TWI607578B - 太陽電池之製造方法 - Google Patents

太陽電池之製造方法 Download PDF

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TWI607578B
TWI607578B TW104136463A TW104136463A TWI607578B TW I607578 B TWI607578 B TW I607578B TW 104136463 A TW104136463 A TW 104136463A TW 104136463 A TW104136463 A TW 104136463A TW I607578 B TWI607578 B TW I607578B
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solar cell
film
passivation film
substrate
light
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TW201633557A (zh
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平松孝浩
織田容征
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東芝三菱電機產業系統股份有限公司
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Description

太陽電池之製造方法
此發明係關於太陽電池之製造方法，特別是關於形成於矽基板上之鈍化(passivation)膜之成膜方法。
於結晶矽太陽電池之領域中，以減少矽使用量及提升矽基板之轉換效率為目的，正進行著矽基板的薄型化。然而，隨著矽基板進行薄型化，轉換效率明顯變低。此情形係例如以大量存在於具有導電性之矽基板的表面之缺陷為主要因素，使因光照射而產生的少數載體(P型時為電子)的壽命(生命週期，lifetime)減少之故。換言之，減少此種少數載體之消失，係與提升太陽電池之轉換效率有所相關。
為了抑制載體之生命週期減少，一般而言，係於矽基板的表面上形成鈍化膜。在多種鈍化膜之中，尤以對P型矽基板具有高鈍化效果(抑制生命週期減少之功能)之氧化鋁膜受到注目。
氧化鋁膜係於膜中具有負的固定電荷，已知係藉由此種固定電荷所產生的場效而產生鈍化效果。換言之，藉由在P型矽基板的表面上形成具有負的固定電荷的 包含氧化鋁膜之鈍化膜，抑制了少數載體之電子擴散至基板的表面，結果可防止載體消失。
而且，對P型矽基板進行作為鈍化膜之氧化鋁膜之成膜的方法，已揭示有採用霧化法之方法，例如，專利文獻1之太陽電池之製造方法。此製造方法係藉由霧化法成膜為鈍化膜，藉此達到製造成本低、不對矽基板造成損傷，且以高生產效率成膜為鈍化膜之效果。
先前技術文獻 專利文獻
專利文獻1：國際公開第2015/004767號小冊
然而，以霧化法形成鈍化膜時，與以ALD(原子層沉積，Atomic Layer Deposition)法、電漿CVD(化學氣相沈積，Chemical Vapor Deposition)法等來形成鈍化膜時相比，有膜質可能較差之問題。
本發明之目的在於提供一種太陽電池之製造方法，其係解決如上所述之問題，可形成製造成本低，不對基板造成損傷，高生產效率且膜質佳之鈍化膜。
此種發明之太陽電池之製造方法，係具備：(a)製作具有一個主面及另一個主面之矽基板(4)之程序；(b)將包含金屬元素的溶液(14)霧化之程序；(c)在非真空下，將經前述霧化之前述溶液對前述矽基板的一個主 面進行噴霧，藉此將包含金屬氧化膜之鈍化膜(5)於前述矽基板的一個主面上成膜之程序；(d)使用前述形成有鈍化膜之前述矽基板製作太陽電池構造之程序；(e)對前述鈍化膜與前述矽基板的界面進行照射預定的光(21)之光照射處理程序。
此種發明之太陽電池之製造方法，係實行程序(b)、(c)，將包含金屬氧化膜之鈍化膜成膜於矽基板的一個主面上，藉此，可製造成本低，且不對矽基板造成損傷，而且以高生產效率形成鈍化膜。
此外，如申請專利範圍第1項所述之本案發明，可藉由程序(e)所進行之光照射處理，而得到生命週期經提升之品質佳的鈍化膜。
由以下之詳細說明與所附圖式，可更瞭解此種發明之目的、特徴、型態及優點。
1‧‧‧表面電極
2‧‧‧表面鈍化膜
3‧‧‧N型矽層
4‧‧‧P型矽基板
5‧‧‧內面鈍化膜
6‧‧‧內面電極
11‧‧‧反應容器
13‧‧‧加熱器
14‧‧‧(原料)溶液
15‧‧‧溶液容器
16‧‧‧霧化器
21‧‧‧紫外光
L1、L2‧‧‧通路
第1圖係表示實施形態所製造之太陽電池構造的剖面圖。
第2圖係表示於實施形態中用以實現鈍化膜之成膜方法之成膜裝置的結構之說明圖。
第3圖係表示實施形態1之以紫外光進行之光照射處理的狀況之剖面圖。
第4圖係表示實施形態1之太陽電池之製造方法的效 果之圖表。
第5圖係表示實施形態2之太陽電池之製造方法的效果之圖表。
(太陽電池構造)
第1圖係表示本實施形態(實施形態1、實施形態2)之太陽電池之製造方法所製造之太陽電池構造的剖面圖。
如第1圖所示，在具有P型導電型態之矽基板4(以下稱為「P型矽基板4」)的表面(另一個主面)上，係形成有具有N型導電型態之矽層3(以下稱為「N型矽層3」)。又，第1圖中，係表示以P型矽基板4的表面為上表面，內面為下表面之態樣。
而且，於N型矽層3的表面，係形成有具有透明性之表面鈍化膜2。作為表面鈍化膜2，例如可考慮矽氧化膜或是矽氮化膜、氧化鋁膜、或包含該等之積層膜等。而且，藉由貫通表面鈍化膜2的一部分，並於N型矽層3的表面上選擇性地形成表面電極1，表面電極1係與N型矽層3電性連接。
此外，於P型矽基板4的內面(一個主面)上，係形成有內面鈍化膜5。此內面鈍化膜5係採用氧化鋁膜，或氧化鋁膜與矽氮化膜之積層膜。而且，形成有內面電極6，此內面電極6係貫通內面鈍化膜5的一部分而直接形成於P型矽基板4的內面上，同時形成於內面鈍化 膜5的內面上。因此，與P型矽基板4為電性連接。
於第1圖所示之太陽電池構造中，係從表面鈍化膜2之側入射，而藉由到達N型矽層3及P型矽基板4間之PN接合部的光產生載體，進行發電，所發電之電係從電極1、6被取出。
如上述，為了抑制載體的生命週期減少，而形成鈍化膜2、5。換言之，於N型矽層3的表面或P型矽基板4的內面會產生許多缺陷(晶格缺陷等)，並且會透過該缺陷與經由照射光而產生的少數載體進行再結合。於是，藉由在N型矽層3的表面上及P型矽基板4的內面上形成表面鈍化膜2及內面鈍化膜5，抑制載體的再結合，就結果而言係可提升載體的生命週期。
本發明係關於在太陽電池之製造方法中，提升形成於P型矽基板4的內面上之內面鈍化膜5的膜質者，以下係依表示本發明的實施形態之圖式來具體說明本發明。
<實施形態1>
第2圖係表示於本實施形態(實施形態1、實施形態2)中用以實現內面鈍化膜5的成膜方法之成膜裝置之概略構成的說明圖。
如第2圖所示，本實施形態之成膜方法所用的成膜裝置係由反應容器11、加熱反應容器11之加熱器13、收納(材料)溶液14之溶液容器15及將溶液容器15 內的溶液14霧化之霧化器16所構成。
此種構成中，將經霧化器16霧化之溶液14通過通路L1，噴霧於反應容器11內的P型矽基板4的內面上，藉此可在P型矽基板4的內面上進行包含氧化鋁膜之內面鈍化膜5之成膜。此時，P型矽基板4係以內面為上表面、表面為下表面之態樣，載置於反應容器11內的加熱器13上。
亦即，以於加熱器13上載置有P型矽基板4之狀態，將霧體(粒徑小之液狀溶液14)供給至大氣壓下的反應容器11內，藉由預定之反應，於P型矽基板4的內面上成膜內面鈍化膜5。
加熱器13係發熱器(heater)等，可將載置於該加熱器13之P型矽基板4予以加熱。藉由未具圖示之外部調控部，加熱器13係在成膜時加熱至達到氧化鋁膜所構成之內面鈍化膜5的成膜所需的溫度為止。
於溶液容器15內，係填充有內面鈍化膜5之成膜用的材料溶液之溶液14。此溶液14中，係包含鋁(Al)元素作為金屬源。
作為霧化器16，例如可採用超音波霧化裝置。為超音波霧化裝置之霧化器16，係對溶液容器15內的溶液14施加超音波，藉此使溶液容器15內的溶液14霧化。經霧化之溶液14係通過通路L1而供給到反應容器11內的P型矽基板4的內面(上表面)。
往反應容器11內供給霧狀的溶液14時，溶 液14會於加熱中之大氣壓下的P型矽基板4的內面上進行反應，而在P型矽基板4的內面上成膜內面鈍化膜5。而且，於反應容器11之未反應的溶液14，係通過通路L2而經常性地(連續地)排出至反應容器11外。
(製造方法)
其次，就實施形態1之太陽電池之製造方法(尤其是內面鈍化膜5(氧化鋁膜)之成膜方法)進行說明。
首先，藉由對構成材料為結晶矽之矽基板導入預定之雜質，製作具有P型導電型態之P型矽基板4。而且，此P型矽基板4係載置於反應容器11內的加熱器13上。此時，P型矽基板4係以內面為上面、表面為下面之態樣載置於加熱器13上，反應容器11內係設為大氣壓力。如所述，製作具有內面及表面(一個主面及另一個主面)之P型矽基板4。
而且，藉由加熱器13，將載置於加熱器13上之P型矽基板4加熱至達到包含氧化鋁膜之內面鈍化膜5之成膜溫度為止，並以成膜溫度保持P型矽基板4的溫度。
另一方面，在溶液容器15內，藉由霧化器16將溶液14霧化。經霧化之溶液14(粒徑小之液狀的溶液14)係通過通路L1整流而供給至反應容器11內。其中，於溶液14中，係含有鋁作為金屬源。如所述，將含有金屬元素的鋁之溶液14(材料溶液)霧化。
於大氣壓下，對於加熱狀態之P型矽基板4的內面供給經整流之霧狀的溶液14。當於加熱狀態之P型矽基板4的內面噴霧霧狀的溶液14時，會於P型矽基板4的內面上成膜包含氧化鋁膜之內面鈍化膜5。如所述，於大氣壓下(非真空下)，將經霧化之溶液14對P型矽基板4的內面進行噴霧，藉此於P型矽基板4的內面上成膜包含金屬氧化膜之氧化鋁的內面鈍化膜5。
之後，使用成膜有內面鈍化膜5(氧化鋁膜)之P型矽基板4，製作第1圖所示之太陽電池構造。一般而言，內面鈍化膜5，係於形成表面鈍化膜2及N型矽層3後進行成膜，之後再形成表面電極1及內面電極6。又，表面鈍化膜2及內面鈍化膜5之成膜順序亦可顛倒。
第3圖係表示實施形態1之以紫外光21進行之光照射處理的狀況之剖面圖。如圖所示，係以P型矽基板4的表面為上表面之態樣，從太陽電池構造的表面上(P型矽基板4的表面上)照射具有365nm的波長之紫外光21(預定之光)30秒鐘而實行光照射處理。如所述，從太陽電池構造的表面上通過表面鈍化膜2及N型矽層3，而於P型矽基板4及鈍化膜5的界面照射紫外光21，進行光照射處理，藉由使用紫外光21之光照射處理，完成實施形態1之太陽電池。
如以上所述，實施形態1之太陽電池之製造方法中的內面鈍化膜5(氧化鋁膜)之成膜方法，係藉由霧化法(換言之，係於大氣壓下將液狀的溶液14進行噴霧 之成膜方法)，而於P型矽基板4的內面上形成有內面鈍化膜5。
如所述，實施形態1並非經CVD法、ALD法等將氣化之原料供給至P型矽基板4而成膜為包含氧化鋁膜之內面鈍化膜5，而係將經霧化之液狀的溶液14噴霧於P型矽基板4而成膜為內面鈍化膜5。其中，如上所述，溶液14中係包含鋁元素。藉此，可不使用TMA(三甲基鋁，Tri-Methyl-Aluminum)等高價且難處理之材料，而藉由安全且容易處理的材料於P型矽基板4的內面上形成包含氧化鋁膜之內面鈍化膜5。
此外，實施形態1中，因成膜處理係在大氣壓下，故不須真空處理等，亦可謀求減少製造成本。再者，實施形態1中，係於P型矽基板4噴霧霧狀的溶液14，藉此實施成膜處理。因此，成膜處理中，亦不會對P型矽基板4照射電漿等而造成損傷。
此外，藉由霧化法之內面鈍化膜5之成膜速度為10至15nm/分鐘，與藉由ALD法等的氧化鋁膜之成膜速度相較，係快5倍以上。因此，藉由採用實施形態1的內面鈍化膜5之成膜方法，可謀求提升生產效率。
再者，實施形態1中，係對內面鈍化膜5及P型矽基板4的界面照射紫外光21而實行光照射處理。
第4圖係表示實施形態1之上述光照射處理所致之效果的圖表。於同一圖中，係表示測定內面鈍化膜5之成膜後(光照射(處理)前)之生命週期值，之後， 照射具有365nm波長之紫外光2130秒鐘而進行光照射處理，再測定生命週期值之測定結果。第4圖中，係表示將成膜後(光照射前)之生命週期值設為正規化值“1”時之實效生命週期值。
如第4圖所示，可知光照射後之實效生命週期值上昇至“2.3”左右。如所述，可知以實施形態1之太陽電池之製造方法製造之內面鈍化膜5的鈍化效果(抑制生命週期減少之功能)係經大幅提升。
如上所述，實施形態1之太陽電池之製造方法，係藉由將經霧化之鋁(材料)溶液14對P型矽基板4的內面進行噴霧，成膜包含氧化鋁膜之鈍化膜5，而可形成製造成本低，且不對基板造成損傷，並以高生產效率為內面鈍化膜5。
此外，藉由於內面鈍化膜5之成膜後以紫外光21進行之光照射處理，可於太陽電池之完成階段得到實效生命週期值經大幅提升的膜質佳之鈍化膜5。
而且，藉由使用紫外光21進行光照射處理，可謀求以較短時間(第4圖之例為30秒鐘)的光照射時間提升鈍化膜5之膜質。
又，第4圖所示之例為照射30秒鐘紫外光21之例，而為了謀求確實地提升內面鈍化膜5的實效生命週期值，理想係將光照射時間設定為1秒以上。
<實施形態2>
完成太陽電池時，表面電極1及內面電極6的形成時之煅燒處理一般而言係不可或缺之處理。例如，形成表面電極1及內面電極6時，係在塗佈以金屬作為主成分之電極材料後實行煅燒處理。
實施形態1係敘述不考慮有無上述電極形成時之煅燒處理，而於內面鈍化膜5之成膜後進行光照射處理之方法。亦即，實施形態1大致上是實行以下之程序(1)及(2)的太陽電池之製造方法。
(1)製作P型矽基板4，將含鋁之溶液14進行霧化，在非真空下將經霧化之溶液14對P型矽基板4的內面進行噴霧，藉此於P型矽基板4的內面上形成包含氧化鋁膜之鈍化膜5。
(2)於P型矽基板4及內面鈍化膜5的界面照射紫外光21，實行光照射處理。
然而，在形成構成太陽電池之表面電極1及內面電極6時，上述煅燒處理為實質上不可或缺之處理。亦即，在得到第1圖所示之太陽電池構造之步驟中，包括在P型矽基板4的表面側及內面側形成表面電極1(另一個電極)及內面電極6(一個電極)之步驟，此步驟中，包括以預定之煅燒溫度進行煅燒之煅燒處理。
實施形態2係考慮上述之表面電極1及內面電極6形成時的煅燒處理之影響並進行光照射處理之太陽電池之製造方法，大致上係經由以下的程序(1)、(3)及(2)′實行。
(1)與實施形態1相同，製作P型矽基板4，將含鋁之溶液14霧化，在非真空下將經霧化之溶液14對P型矽基板4的內面進行噴霧，藉此於P型矽基板4的內面上形成包含氧化鋁膜之鈍化膜5。
(3)形成表面電極1及內面電極6而得到第1圖所示之太陽電池構造。此時，係在表面電極1及內面電極6形成時以500℃以上的煅燒溫度實行煅燒處理。
(2)′在上述(3)之煅燒處理後，於P型矽基板4及內面鈍化膜5的界面照射紫外光21，實行光照射處理。
第5圖係表示實施形態2之太陽電池之製造方法所致之效果的圖表。於同一圖中，係測定內面鈍化膜5之成膜後(光照射前)的生命週期值，之後，實行煅燒處理，該煅燒處理為於大氣壓下且煅燒溫度800℃、煅燒時間10秒的熱處理，並測定煅燒(處理)後之生命週期值，之後，與實施形態1相同，照射30秒鐘具有365nm的波長之紫外光21而進行光照射處理，再測定生命週期值。第5圖中係表示將成膜後(光照射前)之生命週期值設為正規化值“1”時之實效生命週期值。
如第5圖所示，可知光照射後之實效生命週期值係上昇至“2.0”左右。亦即，煅燒處理隨後之實效生命週期值雖從“1.0”降低至“0.5”左右，但藉由此後之光照射處理，實效生命週期值係從煅燒處理前之“1.0”被大幅提升至“2.0”。
如所述，實施形態2之太陽電池之製造方法係藉由實行於太陽電池之製造步驟中實質上不可或缺之表面電極1及內面電極6形成用的煅燒處理(程序(3))，使程序(1)所形成之內面鈍化膜5的膜質所表現之實效生命週期值暫時性地降低，但藉由實行之後的程序(2)′之光照射處理，可使內面鈍化膜5之膜質成為較實行程序(2)′之前大幅提升的狀態。
此時，即使在以500℃以上的煅燒溫度之800℃的煅燒溫度實行煅燒處理之狀況下，也可謀求提升內面鈍化膜5的膜質。
<其他>
又，上述實施形態1及實施形態2中，係表示使用紫外光21作為光照射處理所使用之光(預定之光)之例，惟亦可使用其他種類的光。例如，光的光子能量為1.1eV以上(波長1100nm以下)之光，亦即，亦可使用用以實現對P型矽基板4及內面鈍化膜5的界面之光照射，並為P型矽基板4之結晶矽可吸收之光來取代紫外光21。
如所述，作為實施形態1或實施形態2之太陽電池之製造方法的光照射處理，即使採用使用了結晶矽可吸收、光之光子能量係1.1eV以上(波長1100nm以下)的光之光照射處理，亦可謀求內面鈍化膜5之膜質提升。
此外，藉由使用太陽光或是具有AM1.5之近似太陽的光作為實施形態1或實施形態2之太陽電池之製 造方法的光照射處理所使用的光，可謀求以較低價格提升內面鈍化膜5的膜質。
又，實施形態2之太陽電池之製造方法中，將煅燒處理(程序(3))與光照射處理(程序(2)′)之實行順序顛倒時，雖無法期待如實施形態2般大幅提升內面鈍化膜5的膜質，惟與未進行光照射處理之傳統的製造方法相比，可謀求得到提升內面鈍化膜5的膜質之效果，自不待言。
以上雖係就此種發明進行詳細說明，惟上述說明於全部實施型態中係為例示，本發明並不限定為上述說明者。未經例示之無數種變形例，亦非逸脫本發明的範疇之外者。
1‧‧‧表面電極
2‧‧‧表面鈍化膜
3‧‧‧N型矽層
4‧‧‧P型矽基板
5‧‧‧內面鈍化膜
6‧‧‧內面電極

Claims (8)

  1. 一種太陽電池之製造方法，其係具備下述程序：(a)製作具有一個主面及另一個主面之矽基板之步驟；(b)將包含金屬元素的溶液霧化之程序；(c)在非真空下，將經前述霧化之前述溶液對前述矽基板的一個主面進行噴霧，藉此將包含金屬氧化膜之鈍化膜於前述矽基板的一個主面上成膜之程序；(d)使用形成有前述鈍化膜之前述矽基板來製作太陽電池構造之程序；(e)於前述鈍化膜與前述矽基板的界面照射預定之光而進行光照射處理之程序，其中，前述程序(d)係包括：(d-1)於前述矽基板的一個主面側及另一個主面側形成一個電極及另一個電極之程序，前述程序(d-1)係包括以預定之煅燒溫度進行煅燒之煅燒處理；前述程序(e)係於前述程序(d)之後實行。
  2. 如申請專利範圍第1項所述之太陽電池之製造方法，其中，前述金屬元素為鋁，前述金屬氧化膜為氧化鋁。
  3. 如申請專利範圍第1項所述之太陽電池之製造方法，其中，前述矽基板係構成材料的結晶矽具有P型導電性之矽基板。
  4. 如申請專利範圍第1項所述之太陽電池之製造方法，其中，前述程序(e)的前述預定之光係包含光子能量為1.1eV以上之光。
  5. 如申請專利範圍第1項所述之太陽電池之製造方法，其中，前述程序(e)的前述預定之光係包含太陽光或是具有AM1.5之近似太陽的光。
  6. 如申請專利範圍第4項所述之太陽電池之製造方法，其中，前述程序(e)之前述預定的光係包含具有365nm波長之紫外光。
  7. 如申請專利範圍第6項所述之太陽電池之製造方法，其中，前述程序(e)之前述紫外光的照射時間係1秒以上。
  8. 如申請專利範圍第1項所述之太陽電池之製造方法，其中，前述步驟(d-1)中之前述預定之煅燒溫度係500℃以上。
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