TWI405347B - Ｃｉｇｓ太陽能電池 - Google Patents

Ｃｉｇｓ太陽能電池 Download PDF

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TWI405347B
TWI405347B TW099121861A TW99121861A TWI405347B TW I405347 B TWI405347 B TW I405347B TW 099121861 A TW099121861 A TW 099121861A TW 99121861 A TW99121861 A TW 99121861A TW I405347 B TWI405347 B TW I405347B
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solar cell
semiconductor layer
cigs solar
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TW201203583A (en
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Yanway Li
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Gcsol Tech Co Ltd
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Description

CIGS太陽能電池
本發明是有關於一種電池及其製造方法，且特別是有關於一種太陽能電池及其製造方法。
太陽能為一種環保的再生性能源，可轉換為其他形式之能量如熱及電，且太陽能電池應用的範圍非常廣，大到發電系統，小到消費性電子產品，但以太陽能作為在經濟上具有競爭力的再生性能源，仍受到太陽能電池將光能轉換為電能時之低效率所阻礙，因此，有效地提高太陽能電池的產電效率，並降低太陽能電池的生產成本，已成為太陽能電池的發展目標。
有關CIGS太陽能電池之先前技術如美國專利號碼第7018858所揭露之Light absorbing layer producing method專利，該專利用一種沉積前驅物層之雙靶式濺鍍法沉積設備，採取一種雙靶直立面對面設置進行共濺鍍(co-sputter)的鍍膜方式，但因該方式將基板設置於靶材下方，沉積過程若有污染顆粒產生，則容易發生該污染顆粒順勢沉降至基板的缺點。
又如台灣專利號碼第200917508號所揭露之光伏打接收器專利，該技術之缺點在於太陽能接收器及光入射點之間之焦距或點極大，故需大量空間及體積以安裝此接收器，又，該製造方法於匯集陽光時所產生的熱度，必須另外設置一冷卻系統來維持低於一特定溫度，否則所產生之熱能將不利於太陽能電池的光轉電效率。
有鑑於此，得知CIGS太陽能電池仍未臻完善，本發明之目的係提供一高效率之CIGS太陽能電池結構與製作方法。
通常太陽能電池是由p型半導體層、本質半導體層(intrinsic semiconductor layer)以及n型半導體層堆疊而成，且p型半導體層、本質半導體層以及n型半導體層皆為非晶矽(amorphous silicon)材料。而以非晶矽為材料的半導體層往往存在著光吸收效果不佳的缺點，進而導致產電效率不佳，為改善此問題，常利用增加本質半導體層厚度的方式來增加光吸收效果，但同時也增加太陽能電池的整體厚度與生產成本。有鑑於此，本發明在不增加本質半導體層厚度與整體體積的條件之下，利用結構與形成方式上的研發，藉由增加光吸收面積而提升光吸收量，也因此增加光電轉換效率來提高產電效率，並可大幅降低生產成本而提高太陽光能之經濟價值。
緣以達成上述目的之一，本發明在提供一種太陽能電池結構，可使光電轉換效率增加，該發明之主要結構包含玻璃基板、光吸收表面與光電轉換結構。其中，該玻璃基板之至少一表面具有多個陣列式凹凸部，且該陣列式凹凸部之最頂端延伸至最底端之距離為一預定深度；該光吸收表面包含陣列式凹凸部最頂端所形成之表面、陣列式凹凸部最頂端延伸至最底端所形成之表面、以及陣列式凹凸部最底端基板除陣列式凹凸部所形成表面之集合；該光電轉換結構由n型半導體層、p型半導體層與i型半導體層所組成。其中，該n型半導體層為一CIGS類化合物且位於該光吸收表面之上方，該p型半導體層位於該n型半導體層之上方且為一氧化物，且該i型半導體層位於該n型半導體層與該p型半導體層間並為一氧化物，而該光電轉換結構所形成之n-i-p結構則可促進各該層表面之接合效果，藉以產生良好的界面接觸，進一步減少界面孔洞的形成，因此增加量子效率，而能提高光電轉換效率。
再者，本發明之另一目的是在提供一種CIGS太陽能電池之製造方法，由在玻璃基板表面產生之陣列式凹凸部，該陣列式凹凸部之外形為幾何圖形柱體，例如圓柱體或多邊形柱體等，藉以增加整體光吸收表面面積而增加光吸收量，因此提高太陽能電池的產電效率。
又，本發明為一種CIGS太陽能電池之製造方法，該方法包含下列步驟：提供一玻璃基板，塗佈一預定形狀之保護膜於該玻璃基板之預定位置處，並浸泡該玻璃基板於一蝕刻劑中，於一預定時間後取出該玻璃基板清洗且去除該保護膜，使該玻璃基板之預定位置處形成多個預定形狀之陣列式凹凸部；其中，該些陣列式凹凸部之最頂端所形成表面、該凹凸部之最頂端延伸至最底端所形成表面、以及該凹凸部之最底端基板除陣列式凹凸部所形成表面之集合，即為該光吸收表面；再者，依序於該光吸收表面上沉積覆蓋一下電極，於該下電極上沉積覆蓋一中間層，於該中間層上沉積覆蓋一光電轉換結構，其中，該光電轉換結構包含有n型半導體層、p型半導體層與i型半導體層；最後，於該光電轉換結構上沉積覆蓋一上電極，並於該上電極上形成一導線，以及於該導線上沉積覆蓋一抗反射層。
綜上所述，本發明於結構與形成方式上的改變，可以增加太陽能電池之光吸收量、光電轉換效率與其產電效率。
為能更清楚地說明本創作之CIGS太陽能電池結構，茲舉較佳實施例並配合圖示詳細說明如後。
請參照第1A、1B、2A與2B圖，為本發明之一較佳實施例，其分別繪示本發明CIGS太陽能電池之剖面示意圖、局部剖面示意圖、本發明之玻璃基板俯視圖與第2A圖玻璃基板之側視圖。其中：該CIGS太陽能電池100包含玻璃基板110、光吸收表面120與光電轉換結構130。該玻璃基板110之至少一表面包含多個陣列式凹凸部112，各該陣列式凹凸部112之最頂端延伸至最底端之距離為一預定深度h，於本實施例中，該預定深度h為1釐米以上，其中又以2釐米為最佳；又各該陣列式凹凸部之間具有相同之預定間距w與寬度d，其中間距以0.625釐米為最佳；且各該陣列式凹凸部之外形為圓柱體之相同幾何圖案柱體，換言之，每一個陣列式凹凸部112的外型與大小皆相同，且均佈於該玻璃基板110之表面。
另外，該光吸收表面120包含各該陣列式凹凸部最頂端所形成表面122、各該陣列式凹凸部112最頂端延伸至最底端所形成表面124，以及各該陣列式凹凸部112最底端基板除凹凸部112所形成表面126之集合。綜上所述，本發明之太陽能電池可藉由該陣列式凹凸部112之形成而增加該玻璃基板之光吸收表面之表面積。
其中：光電轉換結構130由n型半導體層132、p型半導體層134與i型半導體層136所組成。該n型半導體層132位於光吸收表面120上方，且該n型半導體層132為一CIGS類化合物，該CIGS類化合物之化學式為Sn:Cu(In1-x Gax )Se2 ，於本實施例中，該化學式x值為0.18~0.3；又，該CIGS類化合物包含第一前驅化合物與第二前驅化合物；其中該第一前驅化合物包含銅(Cu)、鎵(Ga)與硒(Se)等元素，例如銅鎵硒合金，且該第二前驅化合物包含銦(In)與硒(Se)等元素，例如銦硒合金。
再者，該光電轉換結構130之該p型半導體層134位於該n型半導體層132之上方，且該p型半導體層134為一氧化物，例如含銅與鋁之氧化物；又該光電轉換結構130之該i型半導體層136則位於n型半導體層132與p型半導體層134間，且為一氧化物。
於本實施例中，該CIGS類化合物之厚度為1500~2500奈米，能階為1.17 eV，該i型半導體層為氧化亞銅(Cu2 O)，其能階為2.1 eV，其厚度為5~50奈米，該p型半導體層134為氧化銅鋁(CuAlO2 )，其厚度為30~120奈米，其能階為3.5 eV，使得太陽能所產生之不同波長可依其波長高低各自被n半導體層、i半導體層、p半導體層所吸收。
由於該p型半導體層134與該n型半導體層132的能階差異大，因此，利用i型半導體層136的氧化物使得p型半導體層134與n型半導體層132具有較好的接合界面，並在界面上有較低之載子復合機率產生，進而提高量子效率。
上述實施方式乃藉由於玻璃基板上設置陣列式凹凸部，在不增加CIGS太陽能電池的整體體積下，達到增加光吸收表面積的目的。(表一)係列出比較例與多個實施例，與其各自所增加的總表面積比例，於該表列出當玻璃基板尺寸為100平方公分時，在具有不同的陣列式凹凸部的數目、寬度以及兩兩陣列式凹凸部間的間距條件下，所產生的總表面積與總表面積增加比例之計算結果；據此得知，在相同尺寸之玻璃基板上，隨著陣列式凹凸部的數目增加、寬度減少、以及排列越密集，則所增加的總表面積越多，亦即表示此種態樣可增加CIGS太陽能電池的光吸收表面積。
再請參照第3圖為本發明CIGS太陽能電池之另一實施方式，係同於第1A圖中所標示範圍M之剖面結構示意圖。該CIGS太陽能電池200包含有玻璃基板210、光吸收表面220、下電極230、中間層240、光電轉換結構250、上電極260、導線270與抗反射層280等結構。其中，該玻璃基板210、該光吸收表面220與該光電轉換結構250之結構皆與前述之實施方式相同，下列敘述僅針對不同之處進行說明。
該下電極230位於該玻璃基板210且為該光吸收表面220之上，且該下電極230可為一金屬材質或為一非金屬氧化物。若該下電極230係為一金屬材質，可選自鈦(Ti)、鉬(Mo)、鉭(Ta)或上述任意合金，其中又以鉬(Mo)為優選材質；又，該中間層240位於光電轉換結構250與下電極230之間，其材質包含錫(Sn)、碲(Te)或鉛(Pb)等元素，其中以錫(Sn)為優選材質。
於本實施例中，該中間層240之厚度為5~50奈米。其中，該中間層240位於該下電極230上，且下電極230為金屬材質，則該基板中的鈉(Na)元素會藉由熱擴散穿越該下電極，以致於該下電極230與該光電轉換結構250間具有較好的介面接觸效果，並減少界面孔洞的形成。
另外，第4圖為本發明CIGS太陽能電池之又一實施方式，係同於第1A圖中所標示範圍M之剖面結構示意圖。請參照第4圖所示，若該下電極230係為一非金屬氧化物，例如氧化銦錫(ITO)，因氧化物具有阻礙鈉(Na)元素擴散的效果，所以必須增設一鈉化合物層242於該中間層240與該光電轉換結構250之間，例如氟化鈉(NaF)，藉由鈉源之補充以輔助吸收層CIGS的成長，此時之太陽能電池具備吸收層前後皆可透光的特性，可增進吸收層的陽光吸收效益。
且該上電極260位於該光電轉換結構250之上方，於本實施例中，該上電極260之厚度為400~1200奈米，材質係為鋁摻雜氧化鋅(AZO，ZnO:Al)；該導線270則位於上電極260之上方；該抗反射層280則位於導線270之上方，於本實施例中，該抗反射層280之厚度為80~150奈米，材質為氮化矽(Si3 N4 :H)。
再者，為了能清楚地說明本創作之CIGS太陽能電池之製造方法，茲舉較佳實施例並配合圖示詳細說明如後。
請參照第5圖係為一種CIGS太陽能電池製造方法之流程示意圖。該太陽能電池製造方法300之步驟包含提供玻璃基板(步驟310)、形成陣列式凹凸部(步驟320)、形成下電極(步驟330)、形成中間層(步驟340)、形成光電轉換結構(步驟350)、形成上電極(步驟360)、形成導線(步驟370)與形成抗反射層(步驟380)。
另請加參照第6圖係為該CIGS太陽能電池製造方法中，形成陣列式凹凸部(步驟320)之流程400示意圖。首先，於一玻璃基板410表面之預定位置處塗佈保護膜420為一預定形狀，於本實施例中該保護膜420係為石蠟；再將該玻璃基板410浸泡於一蝕刻劑例如氫氟酸水溶液中一預定時間進行酸蝕，藉以於該玻璃基板410之表面形成多個陣列式凹凸部430；然而隨著浸泡之時間越長，所形成的陣列式凹凸部之最頂端延伸至最底端距離的深度越大；接著取出該玻璃基板410清洗並藉由例如甲醇加以去除該保護膜420，即可產生一具有多個陣列式凹凸部430之玻璃基板410，此時該陣列式凹凸部430之最頂端所形成表面432、最頂端延伸至最底端所形成之表面434與最底端基板除陣列式凹凸部430所形成表面436之集合，即為本發明之光吸收表面440。
又於該光吸收表面440之輪廓向外延伸方向沉積覆蓋形成一下電極(步驟330)，其中該下電極之材質可選自金屬材質或非金屬氧化物二者之一；又於該下電極上沉積覆蓋一中間層(步驟340)，其中，該中間層可選自錫、碲或鉛等元素，於此實施例中，其厚度設定為5~50奈米，若該下電極係為一非金屬氧化物，則需增設一鈉化合物層於該中間層與該光電轉換結構之間；接著沉積覆蓋一光電轉換結構(步驟350)於該中間層之上，其中，該光電轉換結構依序形成n型半導體層、i型半導體層與p型半導體層之結合。
該n型半導體層之形成步驟係包含於中間層上形成第一前驅物膜與第二前驅物膜，並於ⅥA族元素之氣氛下，藉由熱處理方式形成一CIGS類化合物，該CIGS類化合物之化學式為Sn:Cu(In1-x Gax )Se2 ，其中x值為0.18~0.3，此步驟也同時使該中間層擴散摻入該CIGS類化合物；於此實施例中，該第一前驅物膜包含銅、鎵與硒元素，該第二前驅物膜包含銦與硒元素，且該n型半導體層之厚度為1500~2500奈米。
又，該第一與第二前驅物膜之形成方法可為電鍍、無電電鍍、原子層沉積、化學氣相沉積、金屬－有機化學氣相沉積或物理氣相沉積，其中以物理氣象沉積為優選；而前述熱處理步驟係利用活化一激發源將ⅥA族元素蒸氣活性化，而該活化激發源之方式可為電子束、離子束、電漿共振裝置或熱裂解，其中以熱裂解搭配電漿共振裝置為優選，此時熱處理之實際溫度為380 ℃~600 ℃。
另外，該i型半導體層之形成方式為以原子層沈積法(Atomic layer deposition，ALD)於n型半導體層上沈積銅膜，再通入氧氣以180℃進行熱氧化處理，而形成氧化亞銅層；於本實施例中，所形成之氧化亞銅層厚度為5~50奈米；該p型半導體層則以濺鍍法沈積於i型半導體層上，該p型半導體層包含銅與鋁之氧化物。
承上依序於該光電轉換結構(步驟350)上沉積覆蓋該上電極(步驟360)、於該上電極上形成該導線(步驟370)、以及於該導線上沉積覆蓋該抗反射層(步驟380)。於本實施例中，該上電極與該抗反射層皆利用濺鍍法沈積。
再者，依(表一)之實施例4所示簡述如下：將玻璃基板表面塗佈圓形圖樣之石臘，該圓形直徑為0.0625公分，兩圓形間的間隔為0.0625公分；待石臘硬固，將玻璃基板整個浸入氫氟酸水溶液中進行蝕刻，約30-40分鐘後，於玻璃基板表面形成2公釐高之圓柱凸出物，此時玻璃基板之表面積增加約160%。
接著，進行元件製程。於玻璃基板之具有圓柱凸出物表面以濺鍍法沉積1μm之背電極。隨後分別沉積錫薄膜(中間層)、銅鎵硒膜(CuGaSe)與銦硒(InSe)膜於背電極表面，並對玻璃基板進行熱處理。該熱處理利用兩階段溫度來使錫薄膜、銅鎵硒膜與銦硒膜交互擴散與化合反應；第一階段通入高溫活化後的硒蒸氣以進行硒化，其溫度約為400℃。第二階段則為同時通入高溫活化後的硒蒸氣與硫蒸氣，進行硒化與硫化溫度之約為580℃；最後形成表面硫化的銅銦鎵硒層，厚度約2000奈米；此時Cu/(In+Ga)值為0.85~0.90，Ga/(In+Ga)則約為0.25。
又利用原子層沉積法於180℃下沉積銅膜；於180℃下通入氧氣進行熱氧化處理，使銅銦鎵硒層上形成厚度約30奈米的氧化亞銅薄膜；此時CuAlO2 與AZO薄膜均以濺鍍法沉積製作。
待元件製作完成後，以100mW/cm2 (AM1.5)之光源進行電性量測。請參照第7圖所示為上述實施例之電性量測結果圖。該實施例之開路電壓(Voc)為0.47 V，填充因子(Fill Factor，FF)為64.54%，其太陽能電池效率為10.52%。
由上述本發明實施方式可知，應用本發明具有下列優點：
第一，利用蝕刻技術使得太陽能電池表面具有陣列式凹凸部，增大整體太陽能電池之光吸收表面，以增加光吸收量，進而提高太陽能電池的產電效率。
第二，於下電極與光電轉換結構間沈積中間層，使得下電極表面濕潤，因而使下電極與光電轉換結構間具有較好的接合效果，減少下電極與光電轉換結構的界面孔洞。
第三，i型半導體層的氧化物使得p型半導體層與n型半導體層具有較好的接合界面，進而提高量子效率。
雖然本發明已以實施方式揭露如上，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，當可作各種之更動與潤飾，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。
100．．．CIGS太陽能電池
110．．．玻璃基板
112．．．陣列式凹凸部
120．．．光吸收表面
122．．．表面
124．．．側面
126．．．表面
130．．．光電轉換結構
132．．．n型半導體層
134．．．p型半導體層
136．．．i型半導體層
200．．．CIGS太陽能電池
210．．．玻璃基板
220．．．光吸收表面
230．．．下電極
240．．．中間層
242．．．鈉化合物層
250．．．光電轉換結構
260．．．上電極
270．．．導線
280．．．抗反射層
300．．．太陽能電池製造方法
310-380．．．步驟
400．．．流程
410．．．玻璃基板
420．．．保護膜
430．．．陣列式凹凸部
432．．．最頂端表面
434．．．側面434
436．．．最底端表面
440．．．光吸收表面
d．．．寬度
h．．．預定深度
M．．．範圍
w．．．預定間距
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下：
第1A圖係繪示本發明一較佳實施例的一種CIGS太陽能電池之剖面示意圖。
第1B圖係繪示第1A圖之CIGS太陽能電池中，局部剖面示意圖。
第2A圖係繪示第1A圖之CIGS太陽能電池中，玻璃基板之俯視圖。
第2B圖係繪示第2A圖之玻璃基板的側視圖。
第3圖為本發明CIGS太陽能電池之另一實施方式，係同於第1A圖中所標示範圍M之剖面結構示意圖。
第4圖為繪示本發明又一實施方式依照之一種CIGS太陽能電池，同於第1A圖中所標示範圍M之剖面結構示意圖。
第5圖係為一種CIGS太陽能電池製造方法之流程示意圖。
第6圖係繪示第5圖之CIGS太陽能電池製造方法中，形成陣列式凹凸部之流程示意圖。
第7圖係繪示上述實施例之電性量測結果圖。
100．．．CIGS太陽能電池
110．．．玻璃基板
130．．．光電轉換結構
132．．．n型半導體層
134．．．p型半導體層
136．．．i型半導體層

Claims (19)

  1. 一種CIGS太陽能電池，包含：一玻璃基板，該玻璃基板之至少一表面包含複數個陣列式凹凸部，該些陣列式凹凸部之最頂端延伸至最底端之距離為一預定深度；一光吸收表面，包含該些陣列式凹凸部最頂端形成表面、該些陣列式凹凸部由最頂端延伸至最底端所形成表面與該些陣列式凹凸部最底端基板除陣列式凹凸部所形成表面之集合；以及一光電轉換結構，該光電轉換結構由下列各層所組成：一n型半導體層，位於該光吸收表面上方，且n型半導體層為一CIGS類化合物；一p型半導體層，位於該n型半導體層上方，且該p型半導體層為一氧化物；以及一i型半導體層，位於該n型半導體層與該p型半導體層間，且該i型半導體層為一氧化物。
  2. 如請求項1所述之CIGS太陽能電池，更包含：一下電極，位於該玻璃基板與該光電轉換結構之間，且該下電極為一金屬。
  3. 如請求項2所述之CIGS太陽能電池，其中該金屬係選自鈦、鉬、鉭或由上述任意合金所組成之組合。
  4. 如請求項1所述之CIGS太陽能電池，更包含：一下電極，位該玻璃基板與該光電轉換結構之間，且該下電極為一非金屬氧化物；以及一鈉化合物層，位於該下電極與該光電轉換結構之間。
  5. 如請求項1所述之CIGS太陽能電池，更包含：一上電極，位於該下電極上方。
  6. 如請求項1所述之CIGS太陽能電池，更包含：一中間層，位於該光電轉換結構與該下電極之間。
  7. 如請求項6所述之CIGS太陽能電池，其中該中間層材質為錫、碲或鉛。
  8. 如請求項5所述之CIGS太陽能電池，更包含：一導線，位於該上電極之上方。
  9. 如請求項8所述之CIGS太陽能電池，更包含：一抗反射層，位於該導線之上方。
  10. 如請求項1所述之CIGS太陽能電池，其中該預定深度為1釐米以上。
  11. 如請求項1所述之CIGS太陽能電池，其中該CIGS 類化合物包含一第一前驅化合物與一第二前驅化合物。
  12. 如請求項11所述之CIGS太陽能電池，其中該第一前驅化合物包含銅、鎵與硒。
  13. 如請求項11所述之CIGS太陽能電池，其中該第二前驅化合物包含銦與硒。
  14. 如請求項1所述之CIGS太陽能電池，其中該CIGS類化合物之化學式為Sn：Cu(In1-x Gax )Se2 ，其中x值為0.18-0.3。
  15. 如請求項1所述之CIGS太陽能電池，其中該p型半導體層包含銅與鋁之氧化物。
  16. 如請求項1所述之CIGS太陽能電池，其中該些陣列式凹凸部具有相同之一預定間距。
  17. 如請求項16所述之CIGS太陽能電池，其中該預定間距為0.625釐米。
  18. 如請求項1所述之CIGS太陽能電池，其中該些陣列式凹凸部之外形為幾何圖形柱體。
  19. 如請求項18所述之CIGS太陽能電池，其中該些陣列式凹凸部之外形為圓形柱體。
TW099121861A 2010-07-02 2010-07-02 Ｃｉｇｓ太陽能電池 TWI405347B (zh)

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