TWI466305B - 太陽電池基板用鋼箔、太陽電池基板、太陽電池及各該等的製造方法 - Google Patents

太陽電池基板用鋼箔、太陽電池基板、太陽電池及各該等的製造方法 Download PDF

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TWI466305B
TWI466305B TW100145340A TW100145340A TWI466305B TW I466305 B TWI466305 B TW I466305B TW 100145340 A TW100145340 A TW 100145340A TW 100145340 A TW100145340 A TW 100145340A TW I466305 B TWI466305 B TW I466305B
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solar cell
cell substrate
steel foil
substrate according
steel
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TW201240107A (en
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Yasuhiro Yamaguchi
Atsutaka Honda
Naoki Nishiyama
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Jfe Steel Corp
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    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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Description

太陽電池基板用鋼箔、太陽電池基板、太陽電池及各該等的製造方法
本發明是有關於一種太陽電池基板用鋼箔(steel foil for solar cell substrate)，尤其是有關於厚度20 μm～200 μm的太陽電池基板用鋼箔。
自先前以來，太陽電池基板用材料是使用玻璃(glass)，但近年來，專利文獻1～專利文獻3等中，就強度或耐化學品性(chemical resistance)的觀點考慮，提出了厚度1 mm以下的光澤退火(bright annealing)後的不鏽鋼板(例如SUS430)。若將此種不鏽鋼板用於基板，則可將基板以線圈(coil)的狀態進行處理，因此太陽電池是利用對大量生產有利的稱為輥對輥(Roll-to-Roll)方式的連續製程(continual process)來製造。最近，為了實現成本降低(cost reduction)，而對厚度20 μm～200 μm左右的不鏽鋼箔進行研究。例如，專利文獻4中，提出有絕緣性(insulation properties)或熱穩定性(thermal stability)優異，可製作具有凹凸紋理結構(concave-convex texture structure)的背面反射層(reflective layer of back side)作為太陽電池的以氧化矽系無機聚合物(溶膠-凝膠氧化矽玻璃，sol-gel silica glass)所包覆的不鏽鋼箔。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本專利特開昭64-72571號公報
[專利文獻2]日本專利特開平5-306460號公報
[專利文獻3]日本專利特開平6-299347號公報
[專利文獻4]日本專利特開2006-270024號公報
然而，若將如專利文獻4所記載的不鏽鋼箔帶應用於輥對輥方式的連續製程，則存在以下問題：在箔帶上產生屈曲(buckling)，屈曲部移到輥(roll)上而容易產生皺褶(wrinkle)、彎折(broken surface)、擰絞(drawing)等。
本發明的目的在於提供一種即便應用於輥對輥方式的連續製程亦難以產生屈曲的太陽電池基板用鋼箔及其製造方法。
本發明者等人為了達成上述目的而進行積極研究，結果發現有效的是，使用包含7質量%～40質量%的鉻(Cr)，且在軋延方向(rolling direction)上直角方向的拉伸強度(tensile strength)為930 MPa以上的鋼箔。
本發明是基於上述發現而形成，提供一種特徵在於包含7質量%～40質量%的Cr，且在軋延方向上直角方向的拉伸強度為930 MPa以上的太陽電池基板用鋼箔。
本發明的太陽電池基板用鋼箔中，較佳為：在軋延方向上直角方向的拉伸強度為1000 MPa以上，或者微組織保持為軋延組織的狀態。另外，較佳為0℃～100℃下的線膨脹係數為12.0×10-6 /℃以下，或者微組織是以肥粒鐵組織為主體的組織。
本發明的太陽電池基板用鋼箔可藉由將包含7質量%～40質量%的Cr且厚度1 mm以下的光澤退火後或者退火、酸洗後的鋼板，以50%以上的壓下率(rolling reduction)進行冷軋(cold rolling)而製造。此時，較佳為以70%以上的壓下率進行冷軋，或者使用具有肥粒鐵組織(ferrite structure)的光澤退火後或者退火、酸洗後的鋼板，或者冷軋後在惰性氣體環境(inert gas atmosphere)中實施400℃～700℃的熱處理。
另外，本發明提供一種特徵在於使用上述太陽電池基板用鋼箔的太陽電池基板、或特徵在於使用該太陽電池基板的太陽電池。
本發明進而提供一種特徵在於使用上述太陽電池基板且利用輥對輥方式的連續製程來製造的太陽電池的製造方法。此時，較佳為輥對輥方式的連續製程包括：清潔-背電極濺鍍-太陽電池處理-硒化處理-緩衝層形成-上電極濺鍍-電極形成-開縫的步驟。
[發明的效果]
藉由本發明，可製造即便應用於輥對輥方式的連續製程亦難以產生屈曲的太陽電池基板用鋼箔。
1)太陽電池基板用鋼箔
本發明中，作為基材來使用的鋼箔只要具有太陽電池的基板所必需的耐蝕性，則並無特別限制。但，若Cr量小於7質量%，則長期使用時的耐蝕性(corrosion resistance)不足，存在基板的腐蝕的問題，若超過40質量%，則存在作為鋼箔製造中的中間製品(partly-finished product)的熱軋鋼板(hot rolled steel sheet)的韌性(toughness)顯著降低，而無法通過生產線(manufacturing line)的問題。因此Cr量必需設為7質量%～40質量%。此種鋼可列舉：SUS430(17%Cr鋼)、SUS447J1(30%Cr-2%鉬(Mo)鋼)、9%Cr鋼、20%Cr-5%鋁(Al)鋼、SUS304(18%Cr-8%鎳(Ni)鋼)等。
以下，若表示特別適合的成分組成，則如下所述。此外，對鋼的成分組成進行規定的成分%全部是指質量%。
碳(C)：0.12%以下
由於C與鋼中的Cr結合而導致耐蝕性(corrosion resistance)下降，故而越低越好，若為0.12%以下，則不會使耐蝕性顯著下降。因此，較佳為0.12%以下，更佳為0.04%以下。
矽(Si)：2.5%以下
Si是用於脫氧(deoxidation)的元素，但若過剩含有，則導致延展性下降，故而較佳為2.5%以下。更佳為1.0%以下。
錳(Mn)：1.0%以下
由於Mn與硫(S)結合形成硫化錳(MnS)而使耐蝕性下降，故而較佳為1.0%以下。更佳為0.8%以下。
S：0.030%以下
如上所述，由於S與Mn結合形成MnS而使耐蝕性下降，故而較佳為0.030%以下。更佳為0.008%以下。
磷(P)：0.050%以下
由於P導致延展性下降，故而越低越好，若為0.050%以下，則不會使延展性顯著下降。因此，較佳為0.050%以下，更佳為0.040%以下。
Cr：7%以上、40%以下
若Cr量小於7質量%，則長期使用時的耐蝕性不足，存在基板的腐蝕的問題，若超過40質量%，則存在作為鋼箔製造中的中間製品的熱軋鋼板的韌性顯著下降而無法通過生產線的問題。因此，Cr量必需設為7質量%～40質量%。
以上，已對必需成分進行說明，但本發明中，除此以外可適當含有以下所述的元素。
選自鈮(Nb)、鈦(Ti)、鋯(Zr)中的至少一種合計：1.0%以下
Nb、Ti、Zr均為將鋼中的C、氮(N)固定為碳化物或氮化物、或者碳氮化物，對改善耐蝕性而言有用的元素。但，若含量超過1.0%，則延展性(ductility)的下降變得顯著，因此該些元素在單獨添加或者複合添加的任一種情況下均限定為1.0%以下。此外，為了使該些元素的添加效果充分發揮，較佳為含有0.02%以上。
Al：0.20%以下
Al是用於脫氧的元素，但含量過剩，則導致延展性下降，因此較佳為0.20%以下。更佳為0.15%以下。
N：0.05%以下
由於N與鋼中的Cr結合而導致耐蝕性下降，故而越低越好，若為0.05%以下，則不會使耐蝕性顯著下降。因此，較佳為0.05%以下。更佳為0.015%以下。
Mo：0.02%以上4.0%以下
Mo是對改善鋼箔的耐蝕性、特別是局部腐蝕性(localized corrosion)而言有效的元素，為了獲得該效果，較佳為含有0.02%以上。另一方面，若含量超過4.0%，則延展性的下降變得顯著，因此上限較佳為4.0%。更佳為2.0%以下。
另外，除此以外，以耐蝕性的改善為目的，亦可含有分別為1.0%以下的Ni、銅(Cu)、釩(V)、鎢(W)。進而，以熱加工性(hot workability)的提高為目的，亦可含有分別為0.1%以下的鈣(Ca)、鎂(Mg)、稀土金屬(Rare Earth Metals，REM)、硼(B)。
殘部為(Fe)及不可避免的雜質。不可避免的雜質中，氧(O)較佳為0.02%以下。
利用輥對輥方式的連續製程來製造太陽電池時，必需對線圈狀的基板用鋼箔，例如以清潔(cleaning)-背電極濺鍍(sputtering Mo back contact)-太陽電池處理(光吸收層形成(deposite absorber layer)-硒化處理(selenization)-緩衝層形成(Cds buffer layer(化學浴沈積，chemical bath deposition))-上電極濺鍍(sputtertop electrode)-電極形成(deposite front electrode)-開縫(slitting)等多個步驟進行處理。因此，基板用鋼箔由於受到輥的許多次彎曲 (bend)、彎曲恢復(unbend)的加工，故而被置於容易產生屈曲的狀況。尤其，若在鋼箔的軋延方向上直角方向的拉伸強度小(柔軟)，則通過輥時會產生由平行於軋延方向的屈曲引起的皺褶(皺曲)。為了防止該屈曲，有效的是如上所述，在基板用鋼箔的軋延方向上將直角方向的拉伸強度設為930MPa以上、較佳為1000MPa以上，來提高箔的剛性(stiffness)。
另外，微組織較佳為如圖2A~圖2C所示的軋延組織的狀態。此處，所謂圖2A~圖2C所示的軋延組織的狀態是指在冷軋的狀態下或者在惰性氣體環境中實施400℃~700℃、0分鐘~5分鐘的熱處理的組織是軋延組織的一部分或者全部在熱處理中並不再結晶而以扁平粒的狀態殘存的組織。軋延組織的體積率為50vol%以上，較佳為90vol%以上。此外，圖2D表示退火材料(再結晶材料)，若導致再結晶，則縱橫比(長軸÷短軸)大致接近於1。圖2A~圖2D的微組織是在王水蝕刻後以1000倍進行顯微鏡觀察而得。
進而，若將SUS304等的0℃~100℃下的線膨脹係數超過12.0×10-6 /℃的鋼箔用於基板，則Cu(In1-X GaX )Se2 薄膜(以下，稱為CIGS薄膜)由於與基板的線膨脹係數的不同而在製造中產生剝離的問題。因此，0℃~100℃下的線膨脹係數較佳為12.0×10-6 /℃以下。為了使0℃~100℃下的線膨脹係數為12.0×10-6 /℃以下，較佳為形成SUS430或SUH409L等肥粒鐵系不鏽鋼、具有肥粒鐵組織的9質量%Cr鋼等以肥粒鐵組織為主體的組織。所謂以肥粒鐵組織為主體的組織是指肥粒鐵的面積率為95%以上。殘部的組織為沃斯田體(austenite)組織、麻田散體(martensite)組織的1種以上，小於5%。
2)太陽電池基板用鋼箔的製造方法
本發明的太陽電池基板用鋼箔可藉由將包含7質量%～40質量%的Cr且厚度1 mm以下的光澤退火後或者退火、酸洗後的鋼板，以50%以上的壓下率進行冷軋來製造。其原因在於，如圖1所示，在SUS430等的情況下若將壓下率設為50%以上，則獲得930 MPa以上的拉伸強度。若將壓下率設為70%以上，則獲得1000 MPa以上的拉伸強度。
另外，為了製成使0℃～100℃下的線膨脹係數為12.0×10-6 /℃以下的鋼箔，只要使用SUS430或SUH409L等肥粒鐵系不鏽鋼、具有肥粒鐵組織的9質量%Cr鋼等具有肥粒鐵組織的光澤退火後或者退火、酸洗後的鋼板即可。
另外，雖在冷軋的情況下亦能夠達成本發明的目的，但若冷軋後，在氮氣(N2 )、AX氣(或者亦稱為氨分解氣體)(NH3 cracking gas)(75 vol%H2 +25 vol%N2 )、氫氣(H2 )、氫氮氣(HN，5 vol% H2 +95 vol% N2 )、氬氣(Ar)等惰性氣體環境中實施400℃～700℃、0分鐘～5分鐘的熱處理，則雖認為取決於時效硬化(age-hardening)，但可實現進一步的高強度化，對防止屈曲而言更有效果。若熱處理溫度(heat treatment temperature)小於400℃，則不會表現出此種效果，若超過700℃，則軟化，無法獲得930 MPa以上的拉伸強度。尤佳為400℃～600℃。
[實例1]
使用表1所示組成的SUS430(16%Cr)及9%Cr鋼的厚度0.05 mm～0.3 mm的光澤退火後的冷軋鋼板，以表2所示的壓下率進行冷軋而製成厚度30 μm～50 μm的鋼箔，進行脫脂(degreasing)後，直接或者對一部分的鋼箔，在N2 氣環境中以表2所示的熱處理溫度進行熱處理後，藉由包括多源蒸鍍(multi-source deposition)或者濺鍍步驟的太陽電池的輥對輥方式的連續製程進行處理。然後，自冷軋後或者熱處理後的鋼箔上，在軋延方向上採集直角方向的拉伸試驗，測定拉伸強度及伸長率(elongation)，並且測定鋼箔的維氏硬度(Vickers hardness)(Hv)。進而，以目視來檢查藉由連續製程的處理中的皺褶的產生狀況。
將結果示於表2。本發明例中可知，均為拉伸強度為930 MPa以上，且未產生皺褶。另外可知，藉由在冷軋後，在本發明範圍內的熱處理溫度(400℃～700℃)下進行熱處理，能夠提高拉伸強度。
[實例2]
對於表1所示組成的SUS430、11%Cr-1.5%Si鋼及SUS304，以表3所示的壓下率進行冷軋而形成厚度30 μm～50 μm的鋼箔，進行脫脂後，直接或者對一部分的鋼箔，在N2 氣環境中以表3所示的熱處理溫度進行熱處理後，藉由包括多源蒸鍍或者濺鍍步驟的太陽電池的輥對輥方式的連續製程進行處理。然後，自冷軋後或者熱處理後的鋼箔上，在軋延方向上採集直角方向的拉伸試驗，測定拉伸強度及伸長率，並且測定鋼箔的維氏硬度(Hv)。拉伸強度與伸長率是依據JIS Z 2241(1998)來測定，Hv是依據JIS Z 2244(1998)來測定。進而，以目視來檢查藉由連續製程的處理中的皺褶的產生狀況。另外，以目視及顯微鏡來觀察CIGS薄膜的剝離狀態。此外，表3中亦列出各鋼的0℃～100℃下的線膨脹係數。
將結果示於表3。本發明例中可知，均為拉伸強度為930 MPa以上，且未產生皺褶。另外可知，0℃～100℃下的線膨脹係數為12.0×10-6 /℃以下的例子中，亦未產生CIGS薄膜剝離。
圖1是表示壓下率與軋延方向上直角方向的拉伸強度的關係的圖。
圖2A表示本發明材料中SUS430-箔厚度50 μm的軋延組織的微組織。(壓下率83%)
圖2B表示本發明材料中SUS430-箔厚度50 μm的700℃(惰性氣體環境中)的熱處理材料的微組織。(壓下率83%)
圖2C表示本發明材料中SUS430-箔厚度50 μm的400℃(惰性氣體環境中)的熱處理材料的微組織。(壓下率83%)
圖2D表示習知材料(比較材料)中SUS430-箔厚度50 μm的退火材料(再結晶材料)的微組織。(壓下率83%)

Claims (17)

  1. 一種太陽電池基板用鋼箔，其特徵在於：包含7質量%~40質量%的鉻，且在軋延方向上直角方向的拉伸強度為930MPa以上。
  2. 如申請專利範圍第1項所述之太陽電池基板用鋼箔，其中在軋延方向上直角方向的拉伸強度為1000MPa以上。
  3. 如申請專利範圍第1項或第2項所述之太陽電池基板用鋼箔，其中微組織保持為軋延組織的狀態。
  4. 如申請專利範圍第1項或第2項所述之太陽電池基板用鋼箔，其中在0℃~100℃的線膨脹係數為12.0×10-6 /℃以下。
  5. 如申請專利範圍第1項或第2項所述之太陽電池基板用鋼箔，其中微組織是以肥粒鐵組織為主體的組織。
  6. 一種太陽電池基板用鋼箔的製造方法，其特徵在於：包含將包含7質量%~40質量%的鉻且厚度1mm以下的光澤退火後或者退火、酸洗後的鋼板，以50%以上的壓下率進行冷軋的步驟，經由上述步驟製成的太陽電池基板用鋼箔為如申請專利範圍第1項至第5項中任一項所述之太陽電池基板用鋼箔。
  7. 如申請專利範圍第6項所述之太陽電池基板用鋼箔的製造方法，其中以70%以上的壓下率進行冷軋。
  8. 如申請專利範圍第6項或第7項所述之太陽電池基板用鋼箔的製造方法，其中使用具有肥粒鐵組織的光澤退 火後或者退火、酸洗後的鋼板。
  9. 如申請專利範圍第6項至第8項中任一項所述之太陽電池基板用鋼箔的製造方法，其中冷軋後，在惰性氣體環境中實施400℃~700℃的熱處理。
  10. 一種太陽電池基板，其特徵在於：使用如申請專利範圍第1項至第5項中任一項所述之太陽電池基板用鋼箔。
  11. 一種太陽電池，其特徵在於：使用如申請專利範圍第10項所述之太陽電池基板。
  12. 一種太陽電池的製造方法，其特徵在於：使用如申請專利範圍第10項所述之太陽電池基板，藉由輥對輥方式的連續製程而製造。
  13. 如申請專利範圍第12項所述之太陽電池的製造方法，其中輥對輥方式的連續製程包括：清潔-背電極濺鍍-太陽電池處理-硒化處理-緩衝層形成-上電極濺鍍-電極形成-開縫的步驟。
  14. 如申請專利範圍第3項所述之太陽電池基板用鋼箔，其中在0℃~100℃的線膨脹係數為12.0×10-6 /℃以下。
  15. 如申請專利範圍第3項所述之太陽電池基板用鋼箔，其中微組織是以肥粒鐵組織為主體的組織。
  16. 如申請專利範圍第4項所述之太陽電池基板用鋼箔，其中微組織是以肥粒鐵組織為主體的組織。
  17. 如申請專利範圍第14項所述之太陽電池基板用鋼箔，其中微組織是以肥粒鐵組織為主體的組織。
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