TWI413271B - 太陽能電池之製造方法 - Google Patents

太陽能電池之製造方法 Download PDF

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TWI413271B
TWI413271B TW098144619A TW98144619A TWI413271B TW I413271 B TWI413271 B TW I413271B TW 098144619 A TW098144619 A TW 098144619A TW 98144619 A TW98144619 A TW 98144619A TW I413271 B TWI413271 B TW I413271B
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semiconductor layer
transparent conductive
solar cell
laser
conductive layer
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Jeong Woo Lee
Seong Kee Park
Kyung Jin Shim
Tae Youn Kim
Won Seo Park
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Lg Display Co Ltd
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Description

太陽能電池之製造方法
本發明係關於一種太陽能電池，特別是關於一種能夠改善太陽能電池之電光特性並使太陽能電池之效能最大化的太陽能電池之製造方法。
太陽能電池係為一種可將太陽能轉化為電能的半導體裝置。太陽能電池包含透過將p型半導體與n型半導體相互接觸地接合在一起所形成的接面並且具有二極體之基本結構。
通常，太陽能電池包含一p-n接面半導體層之結構，在此p-n接面半導體層之結構中，一p型半導體層與一n型半導體層係設置於相對的電極之間。
為了太陽能電池之光電能量轉換，電子係不對稱地存在於p-n接面半導體層之結構中。也就是說，在p-n接面半導體層之結構中，n型半導體層具有高電子密度及低電洞密度，而P型半導體層則具有低電子密度及高電洞密度。因此，在熱平衡狀態下，由於p-n接面半導體層中載流子之密度不同所引起的擴散將導致電荷不均衡。於此相應地是，將感生出一電場，並且將不存在更多的載流子之擴散。於此同時，當具有大於帶隙能量之能量的光線照射到p-n接面半導體層上時，接收到能量的電子將從價帶被激發至導帶，並且價帶中將產生電洞，上述帶隙能量係為導帶與價帶之間的能量差。激發至導帶的電子可以自由地運動。如上所述所產生的自由電子及電洞可被稱為過剩載流子，並且此過剩載流子可透過於價帶或導帶中的密度差異而被擴散。這裡，過剩載流子，即，在p型半導體層中激發的電子及n型半導體層中產生的電洞係被稱為少數載流子，而在接合之前p型及n型半導體層中的載流子，即，p型半導體層中的電洞及n型半導體層中的電子係被稱為多數載流子。多數載流子之流動係由於電場之能量壘而被阻塞。但p型半導體層中的少數載流子，如電子可移動至n型半導體層。少數載流子的擴散會導致p-n接面半導體層中的電位降。當p-n接面半導體層連接至外部電路時，由於p-n接面半導體層之兩端會產生電動勢，因此其可作為電池來加以使用。
因此，太陽能電池進一步包含位於p-n接面半導體層之外表面上的透明電極及後部電極。透明電極具有一粗糙表面以使得從外部光源發出的光線能夠有效地提供至p-n接面半導體層。
「第1A圖」至「第1F圖」為習知技術之太陽能電池之製造方法的步驟示意圖。
在「第1A圖」中，透明導電層4係透過在攝氏300至600度的溫度下使用噴鍍設備(附圖中未示出)沈積一透明導電氧化物(TCO)而得以形成於透明絕緣的基板1之幾乎整個表面上。於此同時，透過在高溫下使用噴鍍方法沈積透明導電氧化物係伴有部分結晶過程，並且透明導電層4可隨意地包含微結晶部分以及介於結晶部分之間的非結晶部分。
在「第1B圖」中，凸起及凹陷圖案6係透過將包含有透明導電層4之基板1浸入填充有蝕刻劑之蝕刻槽(附圖中未示出)中或者透過於透明導電層4上噴塗蝕刻劑而形成於透明導電層4之表面上，此蝕刻劑可與透明導電氧化物發生化學反應。這裡，將透明導電層4曝露於蝕刻劑中的時間可以被適當地控制，並使得透明導電層4不會被完全蝕刻。透明導電層4之表面的某些表面係被蝕刻，而透明導電層4之表面的其它部分則不會被蝕刻，藉以於透明導電層4之表面上形成凸起及凹陷圖案6。此外，由於結晶部分與非結晶部分之間的差異，凸起及凹陷圖案6係將更加凸起或者凹陷。
在「第1C圖」中，係透過用雷射器(附圖中未示出)將雷射光束照射至包含有凸起及凹陷圖案6之透明導電層4上藉以對「第1B圖」之透明導電層4進行圖案化加工，且進而在每一單元電池中形成透明電極8。位於一個單元電池中的透明電極8係與下一個單元電池中的一個透明電極間隔一定距離。
在「第1D圖」中，一n型半導體層10係透過沈積具有n型雜質之半導體材料進而形成於包含有透明電極8之基板1的幾乎整個表面之上。隨後，係透過沈積具有p型雜質之半導體材料進而於n型半導體層10上形成p型半導體層15。此n型半導體層10與p型半導體層15係構成p-n接面半導體層20。
在「第1E圖」中，p-n接面半導體層20係透過使用雷射器(附圖中未示出)將雷射光束照射至p-n接面半導體層20上進而被圖案化加工。
在「第1F圖」中，係透過在p-n接面半導體層20之表面上方沈積金屬材料並對其進行圖案化加工，進而於p-n接面半導體層20之上形成後部電極30。至此，一太陽能電池50被加工完成。
然而，在太陽能電池50中，凸起及凹陷圖案6係較小且無規則。
「第2圖」為習知技術之太陽能電池之放大部分的剖視圖。在「第2圖」中，係透過對結晶部分及非結晶部分使用不同的蝕刻速率來蝕刻透明導電層4進而形成凸起及凹陷圖案6，結晶部分及非結晶部分係形成於透明導電材料被沈積之時。這裡，結晶部分係隨意地設置，並且係進行微結晶化過程。因此，凸起及凹陷圖案6非常的小，且凸起及凹陷圖案6之側面斜角相對於基板1來說是不規則的。因此，經過基板1之表面的入射光線不能被有效地散射，且太陽能電池50之效能較低。
因此，鑒於以上的問題，本發明在於提供一種太陽能電池之製造方法，係能夠從實質上克服由於上述習知技術之局限及缺點而導致的一個或多個問題。
本發明之一目的在於提供一種太陽能電池之造方法，係能夠有效地吸收外部光線並使太陽能電池之效能最大化
本發明之其他特徵及優點將在如下的說明書中部分地加以闡述，並且本發明的這些特徵及優點可以透過本發明如下的說明得以部分地理解或者可以從本發明的實踐中得出。本發明的這些和其他優點可以透過本發明所記載的說明書與申請專利範圍以及附圖中所特別指明的結構得以實現和獲得。
為了實現本發明的這些及其它優點且依照本發明之目的，現對本發明作具體化和概括性地描述，本發明之一種太陽能電池之製造方法，係包含以下步驟：透過在室溫下於基板上沈積透明導電氧化物而於基板上形成透明導電層；透過使用第一雷射器將雷射光束照射至透明導電層進而使透明導電層結晶化；選擇性地蝕刻結晶化之透明導電層藉以於結晶化之透明導電層之表面上形成凸起及凹陷圖案；透過圖案化加工具有凸起及凹陷圖案之透明導電層而於單元電池中形成透明電極；於透明電極上形成p-n接面半導體層並圖案化加工此p-n接面半導體層；以及透過於圖案化加工後的p-n接面半導體層上形成金屬材料層並圖案化加工此金屬材料層進而於圖案化加工後的p-n接面半導體層上形成後部電極，此後部電極係與單元電池相對應。
可以理解的是，如上所述的本發明之概括說明和隨後所述的本發明之詳細說明均是具有代表性和解釋性的說明，並且是為了進一步揭示本發明之申請專利範圍。
現在，將結合附圖所示之實例對本發明之一實施例進行詳細描述。
「第3A圖」至「第3G圖」為本發明一典型實施例之太陽能電池之製造方法的步驟示意圖。
在「第3A圖」中，透明導電層104係透過在室溫下使用噴鍍設備(附圖中未示出)沈積透明導電氧化物(TCO)而形成於透明絕緣的基板101之幾乎整個表面之上。透明導電層104具有一平滑表面。透明導電氧化物可包含SnO:X或ZnO:X，其中X係為一種金屬材料，例如：鋰、鎂、鎳、鋁等。基板101可為玻璃基板或塑料基板。
也就是說，在習知技術中，透明導電層係於攝氏300至600度的高溫下形成，以使得透明導電層具有結晶部分與非結晶部分，而在本發明中，透明導電層104係透過噴鍍方法在室溫下形成。這就是為何透明導電層104之表面隨後將被結晶化的原因。
在「第3B圖」中，雷射器190係設置於透明導電層104之上方，並且雷射光束LB係在室溫下被照射至透明導電層104之表面上。透明導電層104將從其表面以預定之厚度被熔化並隨後被固化，且透明導電層104將部分地被結晶化。這裡，雷射器190優選為紅外(IR)雷射器藉以迅速地熔化透明導電材料。雷射器190之雷射光束LB具有1064奈米之波長，並且具有5W至10W之功率及40KHz至60KHz之頻率。如果雷射器190之功率大於10W，那麼雷射光束LB在每單位面積上將具有過強的功率，並且在透明導電層104之表面被結晶化之前，透明導電層104就會被汽化和去除。
如此，具備最佳條件的雷射光束LB將被照射至透明導電層104之表面上，並且透明導電層104之表面將被結晶化藉以形成多個顆粒(附圖中未示出)。這些顆粒可在透明導電層104之整個表面上具有均一的尺寸大小。
在「第3C圖」中，凸起及凹陷圖案106係透過將包含具有結晶化表面的透明導電層104之基板101浸入填充有可與透明導電氧化物發生反應的蝕刻劑之蝕刻槽(附圖中未示出)中，或者透過在透明導電層104之結晶化表面之上噴塗蝕刻劑，進而形成於透明導電層104之表面上。這裡，將透明導電層104曝露於蝕刻劑中的時間將被適當地加以控制，並且透明導電層104係不會被完全蝕刻。透明導電層104之表面的某些部分將被蝕刻，而透明導電層104之表面的其它部分將不會被蝕刻，藉以在透明導電層104之表面上形成凸起及凹陷圖案106。在顆粒之間邊界部分上的蝕刻速率與顆粒上的蝕刻速率不同。對邊界部分的蝕刻要快於對顆粒的蝕刻。蝕刻將以顆粒中心為基礎向著每一顆粒的邊緣逐步進行，並且凸起及凹陷圖案106係幾乎形成於具有均一尺寸的各顆粒中。凸起及凹陷圖案106可具有均一的尺寸大小。
請參考「第4圖」，此圖為本發明之太陽能電池之放大部分的剖視圖，與「第2圖」所示之凸起及凹陷圖案6相比，「第4圖」之凸起及凹陷圖案係較大且尺寸均一。此外，凸起及凹陷圖案106之側面斜角相對於基板101是一致的。因此，能夠有效地防止光線被全反射。進而使光線擴散率增加，且光線吸收率提高。
同時，凸起及凹陷圖案106之高度以及相對於基板101的凸起及凹陷圖案106之側面斜角能夠透過控制將透明導電層104曝露於蝕刻劑中的時間而加以調節。在習知技術中，由於透明導電層在高溫下形成並且包含微結晶部分與非結晶部分，透過蝕刻微結晶部分與非結晶部分形成的凸起及凹陷圖案具有各種不同的尺寸。因此，其很難透過控制蝕刻時間來調整相對於基板的凸起及凹陷圖案之側面斜角。然而，在本發明中，由於透過「第3B圖」之雷射器190被結晶化的顆粒具有均一的尺寸大小，因此其能夠透過控制蝕刻時間來調整相對於基板101的凸起及凹陷圖案106之側面斜角。
在「第3D圖」中，「第3C圖」之透明導電層104係透過使用雷射器(附圖中未示出)將雷射光束照射至包含凸起及凹陷圖案106之透明導電層104進而被部分地去除並被圖案化加工，並且由此在每一單元電池中形成透明電極108。在一個單元電池中的透明電極108係與下一個單元電池中的一個透明電極間隔一定距離。這裡，上述雷射器可為紅外雷射器，且在此情形中，該紅外雷射器可具有12W至20W的功率。當此雷射器之功率小於12W時，更具體地說，小於10W時，透明導電層104可被熔化並被結晶化，並且透明導電層104可不被去除。
在「第3E圖」中，n型半導體層110係透過沈積具有n型雜質之半導體材料而形成於包含透明電極108之基板101的幾乎整個表面之上。隨後，p型半導體層115係透過沈積具有p型雜質之半導體材料而形成於n型半導體層110之上。n型半導體層110與p型半導體層115構成p-n接面半導體層120。於此同時，一本征非晶半導體層，例如，一本征非晶矽層可進一步形成於n型半導體層110與p型半導體層115之間。
在「第3F圖」中，p-n接面半導體層120係透過使用雷射器(附圖中未示出)將雷射光束(附圖中未示出)照射至p-n接面半導體層120進而被圖案化加工。經圖案化加工後的p-n接面半導體層120具有不與透明電極108之端部相重合的端部，並且如參考標號123所示，透明電極108係曝露於相鄰的p-n接面半導體層120之間。也就是說，透明電極108之邊界不與p-n接面半導體層120之邊界相重疊並且不同於p-n接面半導體層120之邊界。用於圖案化加工p-n接面半導體層120之雷射器相比於用以圖案化加工透明導電層104之雷射器，其具有較大的功率。用以圖案化加工p-n接面半導體層120之雷射器的雷射光束可具有190奈米至308奈米之波長。用以圖案化加工p-n接面半導體層120之雷射器可為準分子雷射器或釔鋁石榴石雷射器。具有190奈米至308奈米之波長的準分子雷射器或釔鋁石榴石雷射器之雷射光束，由於透明電極108吸收具有不同波長的雷射光束，因此不會影響透明電極108。
在「第3G圖」中，後部電極130係透過在p-n接面半導體層120之整個表面上方沈積金屬材料並對其進行圖案化加工進而形成於p-n接面半導體層120之上。此金屬材料可為具有較高反射率的鋁或者鋁合金。至此，太陽能電池150得以製造完成。
這裡，所沈積的金屬材料可透過照射雷射光束或者透過執行光刻製程而被圖案化加工，此光刻製程中包含施加光阻劑至一薄膜，將光阻劑曝露於光線中，將曝光後的光阻劑顯影以及蝕刻此薄膜之步驟。
同時，當後部電極130被圖案化加工時，p-n接面半導體層120也被圖案化加工，並且透明電極108將被曝露。後部電極140係如圖中所示被圖案化加工以使得從單元電池中的外部光線所產生的電動勢被串聯。太陽能電池150包含許多單元電池，並且每一單元電池中的電動勢非常的低且不夠用於電子設備。因此，一個單元電池的後部電極130係與下一個單元電池的透明電極108相連接。多個單元電池的電動勢被串聯連接，並且能夠使用相對高的電壓。
在本發明之太陽能電池中，由於透明電極之凸起及凹陷圖案相比於習知技術具有均一的和較大的尺寸，因此能夠有效防止入射光線之全反射，進而能夠使入射到p-n接面半導體層上的光線量最大化。而且，吸收光線之能力也被最大化，且提高了太陽能電池之效能。此外，由於透明電極之結晶化表面，因而透明電極具有改善的透射率及內部和接觸電阻，因此太陽能電池之效能被進一步提高。
雖然本發明以前述之實施例揭露如上，然其並非用以限定本發明。任何熟習相像技藝者，在不脫離本發明之精神和範圍內，所為之更動與潤飾，均屬本發明之專利保護範圍。關於本發明所界定之保護範圍請參考所附之申請專利範圍。
1．．．基板
4．．．透明導電層
6．．．凸起及凹陷圖案
8．．．透明電極
10．．．n型半導體層
15．．．p型半導體層
20．．．p-n接面半導體層
30．．．後部電極
50．．．太陽能電池
101．．．基板
104．．．透明導電層
106．．．凸起及凹陷圖案
108．．．透明電極
110．．．n型半導體層
115．．．p型半導體層
120．．．p-n接面半導體層
130．．．後部電極
150．．．太陽能電池
190．．．雷射器
LB．．．雷射光束
第1A圖至第1F圖為習知技術之太陽能電池之製造方法的步驟示意圖。
第2圖為習知技術之太陽能電池之放大部分的剖視圖。
第3A圖至第3G圖為本發明一典型實施例之太陽能電池之製造方法的步驟示意圖。
第4圖為本發明之太陽能電池之放大部分的剖視圖。
108．．．透明電極
110．．．n型半導體層
115．．．p型半導體層
120．．．p-n接面半導體層
130．．．後部電極
150．．．太陽能電池

Claims (13)

  1. 一種太陽能電池之製造方法，係包含：透過在室溫下於一基板上沈積一透明導電氧化物而於該基板上形成一透明導電層；透過使用一第一雷射器將一雷射光束照射至該透明導電層進而使該透明導電層結晶化；選擇性地蝕刻該結晶化之透明導電層藉以於該結晶化之透明導電層之表面上形成多個凸起及凹陷圖案；透過圖案化加工具有該等凸起及凹陷圖案之該結晶化之透明導電層而於多個單元電池中形成多個透明電極；於該等透明電極上形成一p-n接面半導體層並圖案化加工該p-n接面半導體層；以及透過於圖案化加工後的該p-n接面半導體層上形成一金屬材料層並圖案化加工該金屬材料層進而於圖案化加工後的該p-n接面半導體層上形成多個後部電極，該等後部電極係與該等單元電池相對應。
  2. 如請求項第1項所述之太陽能電池之製造方法，其中該透明導電氧化物包含SnO:X或ZnO:X中的一種，其中X係為一金屬材料。
  3. 如請求項第1項所述之太陽能電池之製造方法，其中該第一雷射器係為一紅外雷射器，該紅外雷射器具有40KHz至60KHz之頻率，5W至10W之功率並且能夠產生一具有1064奈米之波長的雷射光束。
  4. 如請求項第1項所述之太陽能電池之製造方法，其中圖案化加工該結晶化之透明導電層係包含使用一功率大於12W之第二雷射器發射一雷射光束。
  5. 如請求項第4項所述之太陽能電池之製造方法，其中該第二雷射器係為一紅外雷射器。
  6. 如請求項第4項所述之太陽能電池之製造方法，其中圖案化加工該p-n接面半導體層係包含使用一功率大於該第二雷射器之第三雷射器發射一雷射光束。
  7. 如請求項第6項所述之太陽能電池之製造方法，其中該第三雷射器係為準分子雷射器及釔鋁石榴石雷射器中的一種，該第三雷射器係能夠產生一具有190奈米至308奈米之波長的雷射光束。
  8. 如請求項第1項所述之太陽能電池之製造方法，其中圖案化加工該p-n接面半導體層係包含曝露出相鄰的經圖案化加工後的p-n接面半導體層之間的該等透明電極。
  9. 如請求項第8項所述之太陽能電池之製造方法，其中圖案化加工該金屬材料層係包含選擇性地去除經圖案化加工後的p-n接面半導體層並曝露出介於相鄰後部電極之間的該等透明電極。
  10. 如請求項第9項所述之太陽能電池之製造方法，其中位於一個單元電池中的該後部電極係與位於下一個單元電池中的該透明電極相接觸。
  11. 如請求項第1項所述之太陽能電池之製造方法，其中形成該p-n接面半導體層係包含於該等透明電極之上形成一p型半導體層以及於該p型半導體層之上形成一n型半導體層。
  12. 如請求項第11項所述之太陽能電池之製造方法，其中形成該p-n接面半導體層係還包含於該p型半導體層與該n型半導體層之間形成一本征非晶半導體層。
  13. 如請求項第1項所述之太陽能電池之製造方法，其中圖案化加工該金屬材料層係包含發射一雷射光束或者執行一光刻製程，該光刻製程中包含施加光阻劑至一薄膜，將該光阻劑曝露於光線中，將曝光後的光阻劑顯影以及蝕刻該薄膜之步驟。
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