澆鑄步驟之最高溫度(T1)為該自撐膜所顯示之熱變形溫度(TM
)以下;該硬化步驟係將該自撐膜以較熱變形溫度TM
低之溫度加熱,之後,使溫度上升,於最高熱處理溫度(T2)470℃~540℃的範圍進行熱處理。
10.如上述9.之聚醯亞胺膜的製造方法,其中,所製造之聚醯亞胺膜的厚度為7.5~75μm。
11.如上述9.或10.之聚醯亞胺膜的製造方法,其中,該澆鑄步驟之聚醯亞胺前趨物之熱處理的最高溫度(T1)為140℃以下。
12.一種疊層體的製造方法,其特徵為利用上述9.~11.中任一項之製造方法製造聚醯亞胺膜後,於該聚醯亞胺膜之表面形成金屬層。
13.一種CIS系太陽電池之製造方法,其特徵為利用上述9.~11.中任一項之製造方法製造聚醯亞胺膜後,於該聚醯亞胺膜的表面形成金屬層,之後,形成黃銅礦構造半導體層,於450℃以上進行加熱處理。
藉由本發明可提供一種可耐受高溫熱處理之具有極高耐熱性與尺寸安定性之聚醯亞胺膜。尤其,本發明之聚醯亞胺膜即使在於膜的兩面直接設置有金屬層等不透氣性層的狀態以高溫熱處理,仍具有尺寸安定性優異,甚至耐彎曲性等優異的機械特性。因此,在可實現高轉換效率之CIS系太陽電池的聚醯亞胺膜基板的應用上極有用。
本發明之聚醯亞胺膜,如前述係由以3,3’,4,4’+-聯苯四羧酸二酐為主成分之芳香族四羧酸成分,與以對苯二胺為主成分之芳香族二元胺成分反應而得,由25℃至500℃為止之升溫過程的尺寸變化率的最大值,以在升溫前之25℃的尺寸(初始尺寸)為基準,為大於0且+1%以下,較佳為大於+0.6%且為+0.9%以下之範圍內,最佳為+0.76%至0.80%之範圍內。
又,由500℃至25℃為止之降溫過程之尺寸變化率的最小值,以在25℃的初始尺寸為基準,宜為0%~-0.8%尤其為0%~-0.3%。
具有上述之由25℃至500℃為止之升溫過程之尺寸變化率、較佳為上述之由25℃至500℃為止之升溫過程的尺寸變化率及上述之由500℃至25℃為止之降溫過程之尺寸變化率之聚醯亞胺膜,在伴隨著CIS系太陽電池等在高溫的熱處理的用途方面有利,防止作為電極之金屬層或半導體層之裂紋的產生,防止由基板剝離,可製造高轉換效率之高品質的CIS系太陽電池。
在此,由25℃至500℃為止的尺寸變化率係指對測定對象之聚醯亞胺膜,以熱機械性分析儀(TMA),在以下條件:將由25℃至500℃的升溫過程及與其連續之由500℃至25℃的降溫過程進行2重複,在第2次的各溫度,測定相對於MD方向(連續製膜方向;膜的長邊方向)及TD方向(垂直於MD方向的方向;膜的寬度方向)之初始尺寸(升溫前於25℃的尺寸)的尺寸變化率。採用第2次的測定係為了排除來自水分的吸收或殘留應力之些許差的影響。
測定模式:拉伸模式、荷重2g、
試料長度:15mm、
試料寬度:4mm、
升溫開始溫度:25℃、
升溫終了溫度:500℃(於500℃無保持時間)、
降溫終了溫度:25℃、
升溫及降溫速度:20℃/min、
測定氣體環境:氮氣
又,尺寸變化率定義如下述式(1)。
惟,升溫過程之尺寸變化率的最大值(%)係以升溫過程中可得到的最大尺寸定為式(1)之L,降溫過程之尺寸變化率之最小值(%)係以降溫過程中可得到的最小尺寸定為式(1)之L而求得。
尺寸變化率(%)=(L-L0
)/L0
×100 (1)
(惟,L係於測定溫度的長度,L0
係於升溫前之25℃的長度。)
接著,聚醯亞胺膜於氮氣氣體環境中以500℃熱處理20分鐘後之重量減少率,較佳為1質量%以下、更佳為0.5質量%以下、又更佳為0.32質量%以下。此意味著:本發明之聚醯亞胺膜即使以500℃以上之高溫進行熱處理也不會分解‧劣化或分解‧劣化的很少,具有高耐熱性。
在此,以500℃熱處理20分鐘後之重量減少率,係對測定對象之聚醯亞胺膜,測定於氮氣氣體環境中,由室溫起至500℃為止以50℃/分升溫達到500℃時,與接著在500℃保持20分鐘後之聚醯亞胺膜的重量,並由下述式(2)求得者。
重量減少率(%)=(W0
-W)/W0
×100 (2)
(惟,W0
為500℃升溫當下的重量,W為於500℃保持20分鐘後的重量。)
因為水分或殘留溶媒等揮發成分在達到500℃以前揮發,以此重量減少率為聚醯亞胺之分解‧熱劣化之指標,值越大表示劣化程度越高。
又,聚醯亞胺膜之25~500℃之線膨脹係數以20ppm/℃以下為佳,0~20ppm/℃為更佳,大於10ppm/℃且為20ppm/℃以下又更佳。係因為若基板之線膨脹係數與作為電極之金屬層(通常為Mo層或W層)之線膨脹係數或黃銅礦構造半導體層之線膨脹係數有很大的差異,則即使抑制高溫範圍之熱收縮,亦會與作為電極之金屬層或半導體層之尺寸變化率產生大的差異。因此,聚醯亞胺膜由於具有上述線膨脹係數,可適用於CIS系太陽電池之基板。又,關於MD方向及TD方向之兩者的線膨脹係數,以上述範圍為佳
在此,25~500℃之線膨脹係數係,由在前述25℃至500℃為止之尺寸變化率的測定中,第2次升溫過程的MD方向及TD方向的尺寸變化,以下述式(3)求得之MD方向與TD方向之平均線膨脹係數。採用第2次測定係為了避免水分的吸收或殘留應力之若干差所造成的影響。
線膨脹係數(ppm/℃)=(L-L0
)/{L0
×(T-T0
)}×106
(3)
(惟,L為於500℃之長度,L0
為第2次升溫前於25℃之長度,T為500℃,T0
為25℃)
上述尺寸變化率及重量減少率之測定中,溫度皆為測定聚醯亞胺膜表面之溫度。
又,聚醯亞胺膜之拉伸斷裂強度宜為300MPa以上。本發明之聚醯亞胺膜,除了上述較佳特性以外,耐彎曲性優異。
本發明之聚醯亞胺膜可利用以下所說明的方法進行製造。
本發明之聚醯亞胺膜,可藉由利用熱醯亞胺化之聚醯亞胺膜的製造方法製得,該製造方法包含以下步驟:前趨物融業製造步驟,使以3,3’,4,4’-聯苯四羧酸二酐為主成分之芳香族四羧酸成分、與以對苯二胺為主成分之芳香族二元胺成分於溶媒中反應;澆鑄步驟,將所製造之聚醯亞胺前趨物溶液流延塗佈於支持體上並加熱以製造自撐膜;硬化步驟將製得之自撐膜加熱以進行醯亞胺化;其特徵為該澆鑄步驟之自撐膜係以下式(A)表示之重量減少率為36~39%之範圍者:
重量減少率(%)=(W1-W2)/W1×100 (A)
(W1係自撐膜之質量,W2係硬化後之聚醯亞胺膜之質量);該澆鑄步驟之最高溫度(T1)為該自撐膜所顯示之熱變形溫度(TM
)以下;該硬化步驟係將該自撐膜以較熱變形溫度TM
低之溫度加熱,之後,使溫度上升,於最高熱處理溫度(T2)470℃~540℃的範圍進行熱處理。
以下詳細說明。
首先,於澆鑄步驟製造聚醯亞胺前趨物溶液之自撐膜。聚醯亞胺前趨物溶液係、提供聚醯亞胺之聚醯亞胺前趨物,即聚醯胺酸之有機溶媒溶液,視需要,添加醯亞胺化觸媒、有機磷化合物或無機微粒。自撐膜係將聚醯亞胺前趨物溶液流延塗佈於支持體上、加熱至變得有自撐性的程度(意指通常之硬化步驟前的階段)為止製造而得。
芳香族四羧酸成分係以3,3’,4,4’-聯苯四羧酸二酐(以下有時簡稱為s-BPDA。)為主成分者,具體而言,包含s-BPDA為75莫耳%以上、更佳為80莫耳%以上、尤佳為90莫耳%以上、又更佳為95莫耳%以上、若為100%也非常佳。芳香族二元胺成分係以對苯二胺(以下有時簡稱為PPD。)為主成分者,具體而言,包含PPD為75莫耳%以上、更佳為80莫耳%以上、尤佳為90莫耳%以上、又更佳為95莫耳%以上、若為100%也非常佳。
又,在不損害本發明之特性的範圍,也可使用其他之四羧酸二酐及二元胺。
本發明中,可與3,3’,4,4’-聯苯四羧酸成分併用之芳香族四羧酸成分,例如:焦蜜石酸二酐、2,3’,3,4’-聯苯四羧酸二酐、3,3’,4,4’-二苯基酮四羧酸二酐、2,2’,3,3’-二苯基酮四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二無水物、2,2-雙(2,3-二羧基苯基)丙烷二無水物、雙(3,4-二羧基苯基)醚二無水物、雙(2,3-二羧基苯基)醚二無水物、2,3,6,7-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、2,2-雙(3,4-二羧基苯基)-1,1,1,3,3,3-六氟丙烷二無水物、2,2-雙(2,3-二羧基苯基)-1,1,1,3,3,3-六氟丙烷二無水物等。又,可與對苯二胺併用之芳香族二胺成分,例如:間苯二胺、2,4-二胺基甲苯、2,6-二胺基甲苯、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯醚、3,4’-二胺基二苯醚、3,3’-二甲基-4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、2,2’-雙(三氟甲基)-4,4’-二胺基聯苯、4,4’-二胺基二苯基酮、3,3’-二胺基二苯基酮、4,4’-雙(4-胺基苯基)硫、4,4’-二胺基二苯基碸、4,4’-二胺基苯甲醯苯胺、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-雙(3-胺基苯氧基)聯苯、2,2-雙(4-胺基苯氧基苯基)丙烷、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷等,尤以具有1個或2個苯核之二胺較佳。
聚醯亞胺前趨物,即聚醯胺酸的合成,可藉由在有機溶媒中將大致等莫耳之芳香族四羧酸二酐與芳香族二元胺進行無規聚合或嵌段聚合而達成。又,也可將其中一成分為過量之2種以上聚醯亞胺前趨物預先合成,將各聚醯亞胺前趨物溶液合在一起後,於反應條件下混合。以此方式得到之聚醯亞胺前趨物溶液可直接或視需要去除或加入溶媒,而使用於自撐膜之製造。
聚醯亞胺前趨物溶液之有機溶媒,例如N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺等。該等有機溶媒可單獨使用也可併用2種以上。最佳為使用N,N-二甲基乙醯胺。
視需要可於聚醯亞胺前趨物溶液添加醯亞胺化觸媒、有機含磷化合物、無機微粒等。
醯亞胺化觸媒,例如:取代或非取代之含氮雜環化合物、該含氮雜環化合物之N-氧化化合物、取代或非取代之胺基酸化合物、具羥基之芳香族烴化合物或芳香族雜環化合物,尤佳為:1,2-二甲基咪唑、N-甲基咪唑、N-苄基-2-甲基咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、5-甲基苯并咪唑等低級烷基咪唑、N-苄基-2-甲基咪唑等苯并咪唑、異喹啉、3,5-二甲基吡啶、3,4-二甲基吡啶、2,5-二甲基吡啶、2,4-二甲基吡啶、4-正丙基吡啶等取代吡啶等。醯亞胺化觸媒之使用量,相對於聚醯胺酸之醯胺酸單位,使用0.01-2倍當量,尤其約0.02-1倍當量為佳。藉由使用醯亞胺化觸媒,能提高得到之聚醯亞胺膜之物性,尤其伸長或撕裂強度。
有機含磷化合物,例如:單己醯基磷酸酯、單辛基磷酸酯、單月桂基磷酸酯、單肉豆蔻基磷酸酯、單鯨蠟基磷酸酯、單硬脂基磷酸酯、三乙二醇單十三烷醚之單磷酸酯、四乙二醇單月桂醚之單磷酸酯、二乙二醇單硬脂基醚之單磷酸酯、二己醯基磷酸酯、二辛基磷酸酯(dioctyl phosphate ester)、二辛基磷酸酯(dicapryl phosphate ester)、二月桂基磷酸酯、二肉豆蔻基磷酸酯、二鯨蠟基磷酸酯、二硬脂基磷酸酯、四乙二醇單新戊醚之二磷酸酯、三乙二醇單十三烷醚之二磷酸酯、四乙二醇單月桂醚之二磷酸酯、二乙二醇單硬脂基醚之二磷酸酯等磷酸酯,或該等磷酸酯之胺鹽。胺,例如:氨、單甲胺、單乙胺、單丙胺、單丁胺、二甲胺、二乙胺、二丙胺、二丁胺、三甲胺、三乙胺、三丙胺、三丁胺、單乙醇胺、二乙醇胺、三乙醇胺等。
無機微粒,例如:微粒狀二氧化鈦粉末、二氧化矽(silica)粉末、氧化鎂粉末、氧化鋁(alumina)粉末、氧化鋅粉末等無機氧化物粉末、微粒狀氮化矽粉末、氮化鈦粉末等無機氮化物粉末、碳化矽粉末等無機碳化物粉末,及微粒狀碳酸鈣粉末、硫酸鈣粉末、硫酸鋇粉末等無機鹽粉末。該等無機微粒也可組合二種以上使用。為了使該等無機微粒均勻分散,可應用本身公知之方法。
聚醯亞胺前趨物溶液之自撐膜,可將如上述聚醯亞胺前趨物之有機溶媒溶液、或於其中添加醯亞胺化觸媒、有機含磷化合物、無機微粒等之聚醯亞胺前趨物溶液組成物,流延塗佈於支持體上,加熱至成為自撐性之程度(意指通常之硬化步驟前之階段),例如能從支持體上剝離之程度而製造。
聚醯亞胺前趨物溶液,以含有聚醯亞胺前趨物約10~30質量%較佳。
支持體以使用平滑基材為佳,例如不銹鋼基板、不銹鋼帶等。為了連續生產,使用無端運送帶等無端基材較佳。
本發明之特徵為在獲得該自撐膜之澆鑄步驟中,以較低之溫度進行熱處理。在此,本發明所謂「自撐膜」係指成為可由支持體剝離之狀態的膜。
具體而言,澆鑄步驟中得到的自撐膜係:以下式(A)表示之重量減少率為36~39%之範圍者,
重量減少率(%)=(W1-W2)/W1×100 (A)
(W1為自撐膜的質量、W2為硬化後之聚醯亞胺膜的質量。)
該澆鑄步驟之最高溫度(T1)為該自撐膜所顯示之熱變形溫度(TM
)以下。
更具體而言,至少聚醯亞胺前趨物溶液藉由乾燥、失去流動性(固化)階段的溫度為TM
以下。在此情況,澆鑄步驟全體的溫度為熱變形溫度(TM
)以下。
簡單記載關於澆鑄步驟之溫度條件的實施形態。在任何情況,T1皆為TM
以下。
1.使澆鑄步驟的溫度階段性地上升。
2.從澆鑄步驟之入口開始初始溫度高,澆鑄步驟之中間階段以後,具體而言藉由使聚醯亞胺前趨物溶液乾燥,失去流動性(固化)階段的後半階段係使溫度較初始溫度低而以較低的溫度進行熱處理。在澆鑄中間階段若可將最高溫度設定為較上述溫度低的溫度,例如澆鑄投入溫度可任意地選擇。在此澆鑄中間階段係指聚醯亞胺前趨物溶液因溶媒蒸發失去流動性的階段。
以下,為了更簡單的表示,有時將「重量減少率為36~39%之範圍之時點,自撐膜所顯示之熱變形溫度」稱為「熱變形溫度TM
」。
在此,重量減少率係以下次式(A)求得:
重量減少率(%)=(W1-W2)/W1×100 (A)
(W1為自撐膜的質量,W2為硬化後之聚醯亞胺膜之質量。)。
又,熱變形溫度可藉由熱機械性分析儀(TMA)在下述條件,於升溫的同時測定伸長(%),由相對於溫度(℃)之伸長(%)的曲線,求出伸長(%)之上升溫度。
測定模式:拉伸模式、荷重4g、
試料長度:15mm、
試料寬度:4mm、
升溫開始溫度:25℃、
升溫終了溫度:500℃(於500℃無保持時間)、
降溫終了溫度:25℃、
升溫及降溫速度:20℃/min、
測定氣體環境:空氣
重量減少率為36~39%之範圍的時點之自撐膜的測定樣本可於支持體上塗佈聚醯亞胺前趨物溶液後,在例如60℃~130℃之範圍、例如80℃或100℃等的溫度、特定時間,將溶媒乾燥而得。其熱變形溫度TM
,會因為成分等而有些許變化,但位於135~140℃之範圍。澆鑄步驟之最高溫度(T1)較佳為140℃以下、更佳為135℃以下。又,澆鑄步驟之最高溫度(T1)通常為100℃以上、較佳為115℃以上、更佳為117℃以上。
用以形成自撐膜的加熱時間可適當地決定,例如約3~60分鐘。
經過澆鑄步驟而得到的自撐膜之由上述式(A)而得之重量減少率較佳為20~50質量%之範圍、更佳為40質量%以下、又更佳為39質量%以下。經過澆鑄步驟而得到的自撐膜也可有超過39質量%之重量減少率,在該情況,於後續的硬化步驟之初始步驟,以不超過「熱變形溫度TM
」之溫度進行加熱的過程中,宜選擇使膜之重量減少率為39質量以下之熱處理條件。
經過澆鑄步驟後而得到之自撐膜的醯亞胺化率較佳為3~50%之範圍、更佳為7~30%之範圍。具有如此範圍之重量減少率及醯亞胺化率之自撐膜其本身的力學特性相當充分,又,於自撐膜之頂面塗佈偶聯劑之溶液時,能容易勻整塗佈偶聯劑溶液,醯亞胺化後得到之聚醯亞胺膜不會觀察到發泡、龜裂、裂紋、裂痕、裂隙等產生,故較佳。
自撐性膜之醯亞胺化率,可利用IR(ATR)測定,並利用膜與全硬化品之振動帶峰部面積或高度之比值,計算醯亞胺化率。振動帶峰部,可係利用醯亞胺羰基之對稱伸縮振動帶或苯環骨架伸縮振動帶等。又,關於醯亞胺化率,可利用日本特開平9-316199記載之卡式水分測定儀(Karl Fisher Moisture Titrator)之方法。
本發明人推定在較低的溫度進行澆鑄步驟具有促進高分子鏈配向的效果。意即,澆鑄步驟中溶媒蒸發脫去的過程中,膜的體積收縮時,因為xy平面方向被固定,實際上僅在厚度方向收縮。因此若由xy方向觀察,外觀上有與在xy方向延伸的情況相同的效果。若說明在實際之澆鑄步驟所發生的現象,初始階段在保持流動性之下,將溶媒蒸發的過程並非促進配向的步驟。接著發生流延膜之固化(聚合物之自由分子運動受到限制的狀態),在之後的溶媒乾燥使xy方向的厚度降低。流延膜之固化以後係實際上進行延伸的步驟,延伸率與固化膜之聚合物濃度有關。此時之溫度為低的情況,固化膜之聚醯胺酸濃度低,更有效率地形成經延伸的自撐膜。於低溫所形成的配向狀態在後續的升溫過程中可能有配向緩和的情形,在實際上可自由移動的溶媒不存在或盡可能少的狀態,有在維持配向狀態的情況固定高次結構的傾向。重量減少率為36~39%之範圍以下,因為溶媒被醯胺酸以鹽等的形態束縛,為自由移動的溶媒難以存在的狀態。在此,假設溶媒與醯胺酸以1:1的比例形成鹽。此時,重量減少率為36%的情況,可自由移動的溶媒(自由的溶媒)為0。又,重量減少率為39%的情況,可自由移動之溶媒理論上為3%。因此,於澆鑄步驟得到之自撐膜的重量減少率為36~39%的範圍的情況,實際上可自由移動的溶媒不存在、或在盡可能少的狀態的可自由移動的溶媒為超過0之3%的範圍。此係澆鑄步驟中得到的自撐膜之重量減少率為36~39%之範圍的一形態,本發明之自撐膜並不限定於此。由於這樣的理由,於熱變形溫度TM
以下之溫度間(包含澆鑄步驟及硬化步驟的初始步驟)進行熱處理(乾燥),使重量減少率為39質量%以下較佳。
本發明中,也可在如此方式得到之自撐膜之單面或兩面,視需要塗佈偶聯劑或螯合劑等表面處理劑之溶液。
表面處理劑,例如:矽烷偶聯劑、硼烷偶聯劑、鋁系偶聯劑、鋁系螯合劑、鈦酸酯系偶聯劑、鐵偶聯劑、銅偶聯劑等各種偶聯劑或螯合劑等使接著性或密著性提升之處理劑。尤其表面處理劑,使用矽烷偶聯劑等偶聯劑時可得優異之效果。
矽烷系偶聯劑,例如:γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基二乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷等環氧矽烷系、乙烯基三氯矽烷、乙烯基參(β-甲氧基乙氧基)矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷等乙烯基矽烷系、γ-甲基丙烯醯氧丙基三甲氧基矽烷等丙烯酸基矽烷系、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷等胺基矽烷系、γ-巰基丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷等。又,鈦酸酯系偶聯劑,例如:異丙基三異硬脂醯基鈦酸酯、異丙基十三烷基苯磺醯基鈦酸酯、異丙基參(二辛基焦磷酸酯)鈦酸酯、四異丙基雙(二辛基亞磷酸酯)鈦酸酯、四(2,2-二烯丙基氧基甲基-1-丁基)雙(二-十三烷基)亞磷酸酯鈦酸酯、雙(二辛基焦磷酸酯)氧基乙酸鹽鈦酸酯、雙(二辛基焦磷酸酯)乙烯鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基三基苯基鈦酸酯等。
偶聯劑,例如矽烷系偶聯劑,尤佳為:γ-胺基丙基-三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基-三乙氧基矽烷、N-(胺基羰基)-γ-胺基丙基三乙氧基矽烷、N-[β-(苯基胺基)-乙基]-γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷等胺基矽烷偶聯劑為適當,其中尤以N-苯基-γ-胺基丙基三甲氧基矽烷較佳。
作為偶聯劑或螯合劑等表面處理劑之溶液之溶媒,例如與聚醯亞胺前趨物溶液之有機溶媒(自撐膜所含有之溶媒)相同者。有機溶媒,以與聚醯亞胺前趨物溶液相溶之溶媒為佳,較佳為與聚醯亞胺前趨物溶液之有機溶媒相同者。有機溶媒可為2種以上之混合物。
偶聯劑或螯合劑等表面處理劑之有機溶媒溶液宜為:表面處理劑之含量為0.5質量%以上、更佳為1~100質量%、特佳為1.2~60質量%,再更佳為1.5~30質量%。又,水分含量宜為20質量%以下、更佳為10質量%以下、特佳為5質量%以下。表面處理劑之有機溶媒溶液之旋轉黏度(於測定溫度25℃、以旋轉黏度計測定之溶液黏度),以0.8~50000厘泊(centipoise)為佳。
表面處理劑之有機溶媒溶液,尤以表面處理劑為0.5質量%以上,特佳為1.2~60質量%,又更佳為1.5~30質量%之濃度均勻溶解於醯胺系溶媒之低黏度者(尤其,旋轉黏度0.8~5000厘泊)者較佳。
表面處理劑溶液之塗佈量可適當決定,例如以1~50g/m2
較佳、2~30g/m2
更佳、3~20g/m2
尤佳。塗佈量,兩面可相同也可不同。
表面處理劑溶液之塗佈,可使用公知方法進行,例如照相凹版塗佈法、旋塗法、絹網法、浸塗法、噴塗法、棒塗法、刀塗法、輥塗法、刮刀塗佈法、壓鑄模塗佈法等公知之塗佈方法。
接著,硬化步驟中,將自撐膜加熱‧醯亞胺化而得到聚醯亞胺膜。
硬化步驟中,自撐膜之熱處理較佳為以約0.05~5小時、更佳為以0.1~3小時緩慢地進行,於其間完成醯亞胺化。熱處理藉由階段性地提升溫度的多段升溫步驟進行較佳。本發明之其中一特徵為最初之加熱步驟中以較前述「熱變形溫度TM
」低的溫度進行加熱,之後,使溫度上升,以最高熱處理溫度(T2)470℃~540℃之範圍進行熱處理。即,澆鑄步驟之最高溫度(T1)為前述自撐膜所顯示之熱變形溫度(TM
)以下且硬化步驟之初始之自撐膜的加熱溫度為前述「熱變形溫度TM
」以下之溫度。前述溫度上昇係以階段性進行為佳。
在此,前述「最初之加熱步驟」係指後述之第1加熱步驟,具體而言由硬化爐之入口開始至未滿熱變形溫度TM
之區域(區段)。
在前述多段升溫步驟也宜為:最初加熱步驟中以較前述熱變形溫度TM
低的溫度進行加熱,之後,使溫度上升,以最高熱處理溫度(T2)470℃~540℃之範圍進行熱處理。
即,本發明之硬化步驟至少具有以下步驟:第1加熱步驟,以較「熱變形溫度TM
」低的溫度、較佳為由較「熱變形溫度TM
」低60℃的溫度至較「熱變形溫度TM
」低的溫度的範圍、更佳為由較「熱變形溫度TM
」低50℃的溫度至較「熱變形溫度TM
」低的溫度的範圍、又更佳為較「熱變形溫度TM
」低40℃的溫度至較「熱變形溫度TM
」低的溫度的範圍進行加熱;中間加熱步驟,以「熱變形溫度TM
」以上、未滿最高熱處理溫度(T2)(470℃以上、較佳為490℃以上、更佳為495℃以上)之溫度進行加熱;高溫加熱步驟,以最高熱處理溫度(T2)即以470℃以上、較佳為490℃以上、更佳為495℃以上之溫度進行加熱;及冷却步驟,為高溫加熱步驟以後的冷却步驟。
(惟,中間加熱步驟之溫度範圍與高溫加熱步驟的溫度範圍不能重複)
第1加熱步驟之處理溫度,上限較佳為較「熱變形溫度TM
」低之溫度、通常較佳為140℃以下、更佳為135℃以下,下限較佳為較「熱變形溫度TM
」低60℃的溫度、通常較佳為100℃以上、更佳為115℃以上、又更佳為117℃以上。第1加熱步驟中,在較低的溫度、盡可能減少可自由移動的溶媒對尺寸安定性佳的膜而言重要。前述盡可能減少可自由移動的溶媒的狀態係指,如澆鑄步驟該項中所述,實際上可自由移動的溶媒不存在或很少的狀態。由該觀點來看,較佳為使第1加熱步驟時間增長,但實際上在不使所有處理時間過長的情況決定溫度模式。第1加熱步驟之處理時間例如約0.5~30分鐘、較佳為約1~20分鐘、更佳為2~15分鐘。
中間加熱步驟,宜緩慢地升溫至未滿最高熱處理溫度(T2),即未滿470℃、較佳為未滿490℃、更佳為未滿495℃,且宜為以多階段方式進行熱處理:由「熱變形溫度TM
」(宜為140℃或135℃)至未滿200℃之溫度,10秒~30分鐘、較佳為30秒~10分鐘;由200℃至未滿350℃的溫度,10秒~30分鐘、較佳為30秒~10分鐘;由350℃至未滿最高熱處理溫度(T2)(470℃以上、較佳為490℃以上、更佳為495℃以上)之溫度,10秒~30分、較佳為30秒~10分。
接著,高溫加熱步驟中,以470℃以上、較佳為490℃以上、更佳為495℃以上之溫度,約5秒~5分鐘、較佳為約10秒~3分鐘、更佳為2分鐘以下進行熱處理。最高熱處理溫度(T2)存在於本高溫加熱步驟。
高溫加熱步驟以後,視需要於降溫步驟將膜進行熱處理較佳,藉此可降低膜內的残留應力。
降溫步驟宜為:以於未滿最高加熱溫度之溫度至300℃的溫度0.5~30分鐘、更佳為約1分~10分鐘,於未滿300℃至室溫的溫度0.5~30分鐘、更佳為約1分鐘~10分鐘之多段方式進行冷卻。
最高硬化溫度(T2),與殘留揮發成分降低、尤其膜的密度提升有關,硬化溫度高就結果來說具有提升耐熱性提升及提升耐彎曲性的効果,若溫度過高,可明顯看到熱分解,因此該溫度以下、較佳為540℃以下、更佳為530℃以下、再更佳為525℃以下。
硬化步驟之加熱處理宜為:於具有特定加熱區段之硬化爐中將自撐膜連續運送而實施。硬化爐中,宜以針梳拉幅機、夾具或框架來固定至少垂直於長形固化膜的長邊方向即固定膜之寬度方向的兩端緣來進行運送。可視需要於寬度方向伸展或收縮而進行加熱處理,但本發明中,藉由僅略佳伸縮或擴張調整之大致固定寬度的加熱處理,可得到具有充分目標特性的膜,其中該調整之目的係以抑制溫度變化所伴隨之尺寸變化產生的皺折。
可再視需要,增加降低留應力的後熱處理步驟。使用無張力或輕微的拉伸力的運送裝置,於250℃以上500℃以下之溫度加熱以達成目的。此步驟可為與製膜連續的連續步驟,也可為離線(off-line)步驟。
藉由以上的製造方法,可得到以在升溫前之25℃的尺寸為基準,由25℃至500℃為止之升溫過程之尺寸變化率的最大值為以下範圍的聚醯亞胺膜:超過0且為+1%以下、較佳為大於+0.6%且為+0.9%以下之範圍內,特佳為由+0.76%至0.80%之範圍內。此聚醯亞胺膜可為500℃20分鐘的熱處理後的重量減少率為1質量%以下、25~500℃之升溫時的線膨脹係數為20ppm/℃以下。
此外,發現此聚醯亞胺膜耐彎曲性非常優異。於聚醯亞胺膜之兩面疊層不透氣性之薄膜的狀態進行加熱處理,理由不明地,尤其可發現基材膜耐彎曲性的劣化。此係作為可撓性太陽電池基板材料的問題。研究的結果發現:此耐彎曲性之劣化與聚醯亞胺膜製膜時之最高硬化溫度有關,至膜本身發生明顯熱分解的溫度為止,越是經高溫處理的膜劣化程度越小。另一方面,因為至少單面疊層膜之耐彎曲性的劣化小,推測在高溫的脫氣成分產生某些作用。
高轉換效率之CIS系太陽電池,係於膜的兩面形成如導電層之不透氣性薄膜的狀態以高溫進行熱處理,故本發明之聚醯亞胺膜極適合作為CIS系太陽電池的基板使用。尤其因為耐彎曲性優異,可適用於使用在車載、其他、反覆受到震動之領域的CIS系太陽電池。
聚醯亞胺膜的厚度並無特別限定,約為7.5~75μm、較佳為約10~60μm。
藉由本發明而得之聚醯亞胺膜,黏著性、濺鍍性或金屬蒸鍍性良好,藉由以濺鍍或金屬蒸鍍等金屬化法設置金屬層(包含合金),可得到密著性優異且具有充分的剝離強度的金屬疊層聚醯亞胺膜。金屬層的疊層可依據公知的方法進行。
金屬層係鎳、鉻、錳、鋁、鐵、鉬、鈷、鎢、釩、鈦、鉭、銅等金屬或此等之合金、或此等金屬之氧化物或金屬之碳化物等的層,例如鉬或鎢係作為CIS系太陽電池等的電極而使用的導電層等。
使用於CIS系太陽電池之製造等之聚醯亞胺金屬疊層體,係於聚醯亞胺膜上形成作為電極之金屬層而得之疊層體,例如於聚醯亞胺膜上形成作為電極之包含鉬或鎢等金屬的層等而得之疊層體。
本發明之疊層體也可為於聚醯亞胺膜的兩面具有金屬層者,在該情況,兩金屬層為CIS系太陽電池之電極與設置於基板背面之保護層。兩金屬層,可為相同或不同,然而以兩者相同為佳。
雖於後述,但本發明中,宜於自撐膜之製造時與膜之支持體相接側之面(B面)形成作為電極之金屬層。因此,本發明之疊層體,當於聚醯亞胺膜單面具有金屬層時,宜在B面上具有作為電極之金屬層,較佳為含鉬或鎢之層、又較佳為含鉬之層。
金屬層,較佳為含鉬或鎢等之作為電極之金屬層,以濺鍍法或蒸鍍法等形成。又,製膜條件可依照公知方法適當決定。
金屬層,較佳為含鉬或鎢等之作為電極之金屬層厚度,視使用目的適當選擇,但較佳為約50nm~500nm。
金屬層的層數可視使用目的適當地選擇,2層以上的多層也可。
接著,說明關於本發明之CIS系太陽電池。本發明之CIS系太陽電池其特徵為使用以上說明之聚醯亞胺膜作為基板。
本發明之CIS系太陽電池,可依據公知的方法製造,例如記載於日本特開2003-179238號公報等之方法。利用圖1、圖2,說明CIS系太陽電池之製造方法的一示例。
首先,如圖1(a)所示,於係基板之聚醯亞胺膜1上形成電極層2。電極層2可為導電性材料層,但通常係金屬層,較佳為Mo層。電極層2可藉由濺鍍法或蒸鍍法形成。
本發明中,在聚醯亞胺膜的2個面中,將電極層2疊層於在自撐膜製造時膜與支持體接觸的面(B面)為佳。於B面形成電極層時,相較於在B面之相對側之面(A面)形成電極層,有時能減少電極層或半導體層之裂紋之發生。
又,視需要可於係基板之聚醯亞胺膜1與電極層2之間設置基底金屬層。基底金屬層,可利用例如濺鍍法或蒸鍍法等金屬化法形成。
接著,如圖1(b)所示,在聚醯亞胺基板1之背面形成保護層8。藉由設置如此之保護層,更能抑制電極層或半導體層之裂紋之發生、基板翹曲。
保護層8不特別限定,以金屬層尤其與電極層2相同之金屬層(Mo層為佳)為佳。保護層8,可藉由濺鍍法或蒸鍍法形成。
保護層8視需要設置即可,當使用如上述具有極高耐熱性與尺寸安定性之聚醯亞胺膜時,即使不設置保護層,仍能充分抑制電極層或半導體層之裂紋之發生。
又,本發明中可於形成保護層8後形成電極層2,但於形成電極層2後形成保護層8為佳。依電極層2、保護層8之順序形成,換言之,將先疊層之金屬層(鉬層)作為電極使用,電極層或半導體層之裂紋之發生會較少。
如前所述,電極層形成於B面為佳。因此,本發明之太陽電池之製造方法,以於聚醯亞胺膜所構成之基板B面形成電極層後,於A面形成保護層尤佳。
其次,如圖1(c)所示,於電極層2上,形成含有Ib族元素及IIIb族元素及VIb族元素之薄膜層3。該薄膜層3,典型上,係僅由Ib族元素與IIIb族元素與VIb族元素所構成之薄膜,由之後的熱處理成為太陽電池之光吸收層。Ib族元素,使用Cu為佳。IIIb族元素,使用擇自於In及Ga所構成之群體中至少1種元素為佳。VIb族元素,使用擇自於Se及S所構成之群體中至少1種元素為佳。
薄膜層3可藉由蒸鍍法或濺鍍法形成。形成薄膜層3時之基板溫度,例如室溫(約20℃)~約400℃程度,較之後熱處理中之最高溫度為低。
薄膜層3可為多數之層所構成之多層膜。
電極層2與薄膜層3之間,可形成含有例如Li、Na、K等Ia族元素之層或其他之層。含Ia族元素之層,例如:Na2
S、NaF、Na2
O2
、Li2
S或LiF所構成之層。該等之層,可藉由蒸鍍法或濺鍍法形成。
其次,藉由將薄膜層3進行熱處理,如圖2(d)所示,形成含有Ib族元素與IIIb族元素與VIb族元素之半導體層(黃銅礦構造半導體層)3a。該半導體層3a作為太陽電池之光吸收層的功能。
薄膜層變換為半導體層之熱處理,於氮氣、氧氣或氬氣氣體環境中進行為佳。或,於擇自於Se及S所構成之群體中至少1種蒸氣氣體環境中進行為佳。
熱處理,係宜將薄膜層3以10℃/秒~50℃/秒之範圍內之升溫速度,加熱至450℃~550℃之範圍內、較佳為480℃~550℃之範圍內、更佳為490℃~540℃之範圍、再更佳為500℃~530℃之範圍內之溫度後,較佳於此範圍內之溫度保持10秒~5分鐘。之後,可將薄膜層3自然冷卻或使用加熱器以慢於自然冷卻之速度將薄膜層3冷卻。
該熱處理可分階段進行。例如,將薄膜層3加熱至100℃~400℃之範圍內之溫度,於該範圍內之溫度保持較佳為10秒~10分鐘後,以較佳為10℃/秒~50℃/秒之範圍內之升溫速度,加熱至上述範圍內的溫度,較佳為於該範圍內之溫度保持10秒~5分鐘。之後,將薄膜層3自然冷卻,或使用加熱器以慢於自然冷卻之速度將薄膜層3冷卻。
以此方式,形成成為光吸收層之Ib族元素與IIIb族元素與VIb族元素之半導體層3a。形成之半導體層3a,例如為CuInSe2
、Cu(In,Ga)Se2
,或該等之Se的一部分取代為S之CuIn(S,Se)2
、Cu(In,Ga)(S,Se)2
半導體層。
半導體層3a可依如下方式形成。
於電極層2上形成不含VIb族元素、含Ib族元素及IIIb族元素之薄膜層3,典型上為僅由Ib族元素及IIIb族元素所構成之薄膜。且,將該薄膜層變換為半導體層之熱處理,於含VIb族元素之氣體環境中,較佳為於擇自於Se及S所構成之群體中至少1種蒸氣氣體環境中進行,可形成含有Ib族元素及IIIb族元素及VIb族元素之半導體層。又,薄膜層之形成方法及熱處理條件與上述相同。
半導體層3a形成後,依照公知方法,例如圖2(e)所示,依序疊層窗層(或緩衝層)4、上部電極層5,形成抽出電極6及7,製作為太陽電池。窗層4例如可使用CdS或ZnO、Zn(O,S)所構成之層。窗層可為2層以上。上部電極層5,例如可使用ITO、ZnO:Al等透明電極。上部電極層5上可設置MgF2
等抗反射膜。
又,各層之構成或形成方法不特別限定,可適當選擇。
本發明中,使用可撓性聚醯亞胺基板,因此能以整捲連續製造方式製造CIS系太陽電池。
以上說明中顯示將聚醯亞胺膜做成不疊層於其他基板之獨立的膜,之後於膜表面形成金屬層作為疊層體的示例。製造本發明之聚醯亞胺膜時,於不銹鋼等金屬基板上流延塗佈聚醯亞胺前趨物溶液,於該基板上形成聚醯胺酸之塗佈被膜,在該基板上進行加熱處理、醯亞胺化,可製造預先形成於基板上之聚醯亞胺膜的疊層體。在形成於金屬基板上之聚醯亞胺絕緣層的表面可形成本發明表示之CIGS太陽電池。此時,為促進金屬層與聚醯亞胺層的密合,金屬基板上可以各種偶聯劑處理。在該情況,熱處理溫度變高、耐熱性之表面處理劑為必要,鋁系偶聯劑等適於使用。
以下,以實施例更詳細說明本發明,但本發明不限於該等實施例。
聚醯亞胺膜之物性(25℃~500℃之尺寸變化率及線膨脹係數及500℃、20分鐘熱處理後之重量減少率)以上述方式求得。又,聚醯亞胺膜之25℃~500℃之尺寸變化率及線膨脹係數之測定,使用SII Technology公司製TMA/SS6100,重量減少率之測定使用島津製作所製TGA-50。
耐彎曲性之評價方法如下。
將Mo膜形成於膜兩面後,實施加熱處理(480℃、2.5分鐘)、使用氯化亞鐵水溶液利用蝕刻將Mo膜以蝕刻去除後,測定MIT次數(斷裂為止的次數;曲率半徑:0.38mm、荷重:9.8N、折彎速度:175回/分、折彎角度:左右135度、試驗的寬度:15mm)。
以RF濺鍍機(功率:2.0kW/m2
)進行前處理後,於該聚醯亞胺膜兩面,以下列條件以DC濺鍍機,依序在B面、A面形成厚度100nm之Mo層,得到鉬疊層聚醯亞胺膜。
功率:40kW/m2
(DC)、
濺鍍機氣體:Ar、
腔室氣壓:0.6Pa、
聚醯亞胺膜寬度:300mm、
運送速度:0.3m/分。
關於聚醯亞胺膜,利用熱機械性分析儀(TMA),以下述條件、將由25℃至500℃的升溫過程及與其連續之由500℃至25℃的降溫過程重複進行2次,測定第2次之各溫度中相對於MD方向(連續製膜方向;膜的長邊方向)及TD方向(垂直於MD方向之方向;膜的寬度方向)之初始尺寸(升溫前25℃之尺寸)的尺寸變化率。
測定模式:拉伸模式、荷重2g、
試料長度:15mm、
試料寬度:4mm、
升溫開始溫度:25℃、
升溫終了溫度:500℃(於500℃無保持時間)、
降溫終了溫度:25℃、
升溫及降溫速度:20℃/min、
測定氣體環境:氮氣
熱變形溫度可利用熱機械性分析儀(TMA),以下述之條件,於升溫的同時測定伸長(%),由相對於溫度(℃)之伸長(%)的曲線,作為伸長(%)之上升溫度而求得。
測定模式:拉伸模式、荷重4g
試料長度:15mm、
試料寬度:4mm、
升溫開始溫度:25℃、
升溫終了溫度:500℃(於500℃無保持時間)、
降溫終了溫度:25℃、
升溫及降溫速度:20℃/min、
測定氣體環境:空氣
於聚合槽放入N,N-二甲基乙醯胺2470質量份,其次,加入3,3’,4,4’-聯苯四羧酸二酐(s-BPDA)294.33質量份及對苯二胺(PPD)108.14質量份,於30℃進行10小時聚合反應,得聚醯胺酸溶液(聚醯亞胺前趨物溶液)。得到之聚醯胺酸溶液之聚合物的對數黏度(測定溫度:30℃、濃度:0.5g/100ml溶媒、溶媒:N,N-二甲基乙醯胺)為2.66,溶液於30℃之旋轉黏度為3100泊。
於參考例1得到之聚醯胺酸溶液,以相對於聚醯胺酸100質量份為0.1質量份之比例添加單硬脂基磷酸酯三乙醇胺鹽,均勻混合得到聚醯胺酸溶液組成物。該聚醯胺酸溶液組成物於30℃之旋轉黏度為3000泊。
將該聚醯胺酸溶液組成物從T模具之狹縫連續流延至平滑的到支持體上,於支持體上形成薄膜。將該薄膜以131℃1.5分鐘-133℃2.3分鐘-119℃2.3分鐘進行加熱並乾燥,從支持體剝離得到固化膜(自撐膜)。澆鑄步驟的最高溫度(T1)為133℃。此133℃的階段係聚醯亞胺前趨物溶液藉由乾燥而失去流動性(固化)的階段。
接著的硬化步驟中,握持自撐膜之寬度方向的兩端部,***到連續加熱爐(硬化爐)中。此時,硬化爐之入口溫度為100℃,膜以1.5分鐘通過100℃的區段,以1.5分鐘通過127℃的區段。至此區段為止的溫度係熱變形溫度(TM
)以下。
又,以1.5分鐘通過170℃的區段。依序通過逐漸升溫的區段,以30秒通過最高溫之約500℃(最高熱處理溫度(T2))的區段,得到捲曲成捲狀之長形、厚度為50μm之聚醯亞胺膜。
得到的聚醯亞胺膜之特性的評價結果如表1所示。
關於此聚醯亞胺膜,將重量減少率為36~39%之範圍時的自撐膜所顯示之熱變形溫度(TM
)如上述般求得,為135℃。自撐膜之重量減少率為39%。
除將實施例1中硬化步驟之最高溫度變更為480℃(實施例2)、520℃(實施例3)、460℃(參考例1)以外,重複實施實施例1,製造長形厚度為50μm之聚醯亞胺膜。得到的聚醯亞胺膜之特性的評價結果如表1所示。
除了實施例1中澆鑄步驟之最高溫度定為145℃以外,重覆實施實施例1,製造長形厚度為50μm之聚醯亞胺膜。製得之聚醯亞胺膜之特性的評價結果如表1所示。
如以上,依照本發明藉由使用耐受於450℃以上、尤其480℃以上之高溫熱處理之具有極高耐熱性及尺寸安定性之聚醯亞胺膜,可得具可撓性且轉換效率高之CIS系太陽電池。
又,除了CIS系太陽電池以外,本發明之聚醯亞胺膜適用於在高溫尤其需要於450℃以上、尤其480℃以上之高溫進行熱處理之用途。
1‧‧‧聚醯亞胺基板
2‧‧‧電極層
3‧‧‧薄膜層
3a‧‧‧半導體層
4‧‧‧窗層
5‧‧‧上部電極層
6、7‧‧‧抽出電極
8‧‧‧保護層
圖1顯示本發明之太陽電池之製造方法之一例的第一步驟圖。
圖2顯示本發明之太陽電池之製造方法之一例的第二步驟圖。
Claims (5)
- 一種聚醯亞胺膜的製造方法,係利用熱醯亞胺化的方法,包含以下步驟:聚醯亞胺前趨物溶液的製造步驟,使以3,3’,4,4’-聯苯四羧酸二酐為主成分之芳香族四羧酸成分,與以對苯二胺為主成分之芳香族二元胺成分於溶媒中反應;澆鑄步驟,將所製造之聚醯亞胺前趨物溶液流延塗佈於支持體上,並加熱以製造自撐膜;硬化步驟,將製得之自撐膜加熱,並進行醯亞胺化反應;其特徵為該澆鑄步驟之自撐膜,係以下式(A)表示重量減少率為36~39%之範圍者:重量減少率(%)=(W1-W2)/W1×100 (A)(W1係自撐膜之質量,W2係硬化後之聚醯亞胺膜之質量);該澆鑄步驟之最高溫度(T1),係該自撐膜所顯示之熱變形溫度(TM )以下;該硬化步驟係將該自撐膜以較熱變形溫度TM 低之溫度加熱,之後,使溫度上升,於最高熱處理溫度(T2)495℃~540℃的範圍進行熱處理。
- 如申請專利範圍第1項之聚醯亞胺膜的製造方法,其中,所製造之聚醯亞胺膜的厚度為7.5~75μm。
- 如申請專利範圍第1或2項之聚醯亞胺膜的製造方法,其中,該澆鑄步驟之聚醯亞胺前趨物之熱處理的最高溫度(T1)為140℃以下。
- 一種疊層體的製造方法,其特徵為利用申請專利範圍第1或2項之製造方法製造聚醯亞胺膜後,於該聚醯亞胺膜之表面形成金屬層。
- 一種CIS系太陽電池之製造方法,其特徵為利用申請專利範圍第1或2項之製造方法製造聚醯亞胺膜後,於該聚醯亞胺膜的表面形成金屬層,之後,形成黃銅礦構造半導體層。
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CN102839375B (zh) * | 2012-09-28 | 2014-06-18 | 哈尔滨理工大学 | 制备cis柔性薄膜太阳能电池的光吸收层的方法 |
JP2014204075A (ja) * | 2013-04-09 | 2014-10-27 | 富士フイルム株式会社 | 光電変換素子および太陽電池 |
EP3019541B1 (en) | 2013-07-09 | 2018-09-19 | Evonik Degussa GmbH | Electroactive polymers, manufacturing process thereof, electrode and use thereof |
JP6254459B2 (ja) * | 2014-02-27 | 2017-12-27 | 東京エレクトロン株式会社 | 重合膜の耐薬品性改善方法、重合膜の成膜方法、成膜装置、および電子製品の製造方法 |
TWI518572B (zh) * | 2014-03-07 | 2016-01-21 | 群創光電股份有限公司 | 觸控面板、顯示面板、以及用於保護基板之強化結構 |
WO2015147106A1 (ja) * | 2014-03-25 | 2015-10-01 | 株式会社カネカ | 化合物半導体太陽電池の製造方法 |
JP6672667B2 (ja) * | 2015-09-24 | 2020-03-25 | 富士ゼロックス株式会社 | ポリイミド前駆体組成物、ポリイミド前駆体組成物の製造方法、及びポリイミド成形体の製造方法。 |
JP7072140B2 (ja) * | 2017-05-31 | 2022-05-20 | Ube株式会社 | ポリイミドフィルム |
WO2019045376A1 (ko) * | 2017-09-04 | 2019-03-07 | 주식회사 엘지화학 | 플렉서블 디스플레이 소자 기판용 폴리이미드 필름 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09148694A (ja) * | 1995-11-20 | 1997-06-06 | Ube Ind Ltd | フレキシブル回路基板 |
JP2007317834A (ja) * | 2006-05-25 | 2007-12-06 | Toyobo Co Ltd | フィルム状太陽電池 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4275185A (en) * | 1979-09-24 | 1981-06-23 | Ici Americas Inc. | Polyimides of bismaleimides and activated methylene compounds |
US4725484A (en) * | 1985-05-17 | 1988-02-16 | Ube Industries, Ltd. | Dimensionally stable polyimide film and process for preparation thereof |
JPH07307114A (ja) | 1994-05-13 | 1995-11-21 | Hitachi Ltd | ポリイミド絶縁膜の形成方法 |
US5849397A (en) * | 1995-10-03 | 1998-12-15 | Ube Industries, Ltd. | Aromatic polyimide film and polyimide/copper foil composite sheet |
JPH09316199A (ja) | 1996-05-24 | 1997-12-09 | Ube Ind Ltd | ポリイミド化合物のイミド化率の測定方法、その利用 |
US6274805B1 (en) | 1997-05-07 | 2001-08-14 | Asahi Kasei Kabushiki Kaisha | Solar cell and manufacturing method thereof |
JP3346228B2 (ja) * | 1997-07-11 | 2002-11-18 | 宇部興産株式会社 | 芳香族ポリイミドフィルム、積層体および太陽電池 |
JP2005161858A (ja) * | 2000-10-02 | 2005-06-23 | Ube Ind Ltd | 線膨張係数を制御したポリイミドフィルムの製造法 |
JP3994696B2 (ja) * | 2000-10-02 | 2007-10-24 | 宇部興産株式会社 | 線膨張係数を制御したポリイミドフィルム及び積層体 |
JP2003179238A (ja) | 2001-12-10 | 2003-06-27 | Matsushita Electric Ind Co Ltd | 薄膜太陽電池の製造方法 |
AU2003230823A1 (en) * | 2002-04-05 | 2003-10-27 | United States Of America As Represented By The Administrator Of The National Aeronautics And Space | Polyimides from 2,3,3',4'-biphenyltetracarboxylic dianhydride and aromatic diamines |
WO2005085333A1 (ja) * | 2004-03-03 | 2005-09-15 | Kaneka Corporation | 分子配向が制御された有機絶縁フィルムおよびそれを用いた接着フィルム、フレキシブル金属張積層板、多層フレキシブル金属張積層板、カバーレイフィルム、tab用テープ、cof用ベーステープ |
WO2006078919A2 (en) * | 2005-01-20 | 2006-07-27 | Hanket Gregory M | Microfiller-reinforced polymer film |
CN101151304B (zh) * | 2005-04-08 | 2012-04-04 | 三井化学株式会社 | 聚酰亚胺膜、使用其的聚酰亚胺金属层叠体及其制造方法 |
JP2008266416A (ja) * | 2007-04-18 | 2008-11-06 | Ube Ind Ltd | ポリイミドフィルムの製造方法およびポリイミドフィルム |
KR101242342B1 (ko) * | 2007-07-27 | 2013-03-11 | 우베 고산 가부시키가이샤 | 폴리이미드 필름 및 배선 기판 |
JP5233298B2 (ja) * | 2008-02-01 | 2013-07-10 | 宇部興産株式会社 | ポリイミドフィルムおよびポリイミドフィルムの製造方法 |
EP2292681B1 (en) * | 2008-05-20 | 2016-06-08 | Ube Industries, Ltd. | Aromatic polyimide film, laminate and solar cell |
CN102089366B (zh) * | 2008-05-20 | 2013-06-19 | 宇部兴产株式会社 | 聚酰亚胺-金属层压制品和太阳电池 |
CN102112293B (zh) * | 2008-06-02 | 2014-12-03 | 宇部兴产株式会社 | 宽度方向的线性膨胀系数比传送方向的线性膨胀系数小的芳族聚酰亚胺薄膜的制备方法 |
JP2009067042A (ja) | 2008-06-02 | 2009-04-02 | Ube Ind Ltd | ポリイミドフィルムの製造法 |
KR101735864B1 (ko) * | 2009-11-20 | 2017-05-15 | 우베 고산 가부시키가이샤 | 방향족 폴리이미드 필름, 적층체 및 태양 전지 |
-
2010
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09148694A (ja) * | 1995-11-20 | 1997-06-06 | Ube Ind Ltd | フレキシブル回路基板 |
JP2007317834A (ja) * | 2006-05-25 | 2007-12-06 | Toyobo Co Ltd | フィルム状太陽電池 |
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US20170040475A1 (en) | 2017-02-09 |
WO2011062271A1 (ja) | 2011-05-26 |
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US20120241005A1 (en) | 2012-09-27 |
KR101735864B1 (ko) | 2017-05-15 |
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EP2502955A1 (en) | 2012-09-26 |
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