TWI513014B - 高性能光電元件 - Google Patents

高性能光電元件 Download PDF

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TWI513014B
TWI513014B TW097118368A TW97118368A TWI513014B TW I513014 B TWI513014 B TW I513014B TW 097118368 A TW097118368 A TW 097118368A TW 97118368 A TW97118368 A TW 97118368A TW I513014 B TWI513014 B TW I513014B
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semiconductor substrate
amorphous structure
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Chiung Wei Lin
Yi Liang Chen
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Tatung Co
Univ Tatung
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Description

高性能光電元件
本發明係關於一種光電元件用二極體及應用此二極體之太陽能電池。
太陽能電池(solar cell)可直接將太陽能轉換為電能,在解決目前石化能源所面臨的污染與短缺的問題時,一直是最受矚目的焦點。
太陽能電池主要是透過光伏特效應來產生光電流。光伏特效應一般而言是指光子射到半導體P-N二極體後,產生光電流之後,藉由P-N二極體的二端電極產生輸出電壓。
典型的太陽能電池,是以擴散的方式在P型矽基板上擴散形成N型摻雜層,再於P型矽基板兩側形成前電極與背電極。由於前電極為金屬材料,會遮蔽下方的N型摻雜層,而降低N型摻雜層的光子吸收率以及嚴重影響電池的轉換效率。此外,為能減少入射光的反射,通常在前電極與N型摻雜層之間插入光子吸收窗層,然而,這將使得製程變得更為複雜,且增加成本。
本發明係提供一種新型P-N二極體結構。
本發明的進一步提供一種P-N二極體之光電元件,其可以使用簡單的製程來製作以降低生產成本。
本發明提出一種光電元件用之二極體,其包括P型半導體基板以及N型透明非晶結構氧化半導體層 (Transparent Amorphous Oxide Semiconductor;TAOS)。
依照本發明實施例所述,上述之光電元件用之二極體中,N型透明非晶結構氧化半導體層之材質包含以氧化鋅(ZnO)、氧化鋅與氧化錫混合物(ZnO-SnO2 )或氧化鋅與氧化銦混合物(ZnO-In2 O3 )為主體,並進一步包含其他的元素。其他的元素包含鋁、鎵、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合。
依照本發明實施例所述,上述之光電元件用之二極體,其中P型半導體基板包括P型矽晶圓或P型矽薄膜層或其他P型半導體材料。
本發明進一步提出一種光電元件,其包括P型半導體基板、N型透明非晶結構氧化半導體層以及背電極。N型透明非晶結構氧化半導體層,位於P型半導體基板的一表面上,N型透明非晶結構氧化半導體層與P型半導體基板構成P-N二極體。背電極位於P型半導體基板的另一表面上。
依照本發明實施例所述,上述之光電元件中,N型透明非晶結構氧化半導體層同時做為光子吸收窗層與前電極層。
依照本發明實施例所述,上述之光電元件中,N型透明非晶結構氧化半導體層之材質包括具有氧化鋅(ZnO)、氧化鋅與氧化錫混合物(ZnO-SnO2 )或氧化鋅與氧化銦混合物(ZnO-In2 O3 )為主體,並進一步包含其他的元素。其他的元素包含鋁、鎵、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、 鉿、氮、鈹或其組合。依照本發明實施例所述,上述之光電元件中,N型透明非晶結構氧化半導體層由單一導電型式材料層所構成。
依照本發明實施例所述,上述之光電元件中,N型透明非晶結構氧化半導體層由兩層具有相同導電型式且不同導電度的材料層所構成,其中導電性較低者較靠近P型半導體基板。
依照本發明實施例所述,上述之光電元件中,N型透明非晶結構氧化半導體層是由具有漸變式導電度的材料層所構成,其中導電性較低的部分較靠近P型半導體基板;導電性較高的部分較遠離P型半導體基板。
依照本發明實施例所述,上述之光電元件更包括金屬、透明導電氧化物或其組合所形成之前電極層,位於透明非晶結構氧化半導體層上。
依照本發明實施例所述,上述之光電元件中,用來形成前電極層之金屬材質包括鋁、銀、鉬、鈦、鐵、銅、銀、錳、鈷、鎳、金、鋅、錫、銦、鉻、鉑、鎢、或其合金。
依照本發明實施例所述,上述之光電元件中,用來形成前電極層之透明導電氧化物之材質包括銦錫氧化物、摻氟氧化錫、摻鋁氧化鋅、摻鎵氧化鋅或其組合。
依照本發明實施例所述,上述之光電元件中,P型半導體基板包括P型矽晶圓、P型矽薄膜層或其他P型半導體材料。
依照本發明實施例所述,上述之光電元件中,光電元件為太陽能電池。
本發明之P-N二極體,其可以應用於光電元件中。
本發明之光電元件,其可以使用更為簡單的製程來製作之,並且減少用料,降低生產成本。
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂,下文特舉較佳實施例,並配合所附圖式,作詳細說明如下。
圖1為依照本發明實施例所繪示之光電元件用之二極體的剖示意圖。
請參照圖1,本實施例之二極體100包括P型半導體基板10以及N型透明非晶結構氧化半導體層12。P型半導體基板10可以是晶圓或是薄膜,例如其可以是P型矽晶圓或P型矽薄膜層。P型半導體基板10也可以使用其他的P型半導體材料。N型透明非晶結構氧化半導體層12位於P型半導體基板10上。N型透明非晶結構氧化半導體層12的材質例如是以氧化鋅(ZnO),或以氧化鋅與氧化錫(ZnO-SnO2 )混合物,抑或是以氧化鋅與氧化銦(ZnO-In2 O3 )混合物為主體,並再包含其他的元素。其他元素包含鋁、鎵、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合。
N型透明非晶結構氧化半導體層12之材質的具體實例為摻鋁氧化鋅(ZnO:Al)。N型透明非晶結構氧化半導體 層12的形成方法可以採用物理氣相沉積系統、化學氣相沉積系統、旋轉塗佈法、溶膠凝膠法或濺鍍法來形成之。
上述之二極體可以應用於光電元件中,在以下的實施例以太陽能電池為例來說明其應用。
圖2為依照本發明實施例所繪示之一種太陽能電池的剖面示意圖。
請參照圖2,本實施例之太陽能電池200由P型半導體基板10、背電極14與N型透明非晶結構氧化半導體層12所構成。P型半導體基板10可以是一塊材如晶圓,或是一層薄膜,其材質可以是P型半導體,例如其可以是P型矽晶圓或P型矽薄膜層。P型半導體基板10也可以使用其他的P型半導體材料。背電極14位於P型半導體基板10的一表面上,其材質可以是金屬、透明導電氧化物(TCO)或其組合。金屬例如是鋁、銀、鉬、鈦、鐵、銅、銀、錳、鈷、鎳、金、鋅、錫、銦、鉻、鉑、鎢、或其合金。透明導電氧化物例如是銦錫氧化物、摻氟氧化錫、摻鋁氧化鋅、摻鎵氧化鋅或其組合。
N型透明非晶結構氧化半導體層12位於P型半導體基板10的另一個表面上,其材質例如是以氧化鋅(ZnO),或以氧化鋅與氧化錫(ZnO-SnO2 )混合物,抑或是以氧化鋅與氧化銦(ZnO-In2 O3 )混合物為主體,並再包含其他的元素。其他的元素包含鋁、鎵、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合。N型透明非晶結構氧化半導體層12之材質的具體實例例如是摻鋁氧化鋅(ZnO:Al)。
在此實施例中,N型透明非晶結構氧化半導體層12與P型半導體基板10構成P-N二極體,做為光電轉換層。此外,N型透明非晶結構氧化半導體層12還可同時做為光子吸收窗層與前電極,因此,本實施例之太陽能電池可以不需要再額外形成光子吸收窗層與前電極,因此,光線可以不受前電極的阻擋而直接被N型透明非晶結構氧化半導體層12所吸收與P型半導體基板10之接面處產生光電流。
當然本發明並不以上述實施例為限,還可以做各種的更動或潤飾,涵蓋各種的結構組合。在以下的實施例將詳細說明之。
圖3為依照本發明另一實施例所繪示之一種透明型薄膜太陽能電池的剖面示意圖。
請參照圖3,本實施例之透明型薄膜太陽能電池300由P型半導體基板10、背電極14、N型透明非晶結構氧化半導體層18所構成。P型半導體基板10之材質與背電極14之位置與材質如同上述實施例所述,於此不再贅述。N型透明非晶結構氧化半導體層18位於P型半導體基板10的另一個表面上,為一種本質為N型的材料,其是由兩層具有不同導電性的透明材料層18a、18b所構成。導電性較低的材料層18a較靠近P型半導體基板10;導電性較高材料層18b較遠離P型半導體基板10。
在一實施例中,導電性較低的透明材料層18a的組成成分與導電性較高的透明材料層18b的組成成分相同,而藉由調控各成分的配比來使其具有不同的導電性。N型透 明非晶結構氧化半導體層18的材質例如是以氧化鋅(ZnO),或以氧化鋅與氧化錫(ZnO-SnO2 )混合物,抑或是以氧化鋅與氧化銦混合物(ZnO-In2 O3 )為主體,並再包含其他的元素。其他元素包含鋁、鎵、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合。在一具體實施例中,N型透明非晶結構氧化半導體層18中導電性較高的材料層18b之材質為摻鋁氧化鋅(ZnO:Al),導電性較低的材料層18a之材質也為摻鋁氧化鋅(ZnO:Al),但,導電性較高的材料層18b中的氧含量較低。在另一實施例中,導電性較低的材料層18a的組成成分與導電性較高的材料層18b的組成成分相異。導電性較低的材料層18a的材質可以是具有氧化鋅(ZnO)、氧化鋅與氧化錫(ZnO-SnO2 )混合物或氧化鋅與氧化銦混合物(ZnO-In2 O3 )或氧化鋅合金例如是摻鋁氧化鋅。導電性較高的材料層18b的材質可以是氧化鋅(ZnO)、氧化鋅與氧化錫(ZnO-SnO2 )混合物、或氧化鋅與氧化銦(ZnO-In2 O3 )混合物、或氧化鋅合金例如是摻鋁氧化鋅(ZnO:Al)。在一具體實施例中,N型透明非晶結構氧化半導體層18中導電性較高的材料層18b之材質為摻鋁氧化鋅(ZnO:Al),導電性較低的材料層18a之材質為未摻鋁的氧化鋅(ZnO)。在另一具體實施例中,N型透明非晶結構氧化半導體層18中導電性較高的材料層18b之材質為銦錫氧化物,導電性較低的材料層18a之材質為摻鋁的氧化鋅(ZnO:Al)。
在此實施例中,N型透明非晶結構氧化半導體層18 中導電性較低的材料層18a可與P型半導體基板10構成P-N二極體,做為光電轉換層。N型透明非晶結構氧化半導體層18中導電性較高的材料層18b則可同時做為光子吸收窗層與前電極,因此,本實施例之太陽能電池可以不需要再額外形成光子吸收窗層與前電極,因此,光線可以不受前電極的阻擋而直接被N型透明非晶結構氧化半導體層18所吸收P型半導體基板10接面處產生光電流。
圖4為依照本發明另一實施例所繪示之一種太陽能電池的剖面示意圖。
請參照圖4,本實施例之透明型薄膜太陽能電池400由P型半導體基板10、背電極14、N型透明非晶結構氧化半導體層20所構成。本實施例與圖2實施例之P型半導體基板10之材質與背電極14之位置與材質相似,於此不再贅述。本實施例與圖2實施例最大的差異點在於N型透明非晶結構氧化半導體層20。N型透明非晶結構氧化半導體層20同樣是位於P型半導體基板10的另一個表面上,且同樣是一種本質為N型的材料,但,其是以具有漸變式導電度的材料層所構成。N型透明非晶結構氧化半導體層20中,較靠近P型半導體基板10處的部分,其導電性較低;較遠離P型半導體基板10的部分,其導電性較高。N型透明非晶結構氧化半導體層20可在沈積期間藉由調控各成分的配比來使其具有漸變的導電性。N型透明非晶結構氧化半導體層20的材質可以例如以氧化鋅(ZnO),或以氧化鋅與氧化錫(ZnO-SnO2 )混合物,抑或是以氧化鋅與氧 化銦(ZnO-In2 O3 )混合物為主體,並再包含其他的元素。其他的元素包含鋁、鎵、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合。N型透明非晶結構氧化半導體層12之材質的具體實例,例如是摻鋁氧化鋅(ZnO:Al),且其中的氧原子成分比例自靠近P型半導體基板10處向遠離P型半導體基板10處逐漸遞減。
在此實施例中,N型透明非晶結構氧化半導體層20中,導電性較低的部分可與P型半導體基板10構成P-N二極體,做為光電轉換層。N型透明非晶結構氧化半導體層20中,導電性較高的部分則可同時做為光子吸收窗層與前電極。因此,本實施例之太陽能電池可以不需要再額外形成光子吸收窗層與前電極,使得光線可以不受前電極的阻擋,直接被N型透明非晶結構氧化半導體層20所吸收,而在P型半導體基板10接面處產生光電流。
圖5為依照本發明又一實施例所繪示之一種透明型薄膜太陽能電池的剖面示意圖。
請參照圖5,若不考慮開口率的問題,在實際應用時,也可以在圖1所示結構的N型透明非晶結構氧化半導體層12上再額外形成前電極16。前電極16之材質例如是金屬、透明導電氧化物或其組合。金屬例如是鋁、銀、鉬、鈦、鐵、銅、銀、錳、鈷、鎳、金、鋅、錫、銦、鉻、鉑、鎢、或其合金。透明導電氧化物例如是銦錫氧化物、摻氟氧化錫、摻鋁氧化鋅、摻鎵氧化鋅或其組合。換言之,在此實施例中,透明型薄膜太陽能電池500的N型透明非 晶結構氧化半導體層12可與P型半導體基板10構成P-N二極體,做為光電轉換層,並且可同時做為光子吸收窗層。而前電極與背電極16、14則可使以用傳統的金屬材料或透明導電氧化物來製作之。
在一實驗例中,以摻鋁氧化鋅(ZnO:Al)做為N型透明非晶結構氧化半導體層;以P型矽晶圓做為P型半導體基板所製作之P-N二極體其在照光之後,其二極體的輸出特性曲線如圖6所示。以前述二極體來製作太陽能電池,在照光方面其所輸出之電流與電壓的特性曲線如圖7所示,數據如表1所示。
由圖7的照光輸出特性其電流與電壓量測上顯示:摻鋁氧化鋅(ZnO:Al)太陽能電池擁有一個不錯的光照特性。這也證明此結構摻鋁氧化鋅(ZnO:Al)太陽能電池可以有效的將光導入至P型矽晶圓與摻鋁氧化鋅(ZnO:Al)薄膜接面間,形成一內建電場,以有效產生光電流,(FF=42.03%, Voc=0.22 V,Jsc=2.94×10-4 A/cm2,η=0.34%)。另,由電性量測上證明摻鋁氧化鋅(ZnO:Al)薄膜本身特性屬於為具N型半導體層,且直接將摻鋁氧化鋅(ZnO:Al)薄膜沉積於p型矽晶圓基板上可進一步簡化太陽能電池的製作。此外,以透明摻鋁氧化鋅(ZnO:Al)薄膜,可克服傳統半導體層不透光的缺點,且照光面無電極遮蔽的問題,可以讓更多可見光部分有效的進入PN接面產生更多的光電流。而表1的照光輸出數據顯示以本發明之P-N二極體也可用來製作太陽能電池。
圖8之曲線分別為P型矽晶圓以及P型矽晶圓上沉積一層摻鋁氧化鋅(ZnO:Al)N型透明非晶結構氧化半導體層,藉由分子螢光光譜儀(fluorescence spectrophotometer)進行反射率量測的反射率與波長的關係圖。圖8顯示在短波長部份擁有較低的反射率,其代表ZnO:Al薄膜可以吸收短波長範圍;而可見光範圍內與單獨P型矽晶圓相比,也擁有較低的反射率,此表此可見光範圍也擁有吸收效果。故由圖8可以證明在量測波長範圍內(350 nm~1000 nm)反射率低,表示摻鋁氧化鋅(ZnO:Al)能有效吸收大部份光子,證明其可做為光電轉換層和光子吸收層。
本發明以N型透明非晶結構氧化半導體層來製作P-N二極體,其可以應用於光電元件中,使元件具有足夠的轉換效率。由於N型透明非晶結構氧化半導體層具有足夠的導電性,因此,當應用在太陽能電池時,不僅可以做為P-N二極體的一部份,還可做為光子吸收窗層以及前電極,因 此,可以不需要額外再形成光子吸收窗層以及前電極,故,可以簡化製程,減少用料,降低生產成本。
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
10‧‧‧P型半導體基板
12、18、20‧‧‧N型透明非晶結構氧化半導體層
18a‧‧‧導電性較低的材料層
18b‧‧‧導電性較高的材料層
14、16‧‧‧電極
100‧‧‧二極體
200、300、400、500‧‧‧太陽能電池
圖1為依照本發明實施例所繪示之光電元件用之二極體的剖示意圖。
圖2為依照本發明實施例所繪示之一種透明型太陽能電池的剖面示意圖。
圖3為依照本發明又一實施例所繪示之一種透明型太陽能電池的剖面示意圖。
圖4為依照本發明再一實施例所繪示之一種透明型太陽能電池的剖面示意圖。
圖5為依照本發明另一實施例所繪示之一種透明型太陽能電池的剖面示意圖。
圖6為依據本發明實驗例所製作之二極體其所輸出之電流與電壓的特性曲線。
圖7為依據本發明實驗例所製作之太陽能電池其所輸出之電流與電壓的特性曲線。
圖8依據本發明實驗例所製作之太陽能電池與P型矽晶圓以分子螢光光譜儀量測所取得的反射率與波長的關係圖。
10‧‧‧P型半導體基板
12‧‧‧N型透明非晶結構氧化半導體層
14‧‧‧電極
200‧‧‧太陽能電池

Claims (12)

  1. 一種二極體,包括:一P型半導體基板;以及一N型透明非晶結構氧化半導體層(TAOS),位於該P型半導體基板上,其中該N型透明非晶結構氧化半導體層之材質包括以氧化鋅(ZnO)為主體,並且包含鋁、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合;或者以氧化鋅與氧化錫(ZnO-SnO2 )混合物為主體,並且包含鋁、鎵、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合;或者以氧化鋅與氧化銦(ZnO-In2 O3 )混合物為主體,並且包含鋁、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合。
  2. 如申請專利範圍第1項所述之二極體,其中該P型半導體基板包括P型矽晶圓、P型矽薄膜層或其他P型半導體材料。
  3. 一種光電元件,包括:一P型半導體基板,包括一第一表面與一第二表面;一背電極,位於該P型半導體基板的該第二表面上;以及一N型透明非晶結構氧化半導體層,位於該P型半導體基板的該第一表面上,該N型透明非晶結構氧化半導體層與該P型半導體基板構成一P-N二極體,其中該N型透明非晶結構氧化半導體層之材質包括以氧化鋅(ZnO)為主體,並且包含鋁、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、 氮、鈹或其組合;或者以氧化鋅與氧化錫(ZnO-SnO2 )混合物為主體,並且包含鋁、鎵、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合;或者以氧化鋅與氧化銦(ZnO-In2 O3 )混合物為主體,並且包含鋁、銦、硼、釔、鈧、氟、釩、矽、鍺、鋯、鉿、氮、鈹或其組合。
  4. 如申請專利範圍第3項所述之光電元件,其中該N型透明非晶結構氧化半導體層還同時做為一光子吸收窗層與一前電極層。
  5. 如申請專利範圍第4項所述之光電元件,其中該N型透明非晶結構氧化半導體層由單一導電性材料層所構成。
  6. 如申請專利範圍第4項所述之光電元件,其中該N型透明非晶結構氧化半導體層由兩層具有相同導電形式且不同導電度的材料層所構成,其中導電性較低者較靠近P型半導體基板。
  7. 如申請專利範圍第4項所述之光電元件,其中該N型透明非晶結構氧化半導體層由具有漸變式導電的材料層所構成,其中導電性較低的部分較靠近該P型半導體基板;導電性較高的部分較遠離該P型半導體基板。
  8. 如申請專利範圍第3項所述之光電元件,更包括金屬、透明導電氧化物或其組合所形成之一前電極層,位於該透明非晶結構氧化半導體層上。
  9. 如申請專利範圍第8項所述之光電元件,其中該金屬之材質包括鋁、銀、鉬、鈦、鐵、銅、銀、錳、鈷、鎳、 金、鋅、錫、銦、鉻、鉑、鎢、或其合金。
  10. 如申請專利範圍第8項所述之光電元件,其中該透明導電氧化物之材質包括銦錫氧化物、摻氟氧化錫、摻鋁氧化鋅、摻鎵氧化鋅或其組合。
  11. 如申請專利範圍第3項所述之光電元件,其中該P型半導體基板包括P型矽晶圓、P型矽薄膜層或其他P型半導體材料。
  12. 如申請專利範圍第3項所述之光電元件,其中該光電元件為一太陽能電池。
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