TWI416751B - 矽之表面處理 - Google Patents
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- TWI416751B TWI416751B TW099114777A TW99114777A TWI416751B TW I416751 B TWI416751 B TW I416751B TW 099114777 A TW099114777 A TW 099114777A TW 99114777 A TW99114777 A TW 99114777A TW I416751 B TWI416751 B TW I416751B
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- H—ELECTRICITY
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- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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Description
本發明基本上係關於在光阻圖案形成前之抗反射表面處理，例如在矽太陽能電池製造時。
太陽能電池為光伏電池或模組，其係將太陽光直接轉化成電力。光伏(PV)電池係由半導體製造，最常用的是矽。當光線撞擊到電池，它的某些部分在半導體材料內吸收，使得被吸收光線的能量傳遞到半導體，並且產生電流。在PV電池的頂端和底部安置金屬接點，可使電流流出至外部使用。電流和電池的電壓共同決定此太陽電池所可產生的瓦特數。
矽，特別是結晶形態的矽，是一種常用來製造太陽電池的材料。大多數的太陽電池是由結晶矽所製造，摻雜了硼和磷以產生p-型/n-型接面。多晶矽可用於太陽電池製造以降低製造成本，雖然所得之電池無法像單晶矽電池一樣有效率。也可使用沒有結晶結構的非晶矽，同樣是為了降低生產成本。其它可用於製造太陽電池的材料包括砷化鎵、二硒化銅銦和碲化鎘。
矽太陽能電池的典型配置方式如下：
(a)背接點；
(b)P-型Si；
(c)N-型Si；
(d)抗反射塗層；
(e)柵狀接點；
(f)保護玻璃。
由於矽的反射性極強，通常會在電池的頂端施加抗反射塗層以降低反射的損失。保護玻璃板通常是施用於抗反射層之上，以保護電池不與極板接觸。
為了使整體成本儘量降低，較佳係以有效率的方式來製造低及中效率的太陽能電池。因此，這些太陽能電池可以連續的、高產量生產線來製造，使得晶圓的處理程序維持在最少的情況。方法步驟的數目儘量降低，並且方法步驟的選擇須能允許連續加工，而不需要中斷或者是使中斷降到最少。
傳統的太陽能電池可以利用結晶矽晶圓來製造。矽(+4)晶圓剛開始為具有硼(+3)摻雜物的P-型。為了能捕捉更佳的光線，可以氫氧化物或硝酸/氫氟酸使晶圓具有一定的紋理結構，讓光線傾斜地照入矽材。p-n接面係利用氣相沈積藉由磷的擴散而形成，並且，同樣是在真空設備中，施加氮化矽薄膜做為表面保護層。
在矽太陽能電池製造的標準方法中，矽晶圓的正面被塗上一層抗反射的保護層，其通常包括氮化矽。這種氮化矽層可做為雙重目的，其一係使電池吸收光線(非反射)的百分比達到最大，其二則是保護表面，其可避免電子在表面重組，因而提高電池的效率。
在抗反射塗層沈積之後，通常會利用網印方法(screen printing method)，以含玻璃料的銀糊使電池圖案化。為了穿透氮化物保護層並且形成與塊狀矽材的導電性接點，將銀糊予以燃燒。在此同時，在電池的背面也完成了電路，例如以鋁和銀糊，其中銀係用來製造與矽的接點，並且鋁係用來形成背面電場。
例如，如同在美國專利5,698,451號中所述，其完整內容經由引用倂入本文參照，形成矽太陽能電池的典型方法係包括以下步驟：(1)提供一個具有p-n接面的矽基板，並且在其正面有氮化矽層(與接面相鄰)，(2)以含有銀顆粒和玻璃料的糊料或油墨選擇性塗布氮化矽層，使得該塗層在氮化矽上形成選擇的接點圖案，以及(3)將該基板加熱至約750℃以上，其時間足以快速的使得銀/玻璃料塗層穿透氮化矽層，並且在基板的正面形成歐姆接點。
’451專利還揭露了包括以下步驟的方法：(1)提供一個具有p-n接面的矽基板，並且在其正面有氮化矽層，(2)以鋁糊來塗布矽基板的背面，(3)將矽基板加熱，以快速並有效率的使得鋁形成黏著的導電性背面接點，(4)以含有銀顆粒和玻璃料的糊料來塗布氮化矽，使得在氮化矽上形成柵狀電極圖案，以及(5)將該基板加熱至760℃以上，其時間足以使得糊料中的金屬和玻璃料成分穿透氮化矽層，並且形成黏著的導電性正面接點。
目前圖案化矽太陽能電池的方法具有數項明顯的缺點，包括(1)因為網印而造成之接點破損；(2)電池正面被柵極遮蔽所造成電池效率的損失；以及(3)由於銀糊和下方的矽之間的不當電性接觸所造成電池效率的損失，這是因為氮化物溶解不完全和在銀/矽界面在存有其它雜質的緣故。
因此，希望對於目前圖案化太陽能電池的網印方法能夠有所改善。
已有硏究建議以導線形成技術做為網印糊料的替代方案，包括例如光阻的噴墨沈積以及抗反射塗層(ARC)的蝕刻、銀糊的氣溶膠沈積、ARC的雷射剝蝕和微影。之後，可以使用無電鍍和/或電鍍來形成導線。舉例而言，可以用無電鍍鎳的薄層來製造與矽的電性接觸，接著再以銅鍍著一通常為了避免銅毒化矽，鎳的薄層是不可或缺的。
然而，這些替代性的導線形成技術(conductor formation technique)仍需要進一步的改善。
本發明的目的之一係提供一種圖案化矽太陽能電池的改良方法，以在其表面上形成導線。
本發明的另一個目的是提供一種修改抗反射層表面之處理方法，以改善沈積在塗層上之光阻的清晰度。
為此，本發明主要係關於一種在其上具有抗反射層之矽半導體基板上形成光阻圖案的方法，此方法包括步驟：
a)以化學處理組成物來修改抗反射表面的表面能量；
b)將UV抗蝕刻光阻施用於經處理的抗反射表面；以及
c)使抗反射表面接觸濕式化學蝕刻劑組成物，以去除抗反射表面的外露區域。
本發明主要係關於在矽半導體表面上形成光阻圖案，其最終目的係為了導線的形成。在本發明的一個實施實例中，光阻圖案係沈積在已預先塗布抗反射保護層之矽太陽能電池的正面之上。在形成圖案之後，抗反射層的外露區域係藉由濕式化學方法選擇性地蝕刻，並且接著鍍著各種不同的金屬，以形成正面的導線圖案。較佳是在金屬沈積方法之前將光阻自矽表面除去。
本發明主要係關於一種在其上具有抗反射層之太陽能電池矽半導體基板上形成光阻圖案的方法，此方法包括步驟：
a) 使抗反射層與包括含氟界面活性劑的組成物接觸，以修改抗反射層的表面能量；
b) 將抗蝕刻光阻施用於經處理的抗反射層表面，因而產生抗反射層的外露區域和抗反射層的光阻覆蓋區域；
c) 使抗反射層的外露區域與濕式化學蝕刻劑組成物接觸，以去除外露區域的抗反射層；
d) 在外露區域上施加金屬塗層；以及
e) 除去抗蝕刻光阻。
本方法係代表形成正面導線之傳統方法的一種替代方案。在一個實施實例中，藉由非接觸式方法來施用抗蝕刻光阻，例如紫外線(UV)硬化光阻的噴墨沈積。接著將目前已具有UV光阻圖案的矽基板與濕式化學蝕刻劑組成物接觸，以去除抗反射材料的外露區域，並且露出下方的矽。在除去光阻材料並且潔淨矽表面之後，可藉由無電鍍沈積(或是電鍍沈積)鎳、銅、銀和/或其它較佳金屬(包括一或多種此類金屬的組合)的方式，使外露的矽圖案金屬化。為了改善對矽基板的附著力和其電性接觸，也可以對金屬進行熱處理(“燒結”sintering)方法。
接著，外露的基板可以被進一步的金屬化以在其上建立導線圖案。此外，可以將金屬化的導線圖案予以燒結，以改善金屬化導線圖案對矽基板的附著力。
在一個實施實例中，抗反射層的表面係以一種組成物來處理，該組成物可降低抗反射層表面的表面能量。表面能量的降低可提高施用光阻方法的解析度，因而使得光阻影像相對於理論上施加的影像更為精確。本發明人已發現，包括含氟界面活性劑在醇類(如異丙醇)和/或水中之溶液的化學處理組成物將有利於降低抗反射塗層表面的表面能量。此溶液可含有約0.01至約5.0%的含氟界面活性劑以及醇和/或水，並且可以藉由噴塗、浸塗或是浸漬方法來施用。它們可以溶解在水、溶劑(如醇)或其組合物中，其係由所選擇的含氟界面活性劑來決定。
以含氟界面活性劑處理抗反射表面將導致表面的表面能量降低，因而減少光阻材料在沈積期間的展開。減少噴墨沈積樹脂展開將可印刷出更精細的解析度。
適合用於實施本發明之含氟界面活性劑的實例包括全氟烷基磺酸和其鹽類、全氟烷基磷酸鹽、全氟烷基胺、全氟烷基磺酸鹽和全氟烷基氧化物，這些僅為舉例而非限制。這些含氟界面活性劑可以是陽離子、陰離子、非離子或是兩性。以陰離子為含氟界面活性劑為較佳。陰離子含氟界面活性劑包括ZONYLFSO、FSN、FS62、FSA、FSP或FSE，每一項皆來自DuPont。同樣適合的還包括CAPSTONEFS10和FS50。另一種適合的含氟界面活性劑為FLUORADFC-135，其係來自3M。
UV抗蝕刻光阻係依照預設電極圖案的負型來施用，使得之後可在矽基板的外露表面上形成電極圖案。有一種適合的電極圖案是包含連接於匯流排或澆道一端之複數個細窄觸指的柵狀電極。如同前面所討論，希望能藉由非接觸式方法來施用抗蝕刻光阻，如UV噴墨沈積。
一旦施加了UV抗蝕刻光阻，就可使用以氫氟酸或其它含氟物質為基質的濕式蝕刻劑來完成以矽為主的介電材料(例如氮化物、氧化物和氮氧化物)的蝕刻。
在元件成品正面所殘留的氮化矽係做為有效的抗反射塗層。
同時也應瞭解，以下的專利實施範圍係涵蓋本文中所述本發明所有的一般性及特殊性特色，並且本發明範圍的所有陳述之表達文字可在其範疇之內。
Claims (9)
- 一種在其上具有氮化矽抗反射層之矽半導體基板上形成抗蝕刻光阻圖案的方法，此方法包括步驟：a)使抗反射層與包括含氟界面活性劑的組成物接觸，以修改抗反射層的表面能量；b)將抗蝕刻光阻施用於經處理的抗反射層表面，以產生包含抗反射層的外露區域和抗反射層的經抗蝕刻光阻覆蓋區域之抗蝕刻光阻圖案；c)使抗反射層的外露區域與化學蝕刻劑組成物接觸，以去除外露區域的抗反射層；d)除去抗蝕刻光阻；以及e)在外露區域上施加金屬塗層。
- 如申請專利範圍第1項之方法，其中金屬塗層係藉由鍍著方式來施加。
- 如申請專利範圍第2項之方法，其中金屬塗層係藉由無電電鍍或電鍍金屬的方式來產生，該金屬係選自由鎳、銅、銀和一或多種前述金屬的組合所構成之群組。
- 如申請專利範圍第2項之方法，包括燒結金屬塗層的步驟，以改善金屬塗層對矽基板的附著力。
- 如申請專利範圍第1項之方法，其中含氟界面活性劑包括全氟烷基磺酸和其鹽類。
- 如申請專利範圍第5項之方法，其中化學處理組成物包括的含氟界面活性劑大約為0.01至1.0重量%之間。
- 如申請專利範圍第5項之方法，其中含氟界面活性劑係選自由全氟烷基磷酸鹽、全氟烷基胺、全氟烷基氧化物和全氟烷基磺酸鹽所構成之群組。
- 如申請專利範圍第1項之方法，其中抗蝕刻光阻係藉由非接觸式方法施用於基板。
- 如申請專利範圍第1項之方法，其中抗蝕刻光阻係藉由噴墨印刷方式來施用。
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| WO2011014281A1 (en) | 2011-02-03 |
| EP2460178B1 (en) | 2018-10-17 |
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| US7989346B2 (en) | 2011-08-02 |
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| TW201104907A (en) | 2011-02-01 |
| CN102473648A (zh) | 2012-05-23 |
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| CN102473648B (zh) | 2016-05-04 |
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| US20110021023A1 (en) | 2011-01-27 |
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