TWI629803B - CIGS film and CIGS solar cell using same - Google Patents

CIGS film and CIGS solar cell using same Download PDF

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TWI629803B
TWI629803B TW103103784A TW103103784A TWI629803B TW I629803 B TWI629803 B TW I629803B TW 103103784 A TW103103784 A TW 103103784A TW 103103784 A TW103103784 A TW 103103784A TW I629803 B TWI629803 B TW I629803B
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cigs
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solar cell
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寺地誠喜
西井洸人
渡邊太一
山本祐輔
河村和典
峯元高志
賈卡潘 柴塔那
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日東電工股份有限公司
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Abstract

本發明係提供一種可抑制表面氧化之CIGS膜、及使用該CIGS膜來抑制轉換效率的降低與不均之CIGS太陽電池。作為該CIGS太陽電池的光吸收層使用之CIGS膜係具有：第1區域，其Ga/(In+Ga)比會自該CIGS膜的背面起至預定之第1厚度位置為止隨著變厚而逐漸減少；第2區域，其上述Ga/(In+Ga)比會自該第1區域上起至第1厚度位置為止隨著變厚而逐漸增加；並更於上述第2區域上具有上述Ga/(In+Ga)比會朝表面逐漸減少之第3區域。

Description

CIGS膜及使用其之CIGS太陽電池 發明領域
本發明係有關於一種膜內Ga/(In+Ga)比於厚度方向上變化之CIGS膜及使用其作為光吸收層之CIGS太陽電池。
發明背景
非晶矽太陽電池及化合物薄膜太陽電池代表之薄膜型太陽電池，與習知的結晶型矽太陽電池比較下，係可大幅削減材料成本及製造成本。因此，近年來，該等研究開發快速地進行著。其中，以I族、III族、VI族元素作為構成物質之化合物薄膜太陽電池，且為使用由銅(Cu)、銦(In)、鎵(Ga)、硒(Se)合金所構成之CIGS膜作為光吸收層之CIGS太陽電池，因完全不使用矽，且具優異太陽光轉換效率(以下稱為「轉換效率」)，而於薄膜太陽電池中特別受到注目。
上述CIGS太陽電池一般係如圖8所示，為依序積層基板81、背面電極層82、上述CIGS膜83、緩衝層84及透明導電膜85而成者。
所述CIGS太陽電池中之上述CIGS膜(光吸收 層)83的製備方法，則有稱為可獲得高轉換效率之3階段法之方法。該方法係於上述基板81的表面形成上述背面電極層82後，將步驟分成3階段。亦即，於第1階段時，於上述背面電極層82的表面蒸鍍In、Ga、Se，而形成(In,Ga)2Se3膜。接著，於第2階段時，使上述基板81的溫度上升至550℃，並蒸鍍Cu、Se，而形成Cu過多之組成的CIGS膜中間體。該階段中之CIGS膜中間體，其液相Cu(2-x)Se與固相CIGS之2相為共存狀態，故因Cu(2-x)Se而結晶會激烈大粒化。習知已知該Cu(2-x)Se為低電阻，故會對太陽電池特性造成不良影響。因此，於第3階段時，為使上述Cu(2-x)Se降低，進而蒸鍍In、Ga、Se，則CIGS膜83整體會變為僅III族過多的組成。依所述3階段法製得之CIGS膜83，其結晶為大粒徑，且以結晶學來說為高品質的薄膜結晶組織(例如參照專利文獻1)。
由上述所製備出的CIGS膜83，如圖9所示，係呈膜內下述(A)的Ga/(In+Ga)比會自背面(與上述背面電極層82之界面)起至預定厚度位置83a(參照圖8)為止隨著變厚而逐漸減少，且自其上起朝表面逐漸增加之V字狀(雙漸變構造)。將所述構造的CIGS膜83用作光吸收層之CIGS太陽電池(參照圖8)可提升轉換效率。
(A)Ga/(In+Ga)比係其鎵(Ga)的原子數濃度相對於銦(In)的原子數濃度與鎵(Ga)的原子數濃度的和之比。
先行技術文獻 專利文獻
專利文獻1：日本特表平10-513606號公報
發明概要
然而，即便為上述CIGS太陽電池，仍有轉換效率大幅低減、轉換效率嚴重不均者。
因此，本發明人等為究明其原因而積極研究。結果發現，其原因為上述CIGS膜83的表面(與緩衝層84的接觸面)氧化之故。亦即，上述雙漸變構造的CIGS膜83，如上述，因表面側的Ga/(In+Ga)比自預定厚度位置83a起會朝表面逐漸增加，故表面的Ga比率會變高。而其Ga比In更容易氧化，因此上述CIGS膜83的表面曝於空氣(氧)的時間越長，Ga越會氧化。則可知於其Ga氧化的狀態下，於上述CIGS膜83的表面形成緩衝層84、透明導電膜85而製備CIGS太陽電池時，其CIGS太陽電池的轉換效率會大幅降低，而轉換效率的不均亦趨嚴重。
本發明係鑑於所述情事而成者，而以提供可抑制表面氧化之CIGS膜、及使用該CIGS膜來抑制轉換效率的降低與不均之CIGS太陽電池為目的。
為達成上述目，本發明的第1要旨係一種CIGS膜，其係作為CIGS太陽電池之光吸收層者，該CIGS膜具有：第1區域，其下述(A)Ga/(In+Ga)比會自該CIGS膜的背面起至預定厚度為止隨著變厚而逐漸減少；第2區域，係位 於該第1區域上，且其上述Ga/(In+Ga)比會朝著表面側逐漸增加；並且該CIGS膜於上述第2區域上形成有上述Ga/(In+Ga)比朝表面逐漸減少之第3區域；(A)Ga/(In+Ga)比係其鎵(Ga)的原子數濃度相對於銦(In)的原子數濃度與鎵(Ga)的原子數濃度的和之比。
又，本發明的第2要旨係一種依序積層有基板、背面電極、光吸收層、緩衝層及透明導電膜而成之CIGS太陽電池，該CIGS太陽電池中，上述光吸收層係上述CIGS膜，且該CIGS膜的背面係位於上述背面電極側之面。
此外，本發明中，原子數濃度例如可使用能量分散型螢光X射線裝置(堀場製作所公司製，EX-250)或D-SIMS(Dynamic-SIMS)評估裝置(ULVAC-PHI公司製)來測定。
本發明CIGS膜，其表面側所形成之第3區域的Ga/(In+Ga)比係隨著自其下之第2區域上起朝表面逐漸減少，因此易氧化的Ga的比率在表面側呈減少狀態。因此，以該表面側來說，即使曝於空氣(氧)的時間長，亦可抑制氧化。而且，若以該CIGS膜作為光吸收層而使用在CIGS太陽電池的話，該CIGS太陽電池係可抑制轉換效率的降低與不均。
尤其若上述第2區域中Ga/(In+Ga)比的峰值在0.3~0.6的範圍內，且上述第3區域中Ga/(In+Ga)比的減少值在0.02~0.3的範圍內，則將該CIGS膜作為光吸收層而用在 CIGS太陽電池時，可在將其轉換效率維持地較高，且減小其轉換效率的不均之狀態下，抑制CIGS膜表面側的氧化。
又，若上述第3區域的厚度在30~200nm的範圍內的話，可在抑制上述轉換效率的降低及不均並取得平衡的狀態下，使表面側氧化的抑制更加適當化。
而且，本發明CIGS太陽電池係將如上述之本發明CIGS膜用作光吸收層，且其CIGS膜的背面係位於背面電極層側之面。因此，本發明CIGS太陽電池係在抑制了上述CIGS膜表面側的氧化之狀態下，於其表面上積層有緩衝層者，故可有效抑制轉換效率的降低與不均。
1‧‧‧基板
2‧‧‧背面電極層
3‧‧‧CIGS膜
3a‧‧‧第1厚度位置
3b‧‧‧第2厚度位置
4‧‧‧緩衝層
5‧‧‧透明導電膜
31‧‧‧第1區域
31A‧‧‧硒化鎵膜
31B‧‧‧硒化銦膜
31C‧‧‧蒸鍍層
32‧‧‧第2區域
32A‧‧‧硒化鎵膜
32B‧‧‧硒化銦膜
33‧‧‧第3區域
33B‧‧‧硒化銦膜
81‧‧‧基板
82‧‧‧背面電極層
83‧‧‧CIGS膜
83a‧‧‧預定厚度位置
84‧‧‧緩衝層
85‧‧‧透明導電膜
310‧‧‧積層組
320‧‧‧積層組
圖1係示意表示本發明CIGS太陽電池一實施形態之截面圖。
圖2係示意表示本發明CIGS膜一實施形態之厚度方向的Ga/(In+Ga)比的變化之圖表。
圖3(a)~(d)係示意表示上述太陽電池之製法的說明圖。
圖4(a)~(b)係接續圖3之示意表示上述太陽電池之製法的說明圖。
圖5(a)~(b)係接續圖4之示意表示上述太陽電池之製法的說明圖。
圖6(a)~(b)係接續圖5之示意表示上述太陽電池之製法的說明圖。
圖7(a)~(b)係接續圖6之示意表示上述太陽電池之製 法的說明圖。
圖8係示意表示習知CIGS太陽電池之截面圖。
圖9係示意表示習知CIGS膜之厚度方向的Ga/(In+Ga)比的變化之圖表。
用以實施發明之形態
接下來，將以圖示詳細說明本發明之實施形態。
圖1係示意顯示使用本發明CIGS膜之一實施形態作為光吸收層之本發明CIGS太陽電池之一實施形態的截面圖。該實施形態的CIGS太陽電池，係依序積層有基板1、背面電極層2、CIGS膜3、緩衝層4及透明導電膜5者。並且，如圖2所示，上述CIGS膜3的Ga/(In+Ga)比在自位於上述背面電極層2側之上述CIGS膜3的背面起至預定的第1厚度位置3a(參照圖1)為止的第1區域31中，會隨著變厚而逐漸減少，且自該第1區域31上起至預定第2厚度位置3b(參照圖1)為止的第2區域32中，會隨著變厚(朝表面側)而逐漸增加，而自該第2區域32上起至表面為止的第3區域33中，則會隨著變厚(朝表面)而逐漸減少。如所述，本發明的一大特徴係於CIGS膜3的表面側形成易氧化的Ga的比率會減少之第3區域33，並藉此抑制了CIGS膜3表面側之氧化。
上述CIGS太陽電可以下述製法進行製備。
首先，準備上述基板1[參照圖3(a)]。該基板1可用作支持基板者，且為了於之後的加熱步驟中可承受加熱，可使用具有可耐520℃以上之溫度之材料。作為該等材 料例如可舉鈉鈣玻璃(SLG)、SUS、鈦等，其中以作業性的觀點來看，以肥粒鐵系SUS430為佳。
接著，如圖3(a)所示，於上述基板1的表面藉由濺鍍法形成上述背面電極層2。該背面電極層2的形成材料例如可舉鉬、鎢、鉻、鈦等。上述背面電極層2可為單層亦可為多層。而且，該厚度以在100nm~1000nm之範圍內為佳。
接下來，為了於上述背面電極層2的表面形成上述CIGS膜3的第1區域31(參照圖1)，首先，如圖3(b)所示，於上述背面電極層2的表面藉由蒸鍍法形成硒化鎵膜31A後，於硒化鎵膜31A的表面藉由蒸鍍法形成硒化銦膜31B。接著，如圖3(c)所示，與上述同樣地，於該硒化銦膜31B的表面蒸鍍形成硒化鎵膜31A後，在該硒化鎵膜31A的表面蒸鍍形成硒化銦膜31B。反覆進行後，則如圖3(d)所示，而積層一組或多數組(圖為3組)由下層為硒化鎵膜31A與其上層為硒化銦膜31B所構成之積層組310。
此時，如先前所述，為實現所形成之第1區域31的Ga/(In+Ga)比可隨著第1區域31變厚逐漸減少，而設定上述積層組310中硒化鎵膜31A的厚度(Y)與硒化銦膜31B的厚度(X)之膜厚比(Y/X)。在本實施形態中，該設定係使硒化銦膜31B的厚度(X)為固定，使硒化鎵膜31A的厚度(Y)係每反覆積層即會變薄，藉此將上述膜厚比(Y/X)設定為每反覆積層即會變小。上述厚度的設定例如可藉由控制Ga等蒸鍍源的溫度(若提高溫度則會變厚，降低則會變薄)、控制蒸鍍 源的開口徑之尺寸(若擴大開口徑則會變厚，若縮小則變薄)來進行。此外，從使所形成之第1區域31的Ga/(In+Ga)比可更適當化之觀點來看，上述膜厚比(Y/X)宜設最初的積層組310在0.5~1.3之範圍內的值，且最後的積層組310在比其更小之0.2~0.5的範圍內的值。
然後，如圖4(a)所示，積層了最後的積層組310後，為了結晶成長，而於該積層組310上層之硒化銦膜31B的表面蒸鍍Cu與Se，而形成蒸鍍層(硒化銅)31C。依所述，而製備由多數上述積層組310與1層上述蒸鍍層31C所構成之積層體α。於該積層體α之形成步驟中，宜將上述基板1的保持溫度設為251~400℃的範圍內，且設為290~360℃的範圍內更佳。其係因若基板1的保持溫度高於400℃，則於形成上述蒸鍍層31C時，該蒸鍍層31C內容易發生擴散，而於接下來的步驟中無法產生均一的結晶成長，並且自上述多數組的積層組310會發生Se再蒸發，而有使結晶品質降低之傾向。
之後，如圖4(b)所示，於520℃以上將上述積層體α加熱，使結晶成長，而形成上述CIGS膜3的第1區域31。即，藉由上述加熱，上述蒸鍍層(硒化銅)31C會液相化，則其Cu會均勻擴散於上述積層體α整體，而發生結晶成長。因此，所形成之第1區域31會變得比上述積層體α更厚。依所述而形成之上述第1區域31中，Ga/(In+Ga)比係自背面起隨著變厚而逐漸減少(參照圖2)。
接下來，如圖5(a)所示，為了於上述第1區域31 的表面形成上述CIGS膜3的第2區域32(參照圖1)，而於維持上述520℃以上的溫度之狀態下，與上述同樣地[參照圖3(b)~(d)]，於上述第1區域31上積層一組或多數組(圖為2組)由下層為硒化鎵膜32A與其上層為硒化銦膜32B所構成之積層組320。
此時，如先前所述，為了實現所形成之第2區域32的Ga/(In+Ga)比可自上述第1區域31上起朝表面側逐漸增加，而設定上述積層組320中硒化鎵膜32A的厚度(Y)與硒化銦膜32B的厚度(X)之膜厚比(Y/X)。本實施形態中，該設定係使硒化銦膜32B的厚度(X)為固定，使硒化鎵膜32A的厚度(Y)每反覆積層即會變厚，藉此將上述膜厚比(Y/X)設定成每反覆積層即會變大。此外，從可使所形成之第2區域32的Ga/(In+Ga)比更適當化之觀點來看，上述膜厚比(Y/X)宜設最初的積層組320在0.2~0.5的範圍內的值，且設最後的積層組320在比其更大之0.5~1.3的範圍內的值。
該步驟中，如同上述，因係於維持在520℃以上的溫度之狀態下，形成上述硒化鎵膜32A及硒化銦膜32B，故於蒸鍍形成該等各膜32A、32B時，該膜會發生結晶成長。因此，所形成之上述第2區域32會變得比上述各膜32A、32B之合計厚度更厚。依上述，如圖5(b)所示，而形成上述第2區域32。然後，該第2區域32中，Ga/(In+Ga)比係自上述第1區域31上起朝表面側逐漸增加(參照圖2)。由可將所製備的CIGS太陽電池的轉換效率維持地較高，且縮小該轉換效率的不均之觀點來看，該Ga/(In+Ga)比的峰值宜設定在0.3 ~0.6的範圍內。
接下來，如圖6(a)所示，為了於上述第2區域32的表面形成上述CIGS膜3之第3區域33(參照圖1)，而於維持在上述520℃以上的溫度之狀態下，與上述同樣地，於上述第2區域32上蒸鍍形成硒化銦膜33B。而於該步驟中，亦如同上述，因於維持在520℃以上的溫度之狀態下，蒸鍍形成上述硒化銦膜33B，故於蒸鍍形成該硒化銦膜33B時，於該膜33B會發生結晶成長。因此，所形成之上述第3區域33會變得比上述硒化銦膜33B更厚。依上述，如圖6(b)所示，形成上述第3區域33，而形成由上述第1~第3區域31、32、33所構成之CIGS膜3。
於上述第3區域33的形成中，因未形成含鎵之膜，故Ga/(In+Ga)比係自上述第2區域32上起朝CIGS膜3的表面逐漸減少(參照圖2)。從於使所製備之CIGS太陽電池的轉換效率維持地較高，並減少該轉換效率的不均之狀態下，可抑制CIGS膜3表面側的氧化之觀點來看，該Ga/(In+Ga)比的減少值宜設定在0.02~0.3的範圍內。
並且，從在取得上述轉換效率降低及不均之抑制與平衡的狀態下，可更使表面側氧化的抑制適當化之觀點來看，上述第3區域33的厚度宜在30~200nm的範圍內。
而若使上述CIGS膜3之Cu、In、Ga的組成比滿足0.70<Cu/(In+Ga)<0.95(莫耳比)之式，可更阻止上述CIGS膜3內取得過多的Cu(2-x)Se，而可使膜整體呈現Cu有點不夠，故以該方面來說為佳。並且，同族元素之Ga與In的比 宜在0.10<Ga/(In+Ga)<0.40的範圍內。
並且，上述CIGS膜3的厚度宜在1.0~3.0μm的範圍內，又以1.5~2.5μm的範圍為佳。其係因若厚度過薄，則推測會有作為光吸收層使用時光吸收量變少，而使元件的性能降低之傾向，反之，若太厚，則推測會有形成膜時花費的時間增加，而有生產性差之傾向。
接下來，如圖7(a)所示，於上述CIGS膜3的表面形成前述緩衝層4。而作為該緩衝層4，例如可舉由ZnMgO、Zn(O,S)等單層所構成者、由CdS與ZnO之多層所構成者。上述各層可以適當的方法形成，例如上述CdS可藉由化學浴堆積法形成，而上述ZnO可藉由濺鍍法形成。又，上述緩衝層4宜為可與上述CIGS膜3進行pn接合之高電阻的n型半導體。並且，緩衝層4的厚度不論單層或多數層宜設定在30~200nm的範圍內。此外，若重疊多種的層作為緩衝層4使用時，則可更良好地與上述CIGS膜3作pn接合，而當pn接合為非常良好時，則不一定要設置多層。
然後，如圖7(b)所示，於上述緩衝層4的表面藉由濺鍍法等形成前述透明導電膜5。該透明導電膜5可舉氧化銦錫(ITO)、氧化銦鋅(IZO)、氧化鋅鋁(Al：ZnO)等。並且上述透明導電膜5的厚度宜設定在100~300nm的範圍內。
依上述，而製得依序積層有基板1、背面電極層2、CIGS膜3、緩衝層4、透明導電膜5之CIGS太陽電池。
上述CIGS太陽電池之製法中，係於CIGS膜3的表面側形成有易氧化之Ga的比率會減少之第3區域33。因此， 該CIGS膜3為已抑制了表面側氧化者。而且，使用所述CIGS膜3之上述CIGS太陽電池可有效抑制轉換效率的降低與不均。
又，如同上述，因於CIGS膜3的表面側形成有易氧化之Ga的比率會減少之第3區域33，因此於形成該第3區域33後(形成CIGS膜3後)，至於其表面形成緩衝層4為止需要時間等，即便上述第3區域33的表面(CIGS膜3的表面)曝於空氣(氧)的時間長，亦可抑制該表面的氧化。亦即，即便形成上述第3區域33(形成CIGS膜3)後至形成緩衝層4為止的時間長，亦不會對所製造之CIGS太陽電池的轉換效率的降低與不均造成很大的影響。因此，可增加上述CIGS太陽電池生產方法的自由度，且可更將生產管理適當化。
此外，於上述實施形態中，CIGS太陽電池係於基板1、背面電極層2、CIGS膜3、緩衝層4及透明導電膜5依序接觸之狀態下積層而成者，但相接觸之構造層之間，因應需求，亦可於基板1的背面、透明導電膜5的表面形成其他層。
又，於上述實施形態中，在形成CIGS膜3之第1區域31時積層的積層組310、及在形成第2區域32時積層的積層組320，係分別於下層配置了硒化鎵膜31A、32A，且於上層配置了硒化銦膜31B、32B，但該配置亦可顛倒(下層為硒化銦膜31B、32B，且上層為硒化鎵膜31A、32A)。
接下來，將就實施例與習知例一併進行說明。但，本發明並不限定於實施例。
實施例
[實施例1]
<基板的準備，背面電極層的形成>
與上述實施形態同樣地，製出CIGS太陽電池。即，首先準備由鈉鈣玻璃所構成之基板[30mm×30mm×0.55mm(厚度)]，並藉由濺鍍法於其表面形成鉬製的背面電極層(厚度500nm)。
<第1區域的形成>
接著，使用蒸鍍裝置，在將上述基板保持在330℃的狀態下，於上述背面電極層表面形成硒化鎵膜(厚度130nm)。之後，在該硒化鎵膜表面形成硒化銦膜(厚度330nm)。然後，於該硒化銦膜表面蒸鍍Cu、Se，而形成由硒化銅所構成之蒸鍍層(厚度1400nm)。依上述，而製備了由硒化鎵膜及硒化銦膜以及硒化銅(蒸鍍層)所構成之積層體。之後，將該積層體一邊供給微量的Se蒸氣一邊加熱，並將基板保持溫度保持在550℃的狀態5分鐘，使結晶成長，而形成第1區域。
<第2區域的形成>
接下來，於一邊供給微量的Se氣體，一邊將基板保持在550℃的狀態下，與上述同樣地，於上述第1區域的表面形成硒化鎵膜後，於該表面形成硒化銦膜。此時，各膜的厚度係於使基板為330℃時，將硒化鎵膜的厚度形成為30nm，硒化銦膜的厚度形成為80nm。
<第3區域的形成>
接下來，於一邊供給微量的Se氣體，一邊將基板保持在550℃的狀態下，與上述同樣地，於上述第2區域表面蒸鍍形成1層硒化銦膜(厚度10nm)，而形成第3區域。於該第3區域的形成中，因未形成含鎵的膜，因此Ga/(In+Ga)比會自上述第2區域上起朝表面逐漸減少。依上述，而形成由上述第1~第3區域構成之CIGS膜(厚度2.0μm)。
[實施例2]
於上述實施例1之第3區域的形成中，將蒸鍍形成的硒化銦膜的厚度製成20nm。除此之外，與上述實施例1相同。
[實施例3]
於上述實施例1之第3區域的形成中，將蒸鍍形成的硒化銦膜的厚度製成25nm。除此之外，與上述實施例1相同。
[實施例4]
於上述實施例1之第2區域的形成中，於使基板為330℃時，將蒸鍍形成的硒化鎵膜及硒化銦膜的厚度形成成硒化鎵膜的厚度為25nm，硒化銦膜的厚度為85nm。除此之外，與上述實施例1相同。
[習知例]
於上述實施例1中，將CIGS膜藉由習知的3階段法形成，除此之外，與上述實施例1相同地來進行。即，首先，與上述實施例1同樣地，於基板表面形成背面電極層。接著，於使基板的保持溫度在350℃的狀態下，一同蒸鍍In、 Ga、Se，而形成由In、Ga、Se構成之層。接下來，於加熱使基板的保持溫度為550℃之狀態的狀態下，使Cu、Se蒸鍍於該層上，並使結晶成長而製得CIGS膜中間體。並且，對該CIGS膜中間體，於持續供給微量的Se蒸氣，且將基板保持溫度維持在550℃之狀態下，一同蒸鍍In、Ga、Se，而製得CIGS膜(厚度2.0μm)。
<緩衝層，透明電極層的形成>
將上述實施例1~4及習知例的CIGS膜分別製備2個，並就其中1個，於形成上述CIGS膜後，於2小時以內(將CIGS膜曝於空氣中的時間為2小時以內)，於該CIGS膜表面上藉由化學浴堆積法形成CdS層(厚度50nm)後，於該表面上藉由濺鍍法形成ZnO層(厚度70nm)，而形成了由上述CdS層與ZnO層所構成之緩衝層。然後，於該緩衝層表面上藉由濺鍍法形成由ITO所構成之透明電極層(厚度200nm)，而製得CIGS太陽電池。而就剩餘的另1個，則於形成上述CIGS膜後，將該CIGS膜曝於空氣中24小時後，與上述同樣地，於該CIGS膜表面形成緩衝層與透明電極層，而製得CIGS太陽電池。
[轉換效率的測定]
對上述實施例1~4及習知例之CIGS膜形成後，於2小時內形成了緩衝層的CIGS太陽電池、與於24小時後形成了緩衝層的CIGS太陽電池，於表面面積以上的區域照射擬似太陽光(AM1.5)，並藉由太陽模擬光量測系統(Cell Tes ter YSS150，山下電裝公司製)測定轉換效率。將該結果顯 示於下述表1。
[Ga/(In+Ga)比的測定]
就上述實施例1~4及習知例之各CIGS膜，使用Dynamic-SIMS評估裝置(ULVAC-PHI公司製)，測定厚度方向的Ga/(In+Ga)比。並且，下述表1係顯示於第2區域中之Ga/(In+Ga)比的峰值、展現該峰值的部分之CIGS膜表面起的深度(第3區域的厚度)、及於第3區域中之Ga/(In+Ga)比的減少值。
由上述表1結果可知，實施例1~4的CIGS太陽電池比習知例的CIGS太陽電池更具有高轉換效率。並且可知，以實施例1~4來說，相較於習知例，CIGS膜即使長時間曝於空氣中，轉換效率亦不會大幅降低。而其原因可知為實施例1~4的CIGS膜表面比起習知例的CIGS膜表面，即使曝於空氣中亦難被氧化。而其係因實施例1~4的CIGS膜在表面側形成有易氧化的Ga比率少之第3區域，而相對於此，習知例的CIGS膜則未形成該所述的層，因此表面的Ga 比率高。
上述實施例中已表示本發明具體形態，但上述實施例僅為單純例示，並不作為限定解釋。該發明所屬熟知技藝者理當可於本發明範圍內做各種變更。
產業上之可利用性
本發明的CIGS膜可利用於抑制表面氧化的情況，且本發明的CIGS太陽電池可利用於抑制轉換效率的降低與不均的情況。

Claims (3)

  1. 一種CIGS膜，特徵在於係作為CIGS太陽電池的光吸收層使用，且具有第1區域及第2區域，該第1區域之下述Ga/(In+Ga)比會自該CIGS膜的背面起至預定厚度為止隨著變厚而逐漸減少；該第2區域，係位於該第1區域上，且其上述Ga/(In+Ga)比會朝著表面側逐漸增加；並且自上述第2區域上起至表面，形成有上述Ga/(In+Ga)比朝表面逐漸減少之第3區域；上述第2區域的Ga/(In+Ga)比的最大峰值在0.3~0.6範圍內；上述第3區域的Ga/(In+Ga)比從上述最大峰值到在上述表面之值為止的減少值在0.02~0.3範圍內；上述Ga/(In+Ga)比之定義係其鎵(Ga)的原子數濃度對銦(In)的原子數濃度與鎵(Ga)的原子數濃度的和之比。
  2. 如請求項1之CIGS膜，其中上述第3區域的厚度在30~200nm範圍內。
  3. 一種CIGS太陽電池，係依序積層有基板、背面電極、光吸收層、緩衝層及透明導電膜者；該CIGS太陽電池之特徵在於：上述光吸收層係如上述請求項1或2之CIGS膜，且該CIGS膜的背面係位於上述背面電極側之面。
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