TW201428121A - 氧化物燒結體、使用其的濺鍍靶材及氧化物膜、光電轉換元件及其製造方法 - Google Patents

氧化物燒結體、使用其的濺鍍靶材及氧化物膜、光電轉換元件及其製造方法 Download PDF

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TW201428121A
TW201428121A TW102141907A TW102141907A TW201428121A TW 201428121 A TW201428121 A TW 201428121A TW 102141907 A TW102141907 A TW 102141907A TW 102141907 A TW102141907 A TW 102141907A TW 201428121 A TW201428121 A TW 201428121A
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Taiwan
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sintered body
semiconductor layer
film
oxide
type semiconductor
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TW102141907A
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English (en)
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Ryo Akiike
Hideto Kuramochi
Kimiaki Tamano
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Tosoh Corp
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Publication of TW201428121A publication Critical patent/TW201428121A/zh

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Abstract

本發明的目的在於提供一種自化合物薄膜太陽電池的n型半導體層到p型半導體層表面可添加特定元素的濺鍍靶材用氧化物燒結體。本發明的氧化物燒結體是含有鋅、及至少一種電離電位Ip為4.5 eV≦Ip≦8.0 eV且原子半徑d為1.20 Å≦d≦2.50 Å以下的元素X(其中，僅添加Mg的情況除外)的氧化物燒結體，其特徵在於：具有0.0001≦X/(Zn+X)≦0.20的組成比，且燒結密度為95%以上。

Description

氧化物燒結體、使用其濺鍍靶材及氧化物膜
本發明是有關於一種氧化物燒結體、使用其的濺鍍靶材(sputtering target)及氧化物膜。
將CuInSe2膜(以下，有時稱為CIS膜)、或Cu(In,Ga)Se2膜(以下，有時稱為CIGS膜)、Cu(Zn,Sn)S(或Cu(Zn,Sn)Se)(以下，有時稱為CZTS膜)等包含Ib族元素、IIIb族元素及VIb族元素的化合物半p型半導體薄膜用於光吸收層的化合物半導體系的薄膜太陽電池(以下，有時將使用上述例示的化合物半導體薄膜的太陽電池分別稱為CIS太陽電池、CIGS太陽電池、CZTS太陽電池)顯示出高的能量轉換效率，不會因外部環境而使轉換效率劣化，因此受到極大關注。
然而，為了降低發電成本(cost)而必須提高轉換效率。已知對提高轉換效率有效果的方法(approach)之一為控制p型半導體薄膜層與n型半導體層界面的電子狀態。
例如，專利文獻1中提出有一種使用n型半導體層中添加有鹼土金屬元素的膜的薄膜太陽電池。本揭示中，其方法例示 有使用濺鍍法(sputtering method)的方法，但關於該濺鍍法中所使用的濺鍍靶材中所使用的燒結體的物性或製造方法完全未揭示。已知濺鍍法中，濺鍍特性根據用作濺鍍靶材的燒結體的物性而大幅度變化，且會因異常放電或顆粒(particle)的產生而產生對基板的損傷(damage)，其會使如太陽電池般的元件(device)特性顯著劣化，因此必須精密地進行控制。
[現有技術文獻]
[專利文獻]
[專利文獻1]日本專利特開2003-197935號公報
本發明的目的在於提供一種自化合物薄膜太陽電池的n型半導體層到p型半導體層表面可添加特定元素的濺鍍靶材用氧化物燒結體。
鑒於此種背景，本發明者進行努力研究，結果發現，於在p型化合物半導體膜上製成n型半導體膜時，藉由濺鍍而將特定元素添加至n型半導體層中，藉此產生接合狀態得到改善且可提高於光照射時所產生的載子(carrier)壽命等現象，可提高轉換效率，從而完成了本發明。
即，本發明提供一種具有以下特徵的氧化物燒結體、使用其的濺鍍靶材、及氧化物膜。
本發明的實施方式如下所述。
(1)一種氧化物燒結體，其是含有鋅、及至少一種電 離電位(ionization potential)Ip為4.5eV≦Ip≦8.0eV且原子半徑d為1.20Å≦d≦2.50Å以下的元素X(其中，僅添加Mg的情況除外)的氧化物燒結體，其特徵在於：具有0.0001≦X/(Zn+X)≦0.20的組成比，且燒結密度為95%以上。
(2)如(1)所述的氧化物燒結體，其中元素X為選自Li、Mg、Ca、Sc、Ti、Sr、Y、Zr、Nb、La、Ce、Nd、Sm、Eu、Ho、Hf、Ta、W、Bi中的至少一種元素(其中，僅添加Mg的情況除外)。
(3)如(1)或(2)所述的氧化物燒結體，以下述組成含有鋅、Mg、及元素X(X為選自Li、Ca、Sc、Ti、Sr、Y、Zr、Nb、La、Ce、Nd、Sm、Eu、Ho、Hf、Ta、W、Bi中的至少一種元素)，0.0001≦X/(Zn+Mg+X)≦0.01
0.0002≦(Mg+X)/(Zn+Mg+X)≦0.20。
(4)如(1)或(2)所述的氧化物燒結體，以下述組成含有鋅、Mg、及元素X(X為選自Sc、Ti、Y、Zr、Nb、La、Ce、Nd、Sm、Eu、Ho、Hf、Ta、W、Bi中的至少一種元素)，0.0001≦X/(Zn+Mg+X)≦0.01
0.0002≦(Mg+X)/(Zn+Mg+X)≦0.20。
(5)如(1)或(2)所述的氧化物燒結體，以下述組成含有鋅、Mg、及元素X(X為選自La、Ce、Nd、Sm、Eu、Ho中的至少一種元素)，0.0001≦X/(Zn+Mg+X)≦0.01
0.0002≦(Mg+X)/(Zn+Mg+X)≦0.20。
(6)一種濺鍍靶材，其特徵在於：使用如(1)至(5)中任一項所述的燒結體。
(7)一種氧化物薄膜，其特徵在於：其是使用如(6)所述的濺鍍靶材而獲得。
(8)一種光電轉換元件，其特徵在於：其為包括作為p型半導體的光吸收層與n型半導體層的太陽電池，且n型半導體層為如(7)所述的氧化物薄膜。
(9)一種光電轉換元件的製造方法，其是如(8)所述的光電轉換元件的製造方法，其特徵在於：使用如(6)所述的燒結體作為濺鍍靶材而製成n型半導體層。
以下，對本發明的詳情進行說明。本發明是一種含有特 定的添加元素的氧化物燒結體，可適合用於濺鍍靶材。
於本發明中，氧化物燒結體的組成是以0.0001≦X/(Zn+X)≦0.20的組成比(其中，僅添加Mg的情況除外)含有電離電位Ip為4.5eV≦Ip≦8.0eV且原子半徑d為1.20Å≦d≦2.50Å以下的元素X。關於電離電位，可參照美國國立標準技術研究所(National Institute of Standards and Technology，NIST)公布發表的資料庫(database)“中性原子的基態能階和電離能量(Ground levels and ionization energies for the neutral atoms)”的值。
另外，本發明中所謂的原子半徑d是表示獨立、不帶電的狀態的原子的大小、即不受電子的結合狀態影響時的原子的大小，可參照文獻E Clementi,D L Raimondi,W P Reinhardt「化學物理學報(J Chem Phys.)」38(1963),2686.中所記載的值。
作為本發明的氧化物燒結體的組成，元素X的組成比為0.0001≦X/(Zn+X)≦0.20，元素X的組成比較佳為0.10≦X/(Zn+X)≦0.20，元素X的組成比更佳為0.15≦X/(Zn+X)≦0.20。如上所述的組成於將本發明的氧化物燒結體用於n型半導體層時對太陽光顯示出高的透射率，且高電阻及與p型半導體層形成良好的pn接合，故而較佳。
另外，本發明中的元素X較佳為使用Li、Mg、Ca、Sc、Ti、Sr、Y、Zr、Nb、La、Ce、Nd、Sm、Eu、Ho、Hf、Ta、W、Bi(其中，僅添加Mg的情況除外)。該些元素X之中，使用含有 電離電位為5eV≦Ip≦7.5eV且離子(ion)半徑為1.30Å≦d≦2.35Å的元素的本發明而製作的太陽電池顯示出更高的轉換效率的傾向，使用含有電離電位為5.5eV≦Ip≦7.3eV且離子半徑為1.70Å≦d≦2.35Å的元素的本發明而製作的太陽電池顯示出更高的轉換效率的傾向。
另外，更佳為以0.0001≦Mg/(Zn+Mg+X)<0.20的組成比含有Mg，且以0.0001≦X/(Zn+Mg+X)≦0.01的組成比含有選自Li、Mg、Ca、Sc、Ti、Sr、Y、Zr、Nb、La、Ce、Nd、Sm、Eu、Ho、Hf、Ta、W、Bi中的至少一種元素X。上述元素X之中，使用含有電離電位為5eV≦Ip≦7.5eV且離子半徑為1.30Å≦d≦2.35Å的元素的本發明而製作的太陽電池顯示出更高的轉換效率的傾向，使用含有電離電位為5.5eV≦Ip≦7.3eV且離子半徑為1.70Å≦d≦2.35Å的元素的本發明而製作的太陽電池顯示出更高的轉換效率的傾向。滿足該些物性的元素X之中，若使用稀土類元素，則可進一步獲得自太陽光提取的電流的量亦增大的傾向，故而更佳。另外，稀土類元素之中，藉由使用Eu、Nd、Ho可製作轉換效率與所提取的電流的量均高的太陽電池，故而更佳。
在含有Mg的組成的情況下，若元素X的添加量變成為0.01<X/(Zn+Mg+X)，則有對進行製膜而獲得的膜的透射率與電阻造成影響，最終使太陽電池性能的轉換效率惡化。
本發明的特徵在於，燒結體的密度為95%以上。其原因在於，若使用燒結密度低的燒結體作為濺鍍靶材進行n型半導體 層的製膜，則顆粒、結塊(nodule)產生、異常放電頻繁而使穩定的製膜變得困難，此外，亦會產生膜組成的面內分佈的不均、製膜中對太陽電池元件的損傷等，從而導致太陽電池性能的降低。
本發明的氧化物燒結體可適用作濺鍍靶材。可將氧化物燒結體直接用作濺鍍靶材，亦可將氧化物燒結體加工成特定形狀而用作濺鍍靶材。
此時，濺鍍靶材的濺鍍面的表面粗糙度以中心線平均粗糙度(Ra)計較佳為3μm以下，更佳為2μm以下。藉此，於進行n型半導體層的製膜時可進一步抑制異常放電的次數，實現穩定的製膜。中心線平均粗糙度可藉由利用改變了號數的磨石等對氧化物燒結體的濺鍍面進行機械加工的方法、利用噴砂(sand blast)等對氧化物燒結體的濺鍍面進行噴射加工的方法等進行調整。另外，中心線平均粗糙度例如可藉由利用表面性狀測定裝置對測定面進行評價而求出。
使用此種濺鍍靶材而獲得的氧化物薄膜適宜作為太陽電池中的n型半導體層。該n型半導體層具有作為抑制上部電極與下部電極的短路的中間層的作用，因此必須於電性上為高電阻。電阻較佳為1.0E+8Ω/□以上，更佳為1.0E+9Ω/□以上，最佳為1.0E+10Ω/□以上。此外，由於n型半導體層擔負使光透過p型半導體層的窗的作用，故而必須於光學上遍及廣波長而具有高的透射率。具體而言，在玻璃基板上製膜的情況下，較佳為於包含基板的狀態下波長450nm~800nm下的透射率為80%以上，且 800nm~1200nm下的透射率為85%以上。更佳為波長450nm~800nm下的透射率為82%以上且800nm~1200nm下的透射率為88%以上。
此處所謂的透射率是指將透射試樣的光的量除以所入射的光的量所得的值，並以下式定義。
透射率(%)=所透射的光的量/所入射的光的量
氧化物薄膜的製造方法可適當選擇直流(Direct Current，DC)濺鍍法、射頻(Radio Frequency，RF)濺鍍法、交流(Alternating Current，AC)濺鍍法、DC磁控濺鍍法(magnetron sputtering method)、RF磁控濺鍍法、AC磁控濺鍍法、離子束(ion beam)濺鍍法等。尤其就可於大面積均勻且高速地製膜的方面而言，更佳為DC磁控濺鍍法、RF磁控濺鍍法、AC磁控濺鍍法。
製膜時的基板的溫度並無特別限定，在考慮對太陽電池基板的影響的情況下，較佳為儘可能在低溫下進行製膜，尤其更佳為在無加熱下進行。其原因在於，基板溫度的上升會引起構成太陽電池的各種元素的擴散，導致轉換效率的降低。
濺鍍時的環境氣體通常是使用惰性氣體、例如氬氣。視需要亦可使用氧氣、氮氣、氫氣等。
以下對使用上述氧化物薄膜的太陽電池的一例進行說明，但本發明可使用的太陽電池並不限定於此。將太陽電池的剖 面圖示於圖1。該圖的太陽電池包括：基板1，依序積層於基板1上的下部電極膜2、半導體層3(第2半導體層)、n型緩衝層(buffer layer)4a、n型半導體層4b(第1半導體層)、上部電極膜5及抗反射膜6，及形成於上部電極膜5上的提取電極7。即，半導體層4b是配置於較半導體層3更靠光入射側。
基板1可使用例如玻璃、不鏽鋼(stainless)、聚醯亞胺膜等。
下部電極膜2可使用例如包含Mo的金屬膜。
半導體層3(第2半導體層)是作為光吸收層而發揮功能的半導體層，並且為p型半導體層。半導體層3是配置於較半導體層4b更靠背面側。
半導體層3例如可使用包含Ib族元素、IIIb族元素及VIb族元素的化合物半導體層，例如可使用CuInSe2、Cu(In,Ga)Se2、CuInS2、Cu(In,Ga)S2等。此外，半導體層3亦可於半導體層4側的表面具備表面半導體層(以下實施方式中相同)。此處所謂的表面半導體層是為n型半導體層或高電阻(電阻率為104Ωcm以上)的半導體層。高電阻的半導體層例如可列舉CuIn3Se5或Cu(In,Ga)3Se5。
半導體層4b(第1半導體層)是與半導體層3一併形成pn接合的層，並且作為窗層而發揮功能。半導體層4b為n型半導體層。半導體層4b可使用以通式Zn1-aXaO(以0.0001≦X/(Zn+X)≦0.20的組成比含有至少一種電離電位Ip為4.5eV≦Ip≦8.0eV 且原子半徑d為1.20Å≦d≦2.50Å以下的元素X)所表示的氧化物鋅為主成分(含有率為70at%以上)的化合物。
上部電極膜5為透明導電膜，例如可使用ZnO中摻雜(dope)有Al的ZnO：Al、或ZnO中摻雜有Ga的ZnO：Ga、氧化銦錫(Indium Tin Oxide，ITO)。
抗反射膜7是防止入射光於上部電極膜5的界面發生反射的膜，在上部電極膜6為ITO或ZnO：Al、ZnO：Ga的情況下，例如可使用MgF2。
提取電極7可使用例如共蒸鍍NiCr與Au而成的金屬膜。
其次，對太陽電池的製造方法的一例進行說明。首先，藉由例如濺鍍法或蒸鍍法而於基板1上形成下部電極膜2。其後，藉由例如蒸鍍法或濺鍍法而於下部電極膜2上形成半導體層3。其後，藉由例如化學析出法或濺鍍法而於半導體層3上形成n半導體層4b。其後，藉由例如濺鍍法而於n半導體層4b上形成上部電極膜5。其後，藉由例如電子束蒸鍍法而於上部電極膜5上的一部分形成提取電極7。其後，藉由例如蒸鍍法而於上部電極膜5上形成抗反射膜6。如此可形成太陽電池。此外，在半導體層3的表面形成高電阻的n型緩衝層4a的情況下，可利用例如溶液浸漬法、蒸鍍法或氣相擴散法形成。
另外，本發明中的n型半導體層的利用濺鍍的製造方法可適當選擇DC濺鍍法、RF濺鍍法、AC濺鍍法、DC磁控濺鍍法、 RF磁控濺鍍法、AC磁控濺鍍法、離子束濺鍍法等。尤其就可於大面積均勻且高速地成膜的方面而言，更佳為DC磁控濺鍍法、RF磁控濺鍍法、AC磁控濺鍍法。藉由使利用該些濺鍍而生成的高能量粒子擔負製膜功能，可自p型半導體層表面的相對較深的部位形成與n型半導體層的接合。但是，在過度地使用高能量的濺鍍條件的情況下，有時會導致太陽電池特性的惡化。
使用所使用的靶材(target)較佳為含有所需的元素且設為特定組成的一體的靶材的一元濺鍍(單靶濺鍍)。成膜時的基板的溫度並無特別限定，但在考慮對太陽電池基板的影響的情況下，較佳為儘可能在低溫下製膜，尤其更佳為在無加熱下進行。其原因在於，有時基板溫度的上升會引起構成太陽電池的各種元素的擴散，導致轉換效率的降低。濺鍍時的環境氣體通常是使用惰性氣體、例如氬氣。視需要亦可使用氧氣、氮氣、氫氣等。
其次，對本發明的製造方法進行詳細說明。
即，本發明的製造方法是包括如下步驟而成：(1)將鋅化合物的粉末與其以外的化合物粉末以成為特定的原子比的方式混合而調整成形用粉末的步驟；(2)使該成形用粉末成形而製作成形體的步驟；及(3)對該成形體進行煅燒而製作燒結體的步驟。以下，對各個步驟進行詳細說明。
(1)粉末調整步驟
各元素的原料粉末並無特別限定，例如可使用金屬氧化物粉末、金屬氫氧化物粉末、氯化物、硝酸鹽、碳酸鹽等金屬鹽 粉末、金屬烷氧化物等，但若考慮操作性，則較佳為金屬氧化物粉末。此外，本發明中，在使用金屬氧化物粉末以外的原料粉末的情況下，預先在大氣中等氧化性環境下對粉末實施加熱處理等而以金屬氧化物粉末的形式使用，亦可發揮出相同的效果，但由於步驟中包含加熱處理等操作而變得繁雜，故而較佳為使用金屬氧化物粉末作為原料粉末。另外，在金屬氧化物粉末的穩定性差的情況下，尤其在含有Li、Mg、Ca的元素的情況下，若考慮操作性，則更佳為使用碳酸鹽。
以下，以使用金屬氧化物粉末及碳酸鹽粉末作為原料粉末的情況為中心進行說明。關於原料粉末的金屬氧化物粉末的粒徑，微細者的混合狀態的均質性、燒結性優異。因此，通常可較佳地使用一次粒徑為10μm以下的粉末，可尤佳地使用一次粒徑為1μm以下的粉末。鋅以外的其他元素的粉末較佳為使用具有小於氧化鋅粉末的一次粒徑的一次粒徑的氧化物粉末。若氧化鋅粉末的一次粒徑小或為相等時，則有混合狀態的均質性差之虞。
另外，關於平均粒徑，較佳為氧化鋅粉末的平均粒徑大於鋅以外的其他金屬氧化物粉末的平均粒徑。藉此，可將原料粉末均質地混合，從而可獲得包含具有微細的平均粒徑的粒子的本發明的氧化物燒結體。
進而，關於氧化鋅粉末與鋅以外的金屬氧化物或碳酸鹽粉末的布厄特(Brunauer-Emmett-Teller，BET)比表面積，若考慮操作性則較佳為3m2/g~20m2/g，藉此容易獲得本發明的氧化物 燒結體。在BET值小於3m2/g的粉末的情況下，較佳為進行粉碎處理再製成BET值為3m2/g~20m2/g的粉末後使用。另外，亦可使用BET值大於20m2/g的粉末，但由於粉末的體積大，故而為了改善操作性，較佳為預先進行粉末的壓密處理等。藉由為此種粉末特性，可較佳地獲得本發明的氧化物燒結體。
該些粉末的混合方法並無特別限定，可例示使用氧化鋯(zirconia)、氧化鋁(alumina)、尼龍(nylon)樹脂等的球(ball)或珠(beads)的乾式、濕式的介質(media)攪拌型磨機或無介質(medialess)的容器旋轉式混合、機械攪拌式混合等混合方法。具體而言，可列舉：球磨機(ball mill)、珠磨機(beads mill)、磨碎機(attritor)、振動磨機(vibrational mill)、行星研磨機(planetary mill)、噴射磨機(jet mill)、V型混合機、槳式(puddle)混合機、雙軸行星攪拌式混合機等。
另外，與粉末的混合同時進行粉碎，粉碎後的粉末粒徑越微細越好，尤其若利用濕式法進行，則可簡便且較佳地實現混合的均質性、高分散化、微細化，故而進而更佳。此時，在利用濕式法以球磨機或珠磨機、磨碎機、振動磨機、行星研磨機、噴射磨機等進行的情況下，必須將粉碎後的漿料(slurry)乾燥。該乾燥方法並無特別限定，例如可例示：過濾乾燥、流動層乾燥、噴霧乾燥等。
此外，在將氧化物以外的粉末混合的情況下，較佳為於混合後以500℃~1200℃進行預煅燒，並將所獲得的預煅燒粉末粉 碎而使用。藉此，可進一步抑制接下來的成形步驟中進行成形、煅燒時的破裂、缺陷等破損。各原料粉末的純度通常為99%以上，較佳為99.9%以上，更佳為99.99%以上。其原因在於，若純度低，則有因雜質而對使用本發明的氧化物燒結體的濺鍍靶材形成的透明導電膜的特性造成不良影響的情況。
該些原料的調配反應於構成所獲得的氧化物燒結體的元素的原子比，因此以使鋅、元素X的原子比為0.0001≦X/(Zn+X)≦0.20的方式將原料混合。更佳為以0.10≦X/(Zn+X)≦0.20的方式將原料混合，更佳為以0.15≦X/(Zn+X)≦0.20的方式將原料混合。
以此種方式獲得的混合粉末(在進行了預煅燒的情況下為經預煅燒的混合粉末)較佳為於成形前將一次粒徑設為1μm以下，尤佳為進行了預煅燒的情況。更佳為進行造粒。藉此，可提高成形時的流動性，生產性優異。造粒方法並無特別限定，可例示噴霧乾燥造粒、滾動造粒等，通常製成平均粒徑為數μm~1000μm的造粒粉末而使用。
(2)成形步驟
成形方法只要可使金屬氧化物的混合粉末(在進行了預煅燒的情況下為經預煅燒的混合粉末)成形為目標形狀，則並無特別限定。可例示壓製成形法、澆鑄成形法、射出成形法等。成形壓力只要可獲得不產生龜裂(crack)等而可操作的成形體，則並無特別限定，但若於相對較高的成形壓力下、例如壓製成形時 於500kg/cm2~3.0ton/cm2下成形，則本發明的氧化物燒結體中，容易獲得不存在元素X的氧化物粒子的氧化物燒結體，另外，容易獲得燒結密度95%以上的氧化物燒結體。另外，成形密度較佳為儘可能高。因此，亦可使用冷均壓(Cold Isostatic Press，CIP)成形等方法。此外，於進行成形處理時，亦可使用聚乙烯醇、丙烯酸系聚合物、甲基纖維素、蠟類、油酸等成形助劑。
(3)煅燒步驟
其次，將所獲得的成形體於1050℃~1500℃下進行煅燒。藉由在該溫度範圍內進行煅燒，可獲得包含具有微細的平均粒徑的粒子的氧化物燒結體。尤其就抑制氧化鋅特有的揮發消失且提高燒結密度的方面而言，煅燒溫度更佳為1050℃~1450℃的範圍。另外，若將煅燒溫度設為1200℃~1450℃，則容易獲得不存在元素X的氧化物鹽粒子的氧化物燒結體，另外，容易獲得燒結密度95%以上的氧化物燒結體。
另外，在成形時使用成形助劑的情況下，就防止加熱時的破裂等破損的觀點而言，較佳為於煅燒前附加脫脂步驟。
根據本發明，藉由以如上所述的方式控制構成氧化物燒結體的粒子的平均粒徑，可獲得高的燒結密度，於用作靶材時可顯著抑制濺鍍中的異常放電現象。
煅燒時間並無特別限定，雖亦取決於與煅燒溫度的均衡，但通常為1小時~48小時。較佳為3小時~24小時。其是為了確保本發明的氧化物燒結體中的均質性，藉由長於24小時的時 間的保持亦可確保均質性，但若考慮對生產性的影響，則24小時以下即充分。進一步而言，為了獲得包含具有微細的平均粒徑的粒子的氧化物燒結體，尤佳為3小時~10小時。
升溫速度並無特別限定，更佳為於800℃以上的溫度區域內為200℃/h以下。其是為了確保本發明的氧化物燒結體中的均質性。
煅燒環境並無特別限定，例如可適當選擇大氣中、氧氣中、惰性氣體環境中等。另外，煅燒時的壓力亦無特別限定，除常壓以外亦可於加壓狀態、減壓狀態下進行煅燒。亦可利用熱均壓(Hot Isostatic Press，HIP)法進行煅燒。
此外，亦可同時進行(2)成形步驟與(3)煅燒步驟。即，亦可藉由如下方法而製作：將粉末調整步驟中所調整的粉末填充至成形用模具中並進行煅燒的熱壓法；或使該粉末於高溫下熔融並進行噴射而成為特定形狀的方法等。
本發明的太陽電池中，構成n型半導體層的膜為含有至少一種電離電位Ip為4.5eV≦Ip≦8.0eV且原子半徑d為1.20Å≦d≦2.50Å以下的元素的氧化物薄膜。藉由使用本發明的燒結密度95%以上的濺鍍靶材製成該膜，可製作與p型半導體層形成良好的pn接合的n型半導體層，可提高太陽電池的轉換效率。
1‧‧‧基板
2‧‧‧下部電極膜
3‧‧‧p型半導體層
4a‧‧‧n型緩衝層
4b‧‧‧n型半導體層
5‧‧‧上部電極膜
6‧‧‧抗反射膜層
7‧‧‧提取電極
圖1是所較佳地利用的本發明的太陽電池的主要部分剖面圖。
圖2是本發明的實施例中所製作的太陽電池的主要部分剖面圖。
[實施例]
藉由實施例與比較例具體地說明本發明，但本發明並不限定於此。
(太陽電池的製作與評價方法)
首先，於鈉鈣(soda lime)玻璃1上藉由濺鍍將Mo積層400nm而製作下部電極2。p型半導體層3是藉由濺鍍法形成CuGa/In/Se前驅物(precursor)後，將CuGa/In/Se前驅物加熱至約450℃~550℃，藉由固相擴散而形成Cu(Ga,In)Se2膜。其次，於上述CIGS表面藉由濺鍍靶材製成n型半導體層4。繼而，藉由磁控濺鍍法形成表面電極層5的氧化銦錫(Indium Tin Oxide，ITO)透明導電膜，製成抗反射膜MgF2之後，共蒸鍍NiCr與Au而用於提取電極7。
測定利用太陽模擬器(Solar Simulator)對所獲得的太陽電池照射AM1.5(100mW/cm2)的光時的電流-電壓特性，對短路電流、開路電壓、曲線因子、及光電轉換效率進行評價，並進行相對比較。
此處，於光照射時，將使兩電極短路時的電流稱為短路電流，將使兩電極開路時的輸出電壓稱為開路電壓，將以有效受 光面積除短路電流所得者稱為短路電流密度。短路電流與開路電壓的積為該太陽電池中理想地提取的電力值，表示實際上可提取的電力相對於該值的比的是曲線因子(填充因子(fill-factor，FF))。因此，短路電流、開路電壓、曲線因子、轉換效率的值較大者於太陽電池中具有優異的特性。
將所獲得的膜的物性示於表2，將比較例1中所獲得的值設為1.00，將所製作的太陽電池特性的結果換算為相對值而示於表3。
(原料粉末)
所使用的原料粉末的物性如表1所示。
此外，原料粉末是以如下方式進行評價。
(BET比表面積)
使用MONOSORB(美國康塔(QUANTACHROME)公司製造)，藉由BET式一點法而測定。
(粉末的平均粒徑)
使用COULTER LS130(庫爾特電子(COULTER ELECTRONICS)公司製造)，於蒸餾水中利用液體模組(module)進行測定。測定值為體積基準。
(實施例1)
以使鋅、鈣的原子數的比成為表2中所記載的值的方式，利用濕式珠磨機將氧化鋅粉末、氧化鎂粉末混合、粉碎並乾燥後，填充至直徑150mm的模具中，以300kg/cm2進行單軸成形，繼而以3.0ton/cm2進行CIP成形。將所獲得的成形體於升溫速度50℃/h、降溫速度100℃/h、煅燒溫度1200℃、保持時間3小時、氮氣中的條件下進行煅燒而獲得氧化物燒結體。
(實施例2~實施例16、比較例1~比較例6)
以燒結體的組成成為表2中所記載的值的方式變更所使用的粉末，除此以外，以與實施例1相同的方式獲得氧化物燒結體。此外，僅於比較例2中將煅燒溫度變更為1000℃。
．燒結體、濺鍍靶材的特性
(燒結體的密度)
將所製作的燒結體於水中煮沸之後，利用阿基米德(Archimedes)法進行燒結密度的測定。
(濺鍍靶材的製造方法)
將所製作的燒結體加工成特定形狀而用作濺鍍靶材。成為靶材的濺鍍面的面是使用平面研磨盤與鑽石(diamond)研磨粒的磨石進行加工。
．製膜方法、氧化物膜的特性
(利用濺鍍靶材的濺鍍條件)
．裝置：RF磁控濺鍍裝置(愛發科(ULVAC)公司製造)
．磁場強度：1000高斯(Gauss)(靶材正上方，水平成分)
．基板溫度：室溫
．極限真空度：5×10-5Pa
．濺鍍氣體：氬氣
．濺鍍氣壓：1.0Pa
．DC功率(power)：25W/4英吋φ
．膜厚：80nm
膜的組成、電阻及光學特性是使用於與上述相同的製膜條件下在玻璃基板上製膜而成的試樣並利用以下方法進行測定。
(薄膜的組成)
使用ICP發射分光光度分析裝置(emission spectro-photometric analyzers)(精工電子(Seiko Instruments)公司製造)，藉由ICP發射分光光度分析法進行定量。
(薄膜的電阻)
薄膜的電阻是使用Hiresta UP MCP-HT450型(三菱化學分析技術(Mitsubishi Chemical Analytech)公司製造)進行測定。
(薄膜的透射率)
利用分光光度計U-4100(日立製作所製造)測定包括基板在內的透光率，將波長400nm至800nm的透射率的平均值設為可見光區域的透射率，將波長800nm至1200nm的透射率的平均值設為紅外區域的透射率。透射率是以下式定義。
透射率(%)=所透射的光的量/所入射的光的量
根據以上結果可知，本發明的燒結體於太陽電池製作時適宜作為用以製造n型半導體層的濺鍍靶材，所獲得的太陽電池與先前的太陽電池相比，可獲得高的轉換效率。
[產業上之可利用性]
藉由本發明，可提高化合物薄膜太陽電池的轉換效率，可增加可利用的能量的量。
1‧‧‧基板
2‧‧‧下部電極膜
3‧‧‧p型半導體層
4a‧‧‧n型緩衝層
4b‧‧‧n型半導體層
5‧‧‧上部電極膜
6‧‧‧抗反射膜層
7‧‧‧提取電極

Claims (9)

  1. 一種氧化物燒結體，其是含有鋅、及至少一種電離電位Ip為4.5eV≦Ip≦8.0eV且原子半徑d為1.20Å≦d≦2.50Å以下的元素X(其中，僅添加Mg的情況除外)的氧化物燒結體，其特徵在於：具有0.0001≦X/(Zn+X)≦0.20的組成比，且燒結密度為95%以上。
  2. 如申請專利範圍第1項所述的氧化物燒結體，其中元素X為選自Li、Mg、Ca、Sc、Ti、Sr、Y、Zr、Nb、La、Ce、Nd、Sm、Eu、Ho、Hf、Ta、W、Bi中的至少一種元素(其中，僅添加Mg的情況除外)。
  3. 如申請專利範圍第1項或第2項所述的氧化物燒結體，以下述組成含有鋅、Mg、及元素X(X為選自Li、Ca、Sc、Ti、Sr、Y、Zr、Nb、La、Ce、Nd、Sm、Eu、Ho、Hf、Ta、W、Bi中的至少一種元素)，0.0001≦X/(Zn+Mg+X)≦0.01 0.0002≦(Mg+X)/(Zn+Mg+X)≦0.20。
  4. 如申請專利範圍第1項或第2項所述的氧化物燒結體，以下述組成含有鋅、Mg、及元素X(X為選自Sc、Ti、Y、Zr、Nb、La、Ce、Nd、Sm、Eu、Ho、Hf、Ta、W、Bi中的至少一種元素)，0.0001≦X/(Zn+Mg+X)≦0.01 0.0002≦(Mg+X)/(Zn+Mg+X)≦0.20。
  5. 如申請專利範圍第1項或第2項所述的氧化物燒結體，以 下述組成含有鋅、Mg、及元素X(X為選自La、Ce、Nd、Sm、Eu、Ho中的至少一種元素)，0.0001≦X/(Zn+Mg+X)≦0.01 0.0002≦(Mg+X)/(Zn+Mg+X)≦0.20。
  6. 一種濺鍍靶材，其特徵在於：使用如申請專利範圍第1項至第5項中任一項所述的氧化物燒結體。
  7. 一種氧化物薄膜，其特徵在於：其是使用如申請專利範圍第6項所述的濺鍍靶材而獲得。
  8. 一種光電轉換元件，其特徵在於：其為包括作為p型半導體的光吸收層與n型半導體層的太陽電池，且n型半導體層為如申請專利範圍第7項所述的氧化物薄膜。
  9. 一種光電轉換元件的製造方法，其是如申請專利範圍第8項所述的光電轉換元件的製造方法，其特徵在於：使用如申請專利範圍第6項所述的氧化物燒結體作為濺鍍靶材而製成n型半導體層。
TW102141907A 2012-11-19 2013-11-18 氧化物燒結體、使用其的濺鍍靶材及氧化物膜、光電轉換元件及其製造方法 TW201428121A (zh)

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