TWI642820B - N型多晶矽晶體及其製造方法與n型多晶矽晶片 - Google Patents
N型多晶矽晶體及其製造方法與n型多晶矽晶片 Download PDFInfo
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 146
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920005591 polysilicon Polymers 0.000 title 2
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- 235000012431 wafers Nutrition 0.000 claims description 56
- 239000002019 doping agent Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 32
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052733 gallium Inorganic materials 0.000 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- 239000002210 silicon-based material Substances 0.000 claims description 23
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- 239000002699 waste material Substances 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
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- 239000001301 oxygen Substances 0.000 claims description 12
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 239000010439 graphite Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/04—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their crystalline structure, e.g. polycrystalline, cubic or particular orientation of crystalline planes
- H01L29/045—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their crystalline structure, e.g. polycrystalline, cubic or particular orientation of crystalline planes by their particular orientation of crystalline planes
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Abstract
本發明提供一種N型多晶矽晶體及其製造方法與N型多晶矽晶片。所述N型多晶矽晶體具有一電阻率斜率與一缺陷面積佔比之斜率。在座標橫軸單位為固化分率以及座標縱軸單位為歐姆·公分(Ω·cm)時,在固化分率為0.25~0.8的電阻率斜率為0至-1.8。在座標橫軸單位為固化分率以及座標縱軸單位為缺陷面積佔比(%)時,在固化分率為0.4~0.8的所述缺陷面積佔比之斜率小於2.5。
Description
本發明是有關於一種N型多晶矽長晶技術,且特別是有關於一種N型多晶矽晶體及其製造方法與N型多晶矽晶片。
太陽能電池是一種藉由吸收太陽光並利用光伏效應進行光電轉換以產生電能的光電元件。目前太陽能電池的材料大部份都是以矽材為主,如單晶矽、多晶矽或非晶矽。
以多晶矽做為太陽能電池的原材,在成本上比現有的拉晶法(CZ method)以及浮動區域法(FZ method)所製造的單晶矽相對地便宜許多。
一般多晶矽長晶是以鑄造為主,且應用於太陽能電池的多屬P型多晶矽。但是,P型多晶矽因轉換效率較低,難與單晶匹敵並維持多晶的市場佔有率,因此亟需開發轉換效率明顯較高的N型多晶矽。
然而,目前的N型多晶矽晶碇電阻分佈較廣泛,導致生產良率低的問題。
本發明提供一種N型多晶矽晶體,其電阻分佈均勻且晶體品質優良。
本發明另提供一種N型多晶矽晶片,具有較長的少數載子壽命。
本發明再提供一種N型多晶矽晶體的製造方法,能製作出電阻分佈均勻且品質優良的晶體。
本發明的N型多晶矽晶體具有一電阻率斜率與一缺陷面積佔比之斜率。在座標橫軸單位為固化分率以及座標縱軸單位為歐姆·公分(Ω·cm)時,在固化分率為0.25~0.8的電阻率斜率為0至-1.8。在座標橫軸單位為固化分率以及座標縱軸單位為缺陷面積佔比(%)時,在固化分率為0.4~0.8的所述缺陷面積佔比之斜率小於2.5。
在本發明的一實施例中,上述N型多晶矽晶體以µ-PCD (Microwave Photoconductivity Decay)方法量測的少數載子壽命(lifetime)的平均值大於20µs。
在本發明的一實施例中,上述N型多晶矽晶體摻有鎵和磷,且鎵的摻雜量例如在0.3ppma~3ppma、磷的摻雜量例如在0.02ppma~0.2ppma以及鎵和磷的原子比例如在10~20之間。
在本發明的一實施例中,上述N型多晶矽晶體包括晶碇(ingot)、晶棒(brick)或晶片(wafer)。
在本發明的一實施例中,上述N型多晶矽晶體的晶向至少包括{111}、{112}、{113}、{315}與{115}。
在本發明的一實施例中,在固化分率為0.4~0.8的上述N型多晶矽晶體的缺陷面積佔比小於2%。
在本發明的一實施例中,在上述N型多晶矽晶體之氧含量大於或等於5ppma之範圍,其對應位置之碳含量大於或等於4ppma。
在本發明的一實施例中,上述N型多晶矽晶體包括多個矽晶粒,沿一長晶方向成長,其中在所述長晶方向上矽晶粒的平均晶粒尺寸與N型多晶矽晶體的電阻率具有相反的變化趨勢。
上述的在本發明的一實施例中,上述平均晶粒尺寸可小於等於1.3cm。
本發明的N型多晶矽晶片是以上述N型多晶矽晶體切片得到的,以µ-PCD (Microwave Photoconductivity Decay)方法量測的少數載子壽命的平均值為2µs~5µs。
本發明的N型多晶矽晶體的製造方法,包括採用定向凝固系統(directional solidification system,DSS)長晶爐成長N型多晶矽晶體,其中長晶爐中的坩堝內具有矽料與摻雜劑,且N型多晶矽晶體的高度如為H,則摻雜劑是位於自坩堝的底部算起0.1H~0.3H的區域內。
在本發明的再一實施例中,上述的摻雜劑包括顆粒、摻雜片或其組合。
在本發明的再一實施例中,上述的摻雜劑包括鎵與磷。
在本發明的再一實施例中,鎵的摻雜量約在0.3ppma~ 3ppma、磷的摻雜量約在0.02ppma~0.2ppma以及鎵和磷的原子比約為10~20之間。
在本發明的再一實施例中,上述的矽料可包括廢晶片。
在本發明的再一實施例中,上述摻雜劑如為顆粒,則成長N型多晶矽晶體之前還可包括:先利用一個廢晶片覆蓋部分矽料,再於廢晶片上放置上述顆粒,然後用其餘矽料包圍並覆蓋所述顆粒。
在本發明的再一實施例中,上述摻雜劑如為顆粒與摻雜片,則成長N型多晶矽晶體之前還可包括:先利用一個廢晶片覆蓋部分矽料,再於廢晶片上放置上述顆粒,然後使用另一廢晶片覆蓋於上述顆粒,於所述顆粒上的廢晶片上放置上述摻雜片,再添加其餘矽料。
基於上述,本發明在DSS長晶爐成長N型多晶矽晶體的過程中,將摻雜劑置於特定範圍的區域內,因此能製作出電阻分佈均勻且品質優良的N型多晶矽晶體,並藉由這樣的N型多晶矽晶體切片得到品質優良、少數載子壽命較長的N型多晶矽晶片,以得到轉換效率優於P型多晶矽晶片製備的太陽能電池。
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。
上文已經概略地敍述本發明之圖式,俾使下文之本發明詳細描述得以獲得較佳瞭解。構成本發明之申請專利範圍標的之其它技術特徵及優點將描述於下文。本發明所屬技術領域中具有通常知識者應可瞭解,下文揭示之概念與特定實施例可作為基礎而加以修改或設計其它結構或製程,而實現與本發明相同之目的。本發明所屬技術領域中具有通常知識者亦應可瞭解,這類等效的建構並無法脫離後附之申請專利範圍所提出之本發明的精神和範圍。
以下揭示內容提供許多不同的實施方式或範例,用於實施本發明的不同特徵。元件與配置的特定範例之描述如下,以簡化本發明的揭示內容。當然這些僅為範例,並非用於限制本發明的範圍與應用。再者,為了清楚起見,區域或結構元件的相對厚度及位置可能縮小或放大。另外,在各圖式中使用相似或相同的元件符號傾向於標示相似或相同元件或特徵的存在。圖式中的相似元件符號標示相似的元件並且將省略其贅述。
圖1是依照本發明之第一實施例的一種N型多晶矽晶體的製備示意圖。
在圖1中顯示的是定向凝固系統(directional solidification system,DSS)之長晶爐100內的坩堝102,其它構件則可參照已知或現有的DSS長晶爐。
在本實施例中,坩堝102內具有矽料104與摻雜劑106a、106b。若是藉由DSS長晶的N型多晶矽晶體的高度為H,則摻雜劑106a、106b的位置需設置於自坩堝102的底部102a算起0.1H~0.3H的區域內。在圖1中,摻雜劑106a是顆粒、摻雜劑106b是摻雜片,但本發明也可都使用顆粒狀的摻雜劑或者都使用摻雜片作為摻雜劑。
如果使用顆粒狀的摻雜劑106a,如鎵(Ga)摻雜劑,由於其容易揮發且為顆粒狀,故可在上述0.1H~0.3H的區域內利用廢晶片108覆蓋於矽料104上,再以其餘矽料104包圍並覆蓋摻雜劑106a。另外,還可使用另一廢晶片108覆蓋於顆粒狀的摻雜劑106a之後,再放置另一片狀的摻雜劑106b,如摻雜磷矽晶片,然後再添加矽料104。前述摻雜劑106a、106b的設置方式可根據其型態而變化,並不限於上述幾種方式,只要能確保摻雜劑106a、106b的位置固定在0.1H~0.3H的區域內,即可達到降低摻雜劑106a、106b揮發的效果。而且,上述廢晶片亦可視為長晶用的矽料104的一部分。
在一實施例中,摻雜劑106a、106b可包括鎵與磷,其放置位置只要滿足上述範圍即可,而摻雜劑106a、106b中鎵與磷的摻雜量,如以使N型多晶矽晶體的電阻分佈均勻且品質優良的觀點來看,鎵的摻雜量例如在0.3ppma~ 3ppma、磷的摻雜量例如在0.02ppma~0.2ppma,且鎵和磷的原子比例如在10~20之間。
在一實施例中,DSS之長晶過程是在矽料104與摻雜劑106a、106b均如圖1設置完畢,然後進行加熱使坩堝102內的矽料104全部熔化成矽熔湯,並進行方向性凝固製程冷卻坩堝102及其內的矽料104,使得多晶矽晶粒逐漸沿長晶方向V成長,而形成N型多晶矽晶體。
在上述實施例中,長晶爐100內的元件(如碳纖維、隔離材、石墨板等)因為高溫會產生碳元素,所以若沒有上蓋板(未繪示)覆蓋坩堝開口的情形下,上述環境中產生的碳元素會進入矽熔湯,所以製作出的N型多晶矽晶體預期會具有較高的碳含量。
根據第一實施例的製備方式,利用DSS成長的成長N型多晶矽晶體具有一電阻率斜率與一缺陷面積佔比之斜率。在座標橫軸單位為固化分率以及座標縱軸單位為歐姆·公分(Ω·cm)時,於固化分率為0.25~0.8的電阻率斜率為0至-1.8。在座標橫軸單位為固化分率以及座標縱軸單位為缺陷面積佔比(%)時,於固化分率為0.4~0.8的所述缺陷面積佔比之斜率小於2.5。
在本文中,「固化分率(solidified fraction)」是指在N型多晶矽晶體凝固的過程中,其長晶方向V上已凝固部分的高度與矽晶體總高度之比值。越早凝固的晶體之位置的固化分率越小、越晚凝固的晶體之位置的固化分率越大,因此固化分率為0是代表N型多晶矽晶體的底部;固化分率為1.0是代表N型多晶矽晶體的頂部。
在一實施例中,上述N型多晶矽晶體以µ-PCD方法測得的少數載子壽命(lifetime)的平均值大於20µs。此外,上述N型多晶矽晶體可摻有鎵和磷,且鎵的摻雜量例如在0.3ppma~3ppma之間、磷的摻雜量例如在0.02ppma~0.2ppma之間,且鎵和磷的原子比例如在10~20之間。舉例來說,如果鎵和磷的原子比例越小,所成長的N型多晶矽晶體之電阻率就會越低;反之,若是鎵和磷的原子比例越大,則成長的N型多晶矽晶體之電阻率就會越高。
而且,上述N型多晶矽晶體的晶向至少包括{111}、{112}、{113}、{315}與{115},但本發明並不限於此。此外,本實施例之N型多晶矽晶體,於固化分率為0.4~0.8的區段內,其缺陷面積佔比小於2%。上述N型多晶矽晶體一般包括晶碇(ingot)、晶棒(brick)或晶片(wafer)。
在固化分率為0~0.15的部位的N型多晶矽晶體之氧含量可大於或等於5ppma,如在5 ppma~20 ppma之間,較佳是在5 ppma~10 ppma之間。此外,由於長晶過程中不蓋上蓋板,所以在上述N型多晶矽晶體之氧含量大於或等於5ppma之範圍內,其對應位置之碳含量可大於或等於4ppma,如在5 ppma~20 ppma之間,較佳是在6 ppma~13 ppma之間。而且,可發現N型多晶矽晶體中的矽晶粒在長晶方向V上的平均晶粒尺寸與N型多晶矽晶體的電阻率具有相反的變化趨勢。在一實施例中,上述平均晶粒尺寸可小於等於1.3cm。
以下列舉數個實驗用以驗證本發明的功效,但本發明之範圍並不侷限於以下實驗例。
實驗例
1
將矽料與摻雜劑(鎵顆粒與磷摻雜片)如圖1置於石墨坩堝內,摻雜劑的位置設置於自坩堝的底部算起0.25H的區域,其中鎵的摻雜量為1.953ppma、磷的摻雜量為0.180ppma。鎵和磷原子比例為10.85。
在不蓋上蓋板的情況下升溫超過1414°C,讓矽料開始熔化。升溫到1500°C~1570°C矽料會完全熔化為矽熔湯,然後藉由溫度的控制進行長晶。長晶初始溫度設為1385°C~1430°C,最終溫度設為1385°C ~1400°C。長晶完成後,依序完成退火、冷卻過程,所成長的是n型多晶矽晶體。
實驗例
2
採用與實驗例1相同的長晶步驟與摻雜劑擺放位置,但是鎵和磷的摻雜量分別變更為0.632ppma以及0.044ppma。鎵和磷原子比例為14.36。所成長的是n型多晶矽晶體。
對照例
1
採用與實驗例1相同的長晶步驟,只摻雜硼(摻雜量為0.183ppma),因此所成長的是P型多晶矽晶體。
對照例
2
以SCHINDLER等人於2014年9月22-24日在荷蘭阿姆斯特丹的第29屆歐洲光伏太陽能會議與展覽(European PV Solar Energy Conference and Exhibition)中發表的「用於高效率太陽能電池之多晶N型矽的潛力(The Potential of Multicrystalline N-Type Silicon for High Efficiency Solar Cells)」中的相關實驗結果作為對照例2。其中N型摻雜劑為磷。
對照例
3
以SCHINDLER等人發表於2015年11月出刊的光電期刊(IEEE Journal of Photovoltaics,Vol. 5,No. 6)中的「高效多晶矽太陽能電池:n型摻雜的潛力(High-Efficiency Multicrystalline Silicon Solar Cells: Potential of n-Type Doping)」(第1571~1579頁)中的相關實驗結果作為對照例3。其中N型摻雜劑的摻雜量是7~8×10
15cm
-3,亦即0.14~0.16 ppma。
〈分析〉
1. 電阻率:以非接觸式電阻機台檢測多晶矽晶體側面,於多晶矽晶體的各個固化分率對應位置量測四面之均值可視為該固化分率之電阻率。非接觸式電阻量測法是藉由在發射線圈上通入固定頻率交流電,線圈產生的磁場與待測物接近時,待測物出現渦電流,而渦電流的強弱與電阻率成反比,因此可得知待測物電阻率。
2. 多晶矽晶體的少數載子壽命:使用µ-PCD方法量測多晶矽晶體的少數載子壽命相對固化分率的關係曲線。
3. 多晶矽晶片的少數載子壽命:將多晶矽晶體在長晶方向(V)上切割成數片晶片,接著使用少數載子壽命(Lifetime)測試機量測多晶矽晶片的少數載子生命週期相對固化分率的關係曲線。不限制晶片厚度,只要儀器內的分光機(SORTER)可接受乘載的厚度即可,且所有驗片的厚度要相同。
4. 缺陷面積佔比:將多晶矽晶體在長晶方向(V)上切割成數片驗片,接著利用光激致發光(photoluminescence,PL)機台檢測,其利用高於半導體能隙的能量的光打向驗片,以產生的載子躍遷與複合行為所放出的螢光,再藉由量測系統根據螢光譜以判定缺陷位置,進而計算出缺陷面積佔比相對固化分率的關係。
5. 多晶矽晶體的碳含量:將多晶矽晶體在長晶方向(V)上切割成數片驗片,接著利用傅利葉轉換紅外光譜(FTIR)測量儀器並參照SEMI MF 1391-0704標準測量規範,測量每個驗片上九個不同位置的碳含量,最後計算出驗片上九個位置單次的碳含量的平均值,並以重複測5次後的總平均值作為該片碳含量。
6. 多晶矽晶體的氧含量:與上述碳含量的量測方式相同。
7. 平均晶粒尺寸:將多晶矽晶體在長晶方向(V)上切割成數片驗片,接著依據ASTM E112-10標準測量規範測量相對固化分率的關係。
首先依照上述分析方式,對實驗例1~2的多晶矽晶體進行電阻率的量測,將所得結果與對照例2的數據一併顯示於圖2。從圖2可得到,實驗例1的電阻率在1.5Ω·cm~3Ω·cm之間;實驗例2的電阻率在8Ω·cm~9Ω·cm之間;對照例2的電阻率在0.5Ω·cm~3.5Ω·cm之間。若是以座標橫軸單位為固化分率以及座標縱軸單位為歐姆·公分(Ω·cm)時,在固化分率為0.25~0.8的區段中,實驗例1的電阻率斜率為-1.63;實驗例2的電阻率斜率約為-0.3;對照例2的電阻率斜率小於-1.8,為-2.5。因此,與對照例2的N型多晶矽晶體相比,實驗例1~2的電阻率的範圍較對照例2集中,亦即電阻率斜率較為平緩。
然後,對實驗例1~2與對照例1的多晶矽晶體進行少數載子壽命的量測,將所得結果顯示於圖3。從圖3可得到,實驗例1~2的晶體少數載子壽命均在20µs以上,且實驗例1的晶體少數載子壽命之最大值甚至來到40µs以上;相較下,對照例1的P型多晶矽晶體之少數載子壽命不到10µs。
至於實驗例1~2與對照例1的多晶矽晶片之少數載子壽命的結果則顯示於圖4。從圖4可得到,實驗例1的晶片少數載子壽命在3µs~4.2µs;實驗例2的晶片少數載子壽命在2.5µs~3µs;相較下,對照例1的P型多晶矽晶片少數載子壽命約在1.6µs左右。因此,本發明的實驗例1~2的少數載子壽命的平均值在2µs~5µs的範圍內,故具有比對照例1更長的晶片少數載子壽命。
接著,對實驗例1~2與對照例1的多晶矽晶片進行缺陷量測,結果顯示於圖5。從圖5可得到,於固化分率為0.4~0.8的實驗例1~2的缺陷面積佔比均小於2%、平均缺陷面積佔比則小於1.5%;相較下對照例1的缺陷面積佔比來到2.5%左右。而在座標橫軸單位為固化分率以及座標縱軸單位為缺陷面積佔比(%)時,於固化分率為0.4~0.8的實驗例1之缺陷面積佔比斜率約2.25;於固化分率為0.4~0.8的實驗例2之缺陷面積佔比斜率約0.25。因此,本發明的實驗例1~2的缺陷面積佔比斜率均小於2.5。相較下於固化分率為0.4~0.8的對照例1的缺陷面積佔比斜率則為4左右。因此,與對照例1的P型多晶矽晶體相比,實驗例1~2的缺陷面積佔比較少,且缺陷面積佔比斜率較為平緩,所以整體晶棒品質優於對照例1的P型多晶矽晶體。
至於多晶矽柱體的碳含量與氧含量的結果,請見圖6與下表一。 表一
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 固化分率 </td><td> 氧含量(ppma) </td><td> 碳含量(ppma) </td></tr><tr><td> 0.11 </td><td> 6.172 </td><td> 7.015 </td></tr><tr><td> 0.22 </td><td> 3.44 </td><td> 9.518 </td></tr><tr><td> 0.34 </td><td> 2.379 </td><td> 10.388 </td></tr><tr><td> 0.46 </td><td> 1.442 </td><td> 6.351 </td></tr><tr><td> 0.57 </td><td> 1.274 </td><td> 11.699 </td></tr><tr><td> 0.69 </td><td> 0.917 </td><td> 7.244 </td></tr><tr><td> 0.80 </td><td> 0.407 </td><td> 10.362 </td></tr><tr><td> 0.92 </td><td> 0.244 </td><td> 8.539 </td></tr><tr><td> 1.00 </td><td> 0.238 </td><td> 8.035 </td></tr></TBODY></TABLE>
由圖6與表一可得到,實驗例1之N型多晶矽晶體之氧含量大於5ppma之範圍,其碳含量皆大於4ppma。而且,從圖6可得到氧含量在長晶方向(V)上具有相反的變化趨勢,亦即長晶方向V上,越早凝固的晶體內的氧含量較高、越晚凝固的晶體內的氧含量較低,亦即固化分率愈高,氧含量愈低。
最後,對實驗例1~2與對照例1進行晶粒大小的量測,結果顯示於圖7。從圖7可得到,實驗例1~2與對照例1在長晶方向上矽晶粒的平均晶粒尺寸均小於1.3cm,且隨著固化分率增加,晶粒大小有增加的趨勢。因此對照於上述電阻率的結果,可得到在長晶方向V上矽晶粒的平均晶粒尺寸與N型多晶矽晶體的電阻率具有相反的變化趨勢的結論。
應用例
將實驗例1與對照例1的N型多晶矽晶體經過切片而成的N型多晶矽晶片,經過與對照例3的文獻中相同的太陽能電池製程得到測試用太陽能電池。上述太陽能電池製程包括:(1)對晶片正面進行的蝕刻(texturing,或制絨)製程、(2)遮住晶片背面的罩幕(mask)製程、(3)硼擴散製程(890°C;1小時)、(4)移除晶片背面的罩幕的步驟、(5)在晶片背面形成約數埃的穿隧氧化層(tunnel oxide)的步驟、(6)在穿隧氧化層上沉積15nm厚的磷摻雜矽層的步驟、(7)退火製程(800°C;1小時)、(8)對晶片正面進行的鈍化處理(passivation)、(9)金屬化製程(metallization)。
然後對測試用太陽能電池進行I-V量測,並與對照例3的文獻中的轉換效率一起顯示於圖8。從圖8可得到,本發明之實驗例1的N型多晶矽晶片具有高達21.9%的轉換效率,明顯優於對照例1的P型多晶矽晶片18.4%以及對照例3的N型多晶矽晶片19.6%所得結果。因此,可知實驗例1的N型多晶矽晶片的品質優於對照例3的N型多晶矽晶片。
綜上所述,本發明的N型多晶矽晶體具有較緩和的電阻率斜率與缺陷面積佔比斜率,且少數載子壽命也獲得增長,因此能有優良的晶體品質,並可由此種N型多晶矽晶體製作出轉換效率優異的太陽能電池。再者,本發明可藉由在DSS長晶爐成長N型多晶矽晶體的過程中,將摻雜劑置於特定範圍的區域內,來製作出上述電阻分佈均勻且品質優良的N型多晶矽晶體。
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,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。
100‧‧‧長晶爐
102‧‧‧坩堝
102a‧‧‧底部
104‧‧‧矽料
106a、106b‧‧‧摻雜劑
108‧‧‧廢晶片
H‧‧‧N型多晶矽晶體的高度
V‧‧‧長晶方向
圖1是依照本發明之第一實施例的一種N型多晶矽晶體的製備示意圖。 圖2是實驗例1~2與對照例2之多晶矽晶體的電阻率與固化分率之關係曲線圖。 圖3是實驗例1~2與對照例1之多晶矽晶體的少數載子壽命的曲線圖。 圖4是經由實驗例1~2與對照例1之多晶矽晶體所製得的多晶矽晶片之少數載子壽命的曲線圖。 圖5是經由實驗例1~2與對照例1之多晶矽晶體所製得的多晶矽晶片的缺陷面積佔比與固化分率之關係曲線圖。 圖6是實驗例1之多晶矽柱體的碳/氧含量與固化分率之關係曲線圖。 圖7是實驗例1~2與對照例1之多晶矽晶體的平均晶粒尺寸與固化分率之關係曲線圖。 圖8是經由實驗例1與對照例1和對照例3之多晶矽晶體所製得的多晶矽晶片應用於太陽能電池的轉換效率比較圖。
Claims (17)
- 一種N型多晶矽晶體,其特徵在於:所述N型多晶矽晶體具有一電阻率斜率,在座標橫軸單位為固化分率以及座標縱軸單位為歐姆.公分(Ω.cm)時,在所述固化分率為0.25~0.8的所述電阻率斜率為0至-1.8;以及所述N型多晶矽晶體具有一缺陷面積佔比斜率,在座標橫軸單位為所述固化分率以及座標縱軸單位為缺陷面積佔比(%)時,在所述固化分率為0.4~0.8的所述缺陷面積佔比斜率小於2.5。
- 如申請專利範圍第1項所述的N型多晶矽晶體,其中所述N型多晶矽晶體以μ-PCD方法量測的少數載子壽命的平均值大於20μs。
- 如申請專利範圍第1項所述的N型多晶矽晶體,其中所述N型多晶矽晶體摻有鎵和磷,且鎵的摻雜量在0.3ppma~3ppma、磷的摻雜量在0.02ppma~0.2ppma以及鎵和磷的原子比為10~20之間。
- 如申請專利範圍第1項所述的N型多晶矽晶體,其中所述N型多晶矽晶體包括晶碇(ingot)、晶棒(brick)或晶片(wafer)。
- 如申請專利範圍第1項所述的N型多晶矽晶體,其中所述N型多晶矽晶體的晶向至少包括{111}、{112}、{113}、{315}與{115}。
- 如申請專利範圍第1項所述的N型多晶矽晶體,其中在所述固化分率為0.4~0.8的所述N型多晶矽晶體的所述缺陷面積佔比小於2%。
- 如申請專利範圍第1項所述的N型多晶矽晶體,其中在所述N型多晶矽晶體中氧含量大於或等於5ppma之範圍,其對應位置之碳含量大於或等於4ppma。
- 如申請專利範圍第7項所述的N型多晶矽晶體,其中所述N型多晶矽晶體包括多數個矽晶粒,沿一長晶方向成長,其中在所述長晶方向上所述矽晶粒的平均晶粒尺寸與所述N型多晶矽晶體的電阻率具有相反的變化趨勢。
- 如申請專利範圍第8項所述的N型多晶矽晶體,其中所述平均晶粒尺寸小於等於1.3cm。
- 一種N型多晶矽晶片,是以申請專利範圍第1~9項中任一項所述的N型多晶矽晶體切片得到的,其特徵在於:所述N型多晶矽晶片以μ-PCD量測的少數載子壽命的平均值為2μs~5μs。
- 一種如申請專利範圍第1~9項中任一項所述的N型多晶矽晶體的製造方法,包括:採用定向凝固系統(directional solidification system,DSS)之長晶爐成長N型多晶矽晶體,其中所述長晶爐中的坩堝內具有矽料與摻雜劑,且所述N型多晶矽晶體的高度為H,則所述摻雜劑是位於自所述坩堝的底部算起0.1H~0.3H的區域內。
- 如申請專利範圍第11項所述的N型多晶矽晶體的製造方法,其中所述摻雜劑包括顆粒、摻雜片或其組合。
- 如申請專利範圍第11項所述的N型多晶矽晶體的製造方法,其中所述摻雜劑包括鎵與磷。
- 如申請專利範圍第13項所述的N型多晶矽晶體的製造方法,其中所述鎵的摻雜量在0.3ppma~3ppma、所述磷的摻雜量在0.02ppma~0.2ppma以及所述鎵和所述磷的原子比為10~20之間。
- 如申請專利範圍第11項所述的N型多晶矽晶體的製造方法,其中所述矽料包括廢晶片。
- 如申請專利範圍第15項所述的N型多晶矽晶體的製造方法,其中所述摻雜劑包括顆粒,且成長所述N型多晶矽晶體之前,更包括:利用一個所述廢晶片覆蓋部分所述矽料;於所述廢晶片上放置所述顆粒;以及用其餘所述矽料包圍並覆蓋所述顆粒。
- 如申請專利範圍第15項所述的N型多晶矽晶體的製造方法,其中所述摻雜劑包括顆粒與摻雜片,且成長所述N型多晶矽晶體之前,更包括:利用一個所述廢晶片覆蓋部分所述矽料;於所述廢晶片上放置所述顆粒;使用另一個所述廢晶片覆蓋於所述顆粒;於所述顆粒上的所述廢晶片上放置所述摻雜片;以及添加其餘所述矽料。
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