TWI511309B - 具有雙層電池結構之串聯式薄膜矽太陽能電池 - Google Patents
具有雙層電池結構之串聯式薄膜矽太陽能電池 Download PDFInfo
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- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
- H01L31/076—Multiple junction or tandem solar cells
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Description
本發明係關於一種具有雙層電池結構之串聯式薄膜矽太陽能電池。
因其低製造成本衍生的經濟價格,非晶矽(a-Si:H)薄膜太陽能電池已被廣泛的使用,這也導致了對提升其效率之開發的持續進行,且有多種方法已被提出。其中的一個重要方法為,使用疊加的電池以更進一步地提升電池效率。目前使用的串聯式電池具有雙層或三層結構,其中串聯式電池中很重要的一層為i層(i-type layer)。串聯式電池之i層的重要特性是:為吸收不同波長的光,每個電池之i層之光學能隙(optical band gap,Eg
)將不同。一般而言,頂層電池比底層電池具有較大的能隙。舉例來說,非晶矽/非晶鍺化矽(a-Si:H/a-SiGe:H)結構之能隙分別為1.7/1.5 eV,而非晶矽/微晶矽(a-Si:H/μc-Si:H)結構之能隙分別為1.7/1.1 eV。目前對電池結構的開發通常專注在增加太陽能電池電流,進而提升電池效率值。進一步來說,上述之開發也包括了三層電池結構的研發,亦即,非晶矽/非晶鍺化矽/微晶矽(a-Si:H/a-SiGe:H/μc-Si:H)結構和非晶矽/非晶鍺化矽/非晶鍺化矽(a-Si:H/a-SiGe:H/a-SiGe:H)結構的開發。此些三層電池結構中每層之能隙值皆不相同,使串聯式三層電池結構能比雙層電池結構達到更好的效率。
一份對i型非晶氧化矽(a-SiO:H)開發的研究(A. K. Barua et al.,1997)指出其能隙值約在1.8-2.2 eV之間,比非晶矽的能隙值要高。M. Konagai和其研究團隊在2009年發表之單層非晶氧化矽太陽能電池結構可以實現1.04V的工作電壓(electric potential),是目前單層薄膜矽電池所能達到的最高值。根據M. Konagai與其研究團隊在2007年關於溫度對太陽能電池劣化(溫度係數temperature coefficient,TC)的影響的報告,溫度會降低開路電壓(open-circuit voltage,Voc
),進而影響效率,因此非晶矽等具高開路電壓之電池,效率降低的程度會比具低開路電壓結構之電池來得少。這意味著具高開路電壓的電池比具低開路電壓值的電池更適合用在溫度較高的區域。目前對雙層電池的開發中,電池結構可概括成非晶矽/微晶矽(a-Si:H/μc-Si:H,Voc
約為1.40V),非晶矽/非晶鍺化矽(a-Si:H/a-SiGe:H,Voc
約為1.70V)以及非晶矽/非晶矽(a-Si:H/a-Si:H,Voc
約為1.8V)三種。此些結構之優缺點分別為:包括非晶矽的結構容易製造,並且具有約0.9V的高開路電壓,適合當作頂層電池;微晶矽結構具有約0.5V的開路電壓,但可產生高電流,適合作為底層電池;而非晶鍺化矽結構依鍺摻入之比例,具有介於非晶矽與微晶矽之間的開路電壓。泰國的氣候特色為白天充足的陽光與高溫,太陽能電池的工作溫度可達到40-55℃。若將非晶氧化矽(a-SiO:H)列入考慮的話,此結構能比其他結構達到更高開路電壓,且尚未運用於串聯式太陽能電池的開發中。泰國國家技術與科技發展局(NSTDA)的美國專利第7,671,271號揭露一非晶矽/微晶矽結構之串聯式電池,在40-55℃氣候下使用時,由於開路電壓仍然較低(約1.4 eV),效率會大幅地下降。2010年,NSTDA開發一種溫度係數TC為-0.32%/℃,且開路電壓Voc
為1.48eV的非晶氧化矽/微晶矽(a-SiO:H/μc-Si:H)串聯電池結構,此非晶氧化矽/微晶矽結構之溫度係數TC比非晶矽/微晶矽結構高,但因開路電壓低於非晶矽/非晶矽結構,溫度係數亦比非晶矽/非晶矽結構低。
本發明之目的在於製造一種薄膜太陽能電池,此太陽能電池具有非晶氧化矽/非晶矽(a-SiO:H/a-Si:H)結構,此結構位於玻璃基板上,並以i型非晶氧化矽層(i-a-SiO:H layer)做為頂層電池。良好的i型非晶氧化矽層是必須的,以具有高光學能隙(Eg)值或寬帶隙(bandgap)。具寬帶隙之i型非晶氧化矽層通常具有高開路電壓。具高開路電壓的電池比具低開路電壓值的電池更適合用在溫度較高的區域。具有i型非晶氧化矽結構的太陽能電池係使用矽甲烷(SiH4
)、二氧化碳(CO2
)和氫氣(H2
)作為原料,並以電漿輔助化學氣相沉積(plasma enhanced chemical vapor deposition,PECVD)技術製成。二氧化碳氣體係作為摻雜源(doping source),氫氣流速並被精確控制,以完成頂層i型非晶氧化矽層的沉積。
非晶氧化矽/非晶矽串聯式電池,具有下列結構:玻璃/透明導電薄膜/氧化鋅層/p型微晶氧化矽層/緩衝層(非晶氧化矽層)/i型非晶氧化矽層/緩衝層(微晶矽層)/n型微晶氧化矽層/p型微晶矽層/p型微晶氧化矽層/緩衝層(非晶氧化矽層)/i型非晶矽層/n型微晶矽層/氧化鋅層/銀層;此電池之開路電壓可達到1.89 V且效率可達到7.10%。典型的非晶氧化矽/非晶矽太陽能電池之溫度係數TC(與光電轉換效率η有關)比傳統之非晶矽/非晶矽太陽能電池低。此結果清楚的表示,使用於高溫的區域時,非晶氧化矽/非晶矽太陽能電池比非晶矽/非晶矽太陽能電池更具吸引力。
以下提出本發明之一實施例,並配合所附圖式與標號作詳細說明。在不同圖式中相同元件以相同標號表示。然此實施例並非用以限定本發明,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。
在薄膜太陽能電池製程中使用PECVD技術製備一非晶氧化矽薄膜包括下列步驟:
1.裁切兩片10cm*10cm尺寸的乾淨玻璃,以酒精擦拭移除其上灰塵,並風乾。
2.將玻璃放入用以定位基板之基板座(substrate holder)內。在玻璃頂端放置一不鏽鋼板,兩片玻璃係定位於基板座中央。
3.將具有玻璃之基板座送入載鎖室(load lock chamber),抽氣直到載鎖室之內部壓力達到約1*10-3
托耳(Torr)。開啟加熱器加熱玻璃直到溫度達100-130℃,接著將加熱器關閉並將具有玻璃之基板座移出載鎖室。
4.將具有玻璃之基板座送入溫度約為150-190℃之i層塗佈室(coating chamber),兩片玻璃面對電極並與電極平行放置。接著抽氣直到塗佈室之內部壓力達約1*10-6
托耳為止。
5.通入矽甲烷(SiH4
)、氫氣與二氧化碳原料氣體至塗佈室中。矽甲烷與氫氣以固定速率通入;而為找出薄膜生長的最佳值,二氧化碳的通入速率在0.6-20.0sccm(standard cubic centimeter per minute)之間,細節請見下表1。
6.等待基板達到所需溫度以及塗佈室之內部壓力達到約0.5-2托耳之間。
7.經由電極依表一施加所需頻率與功率密度的電磁波,使原料氣體解離,以在玻璃基板上形成一具有非晶氧化矽結構之本質(intrinsic,可簡稱”i”)型薄膜。等待直到薄膜達成所需的厚度為止。
8.關閉電磁波產生器以及停止注入氣體。抽出剩餘的氣體,並將具有玻璃之基板座移出塗佈室。
9.將具有玻璃之基板座移入載鎖室,通入氮氣直至載鎖室之內部壓力達到大氣壓力,然後移開基板座。
10.量測以上述方法在玻璃基板所形成之薄膜的不
同性質(例如吸收度與厚度),以使用這些資料來分析並推出薄膜之光學能隙(optical band gap,Eg
)。
根據製備非晶氧化矽薄膜時調整通入氣體比率的結果,如第1圖所示,調高二氧化碳/矽甲烷的通入比率可得到較高的能隙值。如表2所示,可以預期能隙Eg
的提高應對應地提升電池開路電壓。得到非晶氧化矽薄膜的光學性質後,下一步是將此結果應用在具非晶氧化矽/非晶矽結構之串聯式太陽能電池上。細節與結構說明如下:
製備具非晶氧化矽/非晶矽結構之串聯式太陽能電池的方法包括下列步驟:
1.裁切兩片10cm*10cm尺寸,鍍有透明導電薄膜(Transparent Conductive Oxide,TCO)的玻璃,以酒精擦拭以移除其上之灰塵,並風乾。
2.將鍍有TCO之玻璃放入用以定位基板之基板座內。在玻璃頂端放置一不鏽鋼板。兩片玻璃係定位於基板座中央。鍍有TCO之玻璃連同其附件在下文中以「樣品」稱之。
3.將樣品送入載鎖室,對載鎖室進行抽氣直到載鎖室之內部壓力約為1*10-3
托耳為止。開啟加熱器以加熱玻璃,直到溫度達100-130℃,接著關閉加熱器並將樣品移出載鎖室。
4.將樣品送入氧化鋅濺鍍室(ZnO sputtering
chamber)。等待直至濺鍍形成之膜達到所需厚度。接著關閉氬氣源與電源,並將樣品移出氧化鋅濺鍍室。
5.將樣品送入p層(p-layer)塗佈室,以連續之製程形成一p型微晶氧化矽(p-μc-SiO)薄膜與一緩衝層(buffer layer),其中在形成緩衝層時需通入矽甲烷、氫氣和二氧化碳氣體。接著將樣品移出p層塗佈室。
6.將樣品送入i層塗佈室以形成一i型非晶氧化矽(i-a-SiO:H)薄膜。對塗佈室進行抽氣與加溫直到塗佈室內部壓力達1*10-6
托耳且溫度約達150-190℃。依表1所示之比例通入矽甲烷、氫氣與二氧化碳氣體。等待直到內部壓力變成約0.50-2.00托耳。接著經由電極施加頻率高於13.56MHz,且功率密度約在20-60mW/cm2
之電磁波以解離原料氣體。等待形成之膜達到所需厚度,接著關閉氣體源與電磁波產生器,抽出剩餘氣體並將樣品移出i層塗佈室。
7.將樣品送入n層塗佈室以形成一微晶矽(μc-Si)薄膜與一n型微晶氧化矽(n-μc-SiO)薄膜。過程需通入矽甲烷、氫氣與二氧化碳氣體。完成後將樣品移出n層塗佈室。
8.將樣品送入p層塗佈室,以二氧化碳氣體產生功率密度約10-40mW/cm2
之二氧化碳電漿。
9.以連續之製程分別形成具有微晶矽層(p-μc-Si:H)結構、微晶氧化矽層(p-μc-SiO)結構和緩衝層之p層,
接著將樣品移出p層塗佈室。
10.將樣品送入i層塗佈室以形成一i型非晶矽薄膜(i-a-Si:H)。完成後將樣品移出i層塗佈室。
11.將樣品送入n層塗佈室以形成一n型微晶矽(n-μc-Si)薄膜。完成後將樣品移出n層塗佈室。
12.將樣品送入氧化鋅電極濺鍍室。等待直到濺鍍形成之膜達到所需厚度為止。接著關閉氬氣源與電力,並將樣品移出氧化鋅濺鍍室。
13.將樣品送入銀電極濺鍍室(Ag electrode sputtering chamber),並依鍍上氧化鋅之同樣製程操作。在濺鍍形成之膜達到所需厚度後,將樣品移出銀電極濺鍍室。此步驟完成後製作之太陽能電池應有如第2圖之結構。
14.將樣品移入載鎖室,通入氮氣直至內部壓力達到大氣壓力,接著移出樣品。
15.以波長532nm的雷射切割處理過之樣品至0.73cm2
的尺寸。以符合AM(Air mass)1.5標準光譜、光度100mw/cm2
以及25℃之日光模擬光源(solar simulator)得到效率量測。
串聯式非晶氧化矽/非晶矽電池結構包括:
1)鍍有透明電極之玻璃(第2圖,標號1-2)
2)氧化鋅層(第2圖,標號3)
3)第一p層,具微晶氧化矽結構(第2圖,標號4)
4)第一緩衝層(第2圖,標號5)
5)第一本質(i)層,具非晶氧化矽結構,厚度約在150-500nm之間,能隙值(Eg
value)在1.85-2.2eV之間,暗導電率(dark conductivity)則介於10-12
-10-8
S/cm(第2圖,標號6)
6)第一微晶矽層(第2圖,標號7)
7)第一n層,具微晶氧化矽結構(第2圖,標號8)
8)第二微晶矽層(第2圖,標號9)
9)第二p層,具微晶氧化矽結構(第2圖,標號10)
10)第二緩衝層(第2圖,標號11)
11)第二本質(i)層,具非晶矽結構(第2圖,標號12)
12)第二n層,具微晶矽結構(第2圖,標號13)
13)金屬電極層(第2圖,標號14)
為達成好的效率與高開路電壓,以i型非晶氧化矽層作為頂層電池之串聯式非晶氧化矽/非晶矽太陽能電池之主要部份如下:在氧化鋅層上形成以微晶氧化矽為結構的p層;在頂層電池與底層電池內,以連續之製程形成p層與緩衝層;緩衝層應為非晶氧化矽膜;
為使非晶氧化矽層的能隙值(Eg value)高於非晶矽層,在形成i型非晶氧化矽層之製程中,應依表1之適當的二氧化碳/矽甲烷之比率來使用矽甲烷、氫氣和二氧化碳氣體;鄰近i型非晶氧化矽層的n層應採用微晶氧化矽結構;以及在製造過程中使用之電磁波應採用高頻率(13.56-70.00MHz)範圍,此範圍之電磁波適合形成非晶氧化矽膜。
發明人與其團隊對依本發明之實施方式所述,製得之非晶氧化矽/非晶矽薄膜太陽能電池,量測電池效率(表2),以及對電流密度(Current density)與電壓之關係作圖(J-V Curve,第3圖);表2顯示,當對具有非晶氧化矽/非晶矽結構之太陽能電池與具非晶矽/非晶矽結構之太陽能電池進行比較時,具非晶氧化矽/非晶矽結構之太陽能電池的開路電壓,高於具非晶矽/非晶矽結構之太陽能電池的開路電壓。
於分析在溫度變化於25-75℃之間太陽能電池效率的量測結果之後,如第4圖所示之太陽能電池參數,可以發現溫度於75℃時,非晶氧化矽/非晶矽結構比非晶矽/非晶矽結構效率有更高的效率。
1、2‧‧‧鍍有透明電極之玻璃
3‧‧‧第一氧化鋅層
4‧‧‧第一p層
5‧‧‧第一緩衝層
6‧‧‧第一i層
7‧‧‧第一微晶矽層
8‧‧‧第一n層
9‧‧‧第二微晶矽層
10‧‧‧第二p層
11‧‧‧第二緩衝層
12‧‧‧第二i層
13‧‧‧第二n層
14‧‧‧金屬電極層
第1圖繪示改變二氧化碳/矽甲烷氣體通入比率時,i型非晶氧化矽薄膜之能隙(Eg
)變化。
第2圖繪示串聯式非晶氧化矽/非晶矽太陽能電池之結構。
第3圖繪示具非晶氧化矽/非晶矽結構之太陽能電池之電流密度(Current density)與電壓(Voltage)之間的關係(J-V Curve)。
第4圖繪示非晶氧化矽/非晶矽與非晶矽/非晶矽結構之溫度相關性。
1、2...鍍上透明導電薄膜之玻璃電極
3...第一氧化鋅層
4...第一p層
5...第一緩衝層
6...第一i層
7...第一微晶矽層
8...第一n層
9...第二微晶矽層
10...第二p層
11...第二緩衝層
12...第二i層
13...第二n層
14...金屬電極層
Claims (3)
- 一種具有雙層結構之串聯式薄膜矽太陽能電池,包括:一鍍有透明電極之玻璃;一氧化鋅層;一第一p層,具有微晶氧化矽結構;一第一緩衝層;一第一本質(intrinsic)層,具有非晶氧化矽結構;一第一微晶矽層;一第一n層,具有微晶氧化矽結構;一第二微晶矽層;一第二p層,具有微晶氧化矽結構;一第二緩衝層;一第二本質(intrinsic)層,具有非晶矽結構;一第二n層,具有微晶矽結構;一氧化鋅層或透明導電薄膜(TCO);以及一金屬電極層。
- 如申請專利範圍第1項所述之具有雙層結構之串聯式薄膜矽太陽能電池,其中該第一本質(intrinsic)層的厚度介於150-500nm。
- 一種具非晶氧化矽/非晶矽結構之串聯式太陽能電池,其中該電池具有一本質(intrinsic)層,該i層結構中容納有氧原子,或該i層具有非晶氧化矽結構。
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