TWI549309B - 用於多接面太陽能電池之擬晶式窗口層 - Google Patents

用於多接面太陽能電池之擬晶式窗口層 Download PDF

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TWI549309B
TWI549309B TW101105608A TW101105608A TWI549309B TW I549309 B TWI549309 B TW I549309B TW 101105608 A TW101105608 A TW 101105608A TW 101105608 A TW101105608 A TW 101105608A TW I549309 B TWI549309 B TW I549309B
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埃爾伯圖斯 麗貝卡Ｅ 瓊斯
費倫 蘇萊茲 艾利艾斯
邁克爾 韋斯特 維摩爾
邁克爾Ｊ 謝爾登
霍曼Ｂ 袁
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太陽結公司
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Description

用於多接面太陽能電池之擬晶式窗口層
本發明大體上與光伏打太陽能電池有關，更具體地，有關基於III-V族半導體化合物的高效多接面光伏打太陽能電池。
基於III-V族半導體化合物的多接面太陽能電池已經展示在由太陽輻射發電方面的高效率。這種電池的效率在AMOG光譜(參見http：//www.sharp┐world.com/corporate/news/091022.html)下已經達到35.8%，並且在等同於幾百個太陽的集中光照下已經達到43.5%(參見M.A.Green等人的Progress in Photovoltaics：Research and Applications 19(2011)565-572)。該效率和功率的實現能夠使該技術應用於太空和地球能量市場。迄今為止，具有最高效率的太陽能電池已經採用具有不同能帶間隙的三個子電池，並被設置為允許各子電池吸收太陽光譜的不同部分。每個子電池均包括功能性p-n接面和其它層，諸如窗口層和背面場層。這些子電池通過隧道接面，或者連接至與下層襯底晶格匹配的層，或者連接至生長於變質緩衝層之上的層。
每個子電池通常包括窗口、發射極、基極和背面場(BSF)，並且可以包括或不包括其它層。本領域技術人員還應認識到，可以構造並不包含全部前述層的子電池。窗口和BSF分別將少數載子反射至遠離它們與發射極層和基極層的介面，並且眾所周知，窗口和BSF對高效載子收集至關重要。 用於窗口的材料和摻雜程度被選擇為使能帶排列對少數載子產生大的能量阻障並對多數載子具有最小阻障。這允許多數載子通過窗口擴散，而少數載子被反射。為了使少數載子表面複合速度最小，窗口和發射極之間的介面具有極高品質是很重要的。窗口還通常具有比相鄰發射極更高的帶隙，以使其對入射光的吸收最小。
對於頂部子電池，窗口可以是電流損失的主要來源。窗口吸收太陽光譜中位於其帶隙之上的一部分入射光，並且窗口產生電子-電洞對，或光載子。由於窗口頂部的少數載子的高表面複合速度以及窗口材料中常見的、少數載子的低擴散長度，所以並未對這些光載子進行高效地收集。在位於頂部子電池下方的子電池中，窗口的帶隙不需要像頂部子電池中那樣高，這是因為頂部子電池已經吸收了更高能量的光子。下部的子電池的窗口層會是損失的來源，如果上部的子電池未吸收該窗口的帶隙之上的所有光的話。
本徵材料晶格常數被限定為，使得材料將具有的晶格間距與無支撐晶體一樣。當半導體材料具有與其所生長的襯底或下層基本不同的本徵晶格常數時，該材料將最初採用下層的晶格常數。半導體材料應變，然而，應變的程度與該材料與其所生長的相鄰材料之間的本徵材料晶格常數的差異成正比。隨著該半導體層的厚度的增加，所累積的應變增加，直至達到臨界厚度，在此之後，非常有利於通過錯位(即，原子背離其正常晶體結構)來鬆弛和緩和應變。臨界厚度取決於許多因素，包括所涉及材料、襯底和/或下層、生長技術和生長條件。對於約1%的本徵材料晶格常數的差異，Wanlass等人的第4,935,384號美國專利教導，臨界厚度為約15nm。在該臨界厚度之下，根據Wanlass的披露，半導體層被認為是擬晶式或完全應變的，並且半導體層在垂 直於生長方向的平面中保持其襯底或下層的晶格常數。通常，該層在生長方向上將具有不同的晶格常數，並且所有晶格常數都不同於該材料的本徵材料晶格常數。當充分錯位已經形成該層已經基本恢復至其本徵材料晶格常數時，該半導體層被認為是完全鬆弛。通常，當通過基本不同的晶格常數生長於襯底或層的頂部時，層可以完全應變、完全鬆弛、或部分應變和部分鬆弛。該討論係假定材料具有本徵材料晶格常數在所有三個晶體方向上都相同的立方晶體結構。類似的討論適於不是立方的材料。
現有技術主要是具有窗口層的光伏打電池，其中窗口層的本徵材料晶格常數標稱上與它們下方的電池層相同。對於給定的合金系統，晶格常數的選擇決定了材料的成分並因此決定其有關特性，諸如其帶隙能量。例如，完全無序的AlxIn1-xP具有與GaAs襯底基本相同的本徵材料晶核常數，其中x=0.52。該成分在300K下具有2.29eV的間接帶隙以及2.37eV的直接帶隙。應變的、擬晶式的窗口層被Wanlass等人和King等人(第7,119,271號美國專利)提到，但如上所述，該教導為，對於晶格常數的1%的差異，臨界厚度為15nm。15nm或更少的厚度對於許多多接面太陽能電池的實際使用來說太薄，因此，King等人關注完全鬆弛而非擬晶式的窗口層。
King等人使用併入錯位之完全鬆弛的高帶隙窗口層，以達成光伏打電池的鬆弛。雖然經由錯位的鬆弛已經被要求以改進介面品質並使缺陷傳輸最小化，但文獻中的更大的工作主體顯示，錯位為劣化材料品質並降低其電流收集效率的非輻射複合中心。此外，發射極和窗口的介面處的缺陷可以增加少數載子的表面複合速度，並進一步劣化太陽能電池的效率。因此，對於高效太陽能電池來說，完全鬆弛的窗口層並不理想。
為了改善高效太陽能電池的效率，期望使頂部子電池的窗口層的帶隙最大化，這通常降低窗口中的光吸收率並增加太陽能電池的電流，並且避免鬆弛所產生的錯位。
根據本發明，提供了具有一個或多個子電池的光伏打太陽能電池，其中至少一個子電池具有寬頻隙的擬晶式窗口層，該窗口層具有至少15nm的厚度並且其本徵材料晶格常數與相鄰發射極層的本徵材料晶格常數相差至少1%。相比於與相鄰發射極層具有基本相同的本徵材料晶格常數的窗口層，該窗口層具有更高帶隙，這增加了光穿過窗口的透射，從而增加了太陽能電池中的電流產出。生成擬晶式材料的品質保證窗口與發射極之間的良好介面，從而降低了少數載子表面複合速度，因而具有更高效率。
在根據本發明的方法中，生長了光伏打電池的寬頻隙的擬晶式(Al)In(Ga)P窗口層，其晶格常數與相鄰發射極層的晶格常數相差至少1%。該方法利用300-550攝氏度的生長溫度以及至少0.1微米每小時的生長速率來沈積15-60nm厚的完全應變層。用於生長該層的單質和分子原材料具有至少99.9999%的純度。在小於10-5托的背景壓力下，分子束磊晶是沈積窗口層的較佳技術。通過使用該生長方法來抑制為了適應晶格常數的改變而導致的鬆弛或錯位的形成。
10‧‧‧接觸層
11‧‧‧帽
12‧‧‧AlxIn1-xP窗口
13‧‧‧(Al)GaInP發射極
14‧‧‧GaInP基極
15‧‧‧AlGaInP背面場
16‧‧‧緩衝層
17‧‧‧襯底
20‧‧‧接觸部
21‧‧‧帽
22‧‧‧抗反射層
23‧‧‧窗口
24‧‧‧發射極
25‧‧‧基極
26‧‧‧背面場
27‧‧‧隧道接面
28‧‧‧窗口
29‧‧‧發射極
30‧‧‧基極
31‧‧‧背面場
32‧‧‧隧道接面
33‧‧‧窗口
34‧‧‧發射極
35‧‧‧基極
36‧‧‧背面場
37‧‧‧緩衝層
38‧‧‧襯底
圖1顯示根據本發明的單接面太陽能電池的實施例的示意性截面圖； 圖2A顯示具有通過隧道接面連接的三個子電池的光伏打電池的示意性截面圖，其中每個子電池包括窗口、發射極、基極和背面場；圖2B顯示根據本發明的多接面太陽能電池的一個子電池的示意性截面圖；圖3顯示測量到的不具有抗反射塗層(ARC)的兩個GaInP太陽能電池的外部量子效率(EQE)和內部量子效率(IQE)；圖4顯示測量到的不具有抗反射塗層(ARC)的兩個GaInP太陽能電池結構的反射率；圖5A1顯示使用兩個GaInP太陽能電池的外部量子效率和內部量子效率的資料計算的短路電流(Jsc)以及這兩個太陽能電池之間的Jsc的差；圖5A顯示測量到的兩個多接面太陽能電池的GaInP子電池的內部量子效率(IQE)；圖5A2顯示使用多接面太陽能電池的兩個GaInP子電池的外部量子效率和內部量子效率的資料計算的短路電流(Jsc)以及這兩個子電池之間的Jsc的差；圖5B顯示測量到的兩個多接面太陽能電池的GaInP子電池的外部量子效率(EQE)；圖6顯示測量到的兩個多接面太陽能電池的反射率；圖7顯示根據本發明在頂部子電池中具有完全應變的AlInP窗口的三接面太陽能電池的三軸x射線衍射掃描； 圖8顯示根據本發明沿著GaAs襯底上的三接面太陽能電池的不對稱方向(224)的倒空間圖，該三接面太陽能電池包括具有完全應變的Al0.73In0.27P窗口的一個子電池；圖9顯示根據本發明沿著GaAs襯底上的三接面太陽能電池的對稱方向(004)的倒空間圖，該三接面太陽能電池包括具有完全應變的Al0.73In0.27P窗口的一個子電池。
根據本發明，提供了具有一個或多個子電池的光伏打電池，其中子電池中的至少一個具有擬晶式窗口層，擬晶式窗口層的本徵材料晶格常數與該子電池的相鄰發射極層相差大於1%。該窗口層的厚度大於15nm至等於或小於60nm的量級。該窗口層的帶隙比與相鄰發射極層具有基本相同的本徵材料晶格常數的材料或成分更高。在本徵材料晶格常數上與相鄰發射極層差異大於1%而不是更小的量，使窗口層中的帶隙的增加最大化。期望更高的帶隙，這是因為它們通過降低可被窗口層吸收的一部分太陽光譜使太陽能電池效率獲得更大的增加。
例如，圖1顯示根據本發明的具有一個子電池的光伏打電池(又稱為單接面太陽能電池)的示意性截面圖。各層並不按比例繪製。除了緩衝層16、襯底17、帽11和接觸層10之外，電池還包括薄窗口12(例如，AlxIn1-xP)、發射極13(例如，(Al)GaInP)、基極14(例如，GaInP)和背面場15(例如，AlGaInP)。背面接觸部未顯示。發射極、基極和背面場具有與襯底基本相同的本徵材料晶格常數。窗口層的本徵材料晶格常數與相鄰發射極以及襯底的本徵材料晶格常數相差至少1%。這意味著襯底的本徵材料晶格常數減去窗口的 本徵材料晶格常數的結果除以襯底的本徵材料晶格常數得到至少0.01(或1%)的絕對值。窗口層是完全應變的，而不存在經由錯位的鬆弛。在一個實施例中，窗口層是厚度為15nm至60nm的AlxIn1-xP(x>0.65)，並且襯底為GaAs或Ge。AlxIn1-xP(x>0.65)的帶隙比具有與襯底基本相同的本徵材料晶格常數的成分(x=0.52)更寬，從而增加了光向發射極和基極的透射並增加光伏打電池的效率。由於上述原因，發射極和基極中的電流收集效率比窗口層中更高。增加光向發射極和基極的透射並減少窗口層中的吸收將增加太陽能電池的總體電流收集和效率。
圖2A顯示示例性光伏打電池的示意性截面圖，該光伏打電池包括三個子電池(可被識別為頂部電池、中部電池和底部電池，其中方向參考接近光源上方)，其中每個子電池均包括窗口層23、28、33、發射極層24、29、34、基極層25、30、35、以及背面場(BSF)層26、31、36。這些子電池通過隧道接面27、32連接。襯底38、緩衝層37、帽21、頂部接觸部20和抗反射塗層22(AR)也被顯示。背面接觸部則未顯示。圖2B顯示根據本發明的對應於元件23、24、25和26的光伏打電池的子電池的示意性截面圖。擬晶式窗口層的厚度至少為15nm並且其本徵材料晶格常數與相鄰發射極層的本徵材料晶格常數相差至少1%。在本發明的較佳實施例中，窗口層由AlxIn1-xP(x>0.65)構成，其中x=0.52所表示的成分具有與Ga0.51In0.49P發射極和基極、以及GaAs或Ge襯底基本相同的本徵材料晶格常數。相比於x=0.52，光向發射極和基極的透射係通過由AlxIn1-xP(x>0.65)構成的窗口增加，這可增加光伏打電池的效率。
在某些實施例中，結合本發明的子電池將是光伏打電池的頂部子電池。在這種情況下，窗口可以直接與抗反射塗層相鄰，如圖2A中的窗口 23所示。在這種情況下，也可以將窗口層視為是抗反射塗層的一部分。對於AlInP窗口的示例，AlxIn1-xP的折射率有助於減小抗反射塗層的低折射率與太陽能電池結構中的餘下半導體層的折射率的之間的差異。
本發明提供一種用於在光伏打電池中製造完全應變的AlxIn1-x-yGayP窗口層的方法，其中AlxIn1-x-yGayP材料的晶格常數與相鄰發射極層的晶格常數相差至少1%。例如，在Ga0.51In0.49P發射極的情況下，AlxIn1-xP窗口(x>0.65)的本徵材料晶格常數與該發射極的本徵材料晶格常數相差至少1%。根據該加工方法，生長溫度位於300與550攝氏溫度之間，生長速率為至少0.1微米每小時。用於窗口的原材料包括元素鋁、元素銦、元素鎵和分子磷，它們中的每一個的純度都至少為99.9999%。反應器的背景壓力少於10-5托。在這些非平衡的生長條件下，錯位的形成受到有力地限制，故可以獲得具有15-60nm厚度的完全應變層。在本發明的具體實施例中，分子束磊晶被用於形成完全應變的窗口層。
圖3顯示測量到的具有圖1所示結構的兩個光伏打電池的外部量子效率(EQE)和內部量子效率(IQE)。該電池不具有抗反射塗層。EQE使用校準檢測器測量，並利用標準的參考太陽能電池驗證。用於這些結構的AlxIn1-xP窗口具有約35nm的厚度並且x=0.52和x=0.70，其中Al0.70In0.30P是根據本發明的完全應變層。窗口與GaAs襯底之間的本徵材料晶格常數的差為~0%(x=0.52)和1.3%(x=0.70)。使用圖4中所示的分別測量到的兩個樣本的反射率從EQE獲得IQE。對於350nm至~450nm的波長範圍，樣本在x=0.70下的EQE響應高於樣本在x=0.52下的EQE回應，這是因為光通過窗口的透射率更大。在AM1.5D光譜下，EQE的增加轉換為0.4mA/cm2的電池電流的增加。然 而，窗口中的樣本在x=0.70下的反射率低於樣本在x=0.70下的反射率(見圖4)。因此，在AM1.5D光譜下，當使用IQE資料進行計算時，電流的提升更低(0.2mA/cm2)(圖5A1)。
圖5A顯示IQE與圖5B顯示測量到的具有抗反射塗層(ARC)的多接面光伏打電池的GaInP子電池的EQE。該子電池的結構在圖2B中顯示，並且GaInP層和(Al)InGaP層具有與GaAs襯底基本相同的本徵材料晶格常數。這些結構的AlxIn1-xP窗口具有約35nm的厚度並且x=0.52和x=0.70，其中Al0.70In0.30P是根據本發明的完全應變層。窗口層與相鄰發射極層之間的本徵材料晶格常數的差為~0%(x=0.52)和1.3%(x=0.70)。使用圖6中所示的分別測量到的兩個樣本的反射率從EQE獲得IQE。此外，對於短的波長範圍，EQE和IQE增加，並且子電池電流也相應增加。在AM1.5D光譜下，子電池電流的增加為0.5mA/cm2，無論電流是從IQE還是EQE確定(見圖5A2)。對於具有三個子電池的多接面太陽能電池，底部子電池常常比上部和中部子電池具有更高的電流產出，這可以是電流匹配的。因此，頂部子電池電流的增加可以通過增加頂部子電池帶隙或減小頂部子電池厚度而在頂部和中部子電池之間分配。隨後根據本發明的該實施例的電流的0.5mA/cm2的增益，將使總的多接面電池電流增加0.25mA/cm2。
倒空間圖和三軸搖擺曲線是用於研究半導體磊晶層中的應變和鬆弛的公知的高解析度、x射線衍射技術。當在具有不同本徵材料晶格常數的襯底上擬晶式地生長層時，使該層的晶格採用襯底的晶格導致膜的晶胞的四邊形無序。磊晶膜襯底系統的Bragg反射將分為兩個反射峰，一個對應於該層，一個對應於襯底。這在圖7中清楚可見，圖7顯示根據本發明的包括具有完全應 變的AlInP窗口層的頂部子電池的多接面太陽能電池的三軸x射線衍射掃描。與AlInP窗口層相鄰的Ga0.51In0.49P發射極具有與GaAs襯底基本相同的本徵材料晶格常數。在(004)方向上，該掃描顯示0 arcsec處的襯底峰值和4300 arcsec附近的Al0.73In0.27P層峰值。使用GaAs和AlInP合金系統的已知晶格常數從適合三軸x射線衍射掃描，對於完全應變層，確定Al0.73In0.27P成分和厚度(42nm)。AlInP膜與GaAs襯底之間的本徵材料晶格常數相差1.5%。
為了導出鬆弛的程度以及AlInP成分，需要比從單一的三軸搖擺曲線的測量獲得的資訊更加結構化的資訊。這就是倒空間圖有用的地方。執行倒空間映射，使得研究中的Bragg反射被完全映射至Q空間中的限制區域中。倒空間圖可以通過將Q空間中的連續的一維掃描結合在一起而獲得。具有不同本徵材料晶格常數的完全應變層將沿著穿過襯底的垂直線具有倒格子點。完全鬆弛層將沿著連接襯底與倒空間原點的直線具有倒格子點。對於襯底上的完全鬆弛的磊晶層，磊晶層的Qx將不同於襯底的Qx。
圖8和9顯示根據本發明的沿著多接面太陽能電池的兩個方向完成的倒空間圖，其中多接面太陽能電池具有頂部子電池，頂部子電池具有Al0.73In0.27P窗口，該窗口具有42nm的厚度，並且其本徵材料晶格常數與襯底和相鄰發射極的本徵材料晶格常數相差1.5%。該圖顯示Al0.73In0.27P窗口是擬晶式的(即，完全應變的)。圖8顯示沿著(224)方向的倒空間圖，其是不對稱掃描。圖9是沿(004)方向的表示圖，其是對稱掃描。對於沿(224)方向的空間圖，襯底與AlInP層的Qx是相同的，並且AlInP層的倒格子點沿著表面法向的垂直直線分佈。這意味著該層是完全應變的，並且具有與襯底相同的面內晶格參數。在對稱掃描的情況下，存在沿著襯底法向的散射向量的非零分量。這意 味著對稱θ-2θ掃描沿著倒空間中的y軸，而搖擺曲線θ掃描沿著倒空間中的x軸。從不與襯底法向平行的一組平面開始的θ-2θ將位於x-y平面中。因此，在相對於襯底觀察的層中不存在鬆弛或傾斜的指示。
本發明已經參照具體實施例進行了說明。對於本領域技術人員來說，其它實施例將是顯而易見的。因此，除了所附申請專利範圍所指示的之外，並非對本發明進行限制。
10‧‧‧接觸層
11‧‧‧帽
12‧‧‧AlxIn1-xP窗口
13‧‧‧(Al)GaInP發射極
14‧‧‧GaInP基極
15‧‧‧AlGaInP背面場
16‧‧‧緩衝層
17‧‧‧襯底

Claims (20)

  1. 一種光伏打電池，包括：至少一個子電池，該至少一個子電池具有發射極層，該發射極層包括具有第一本徵材料晶格常數的第一材料，該至少一個子電池還具有窗口層，該窗口層鄰近於該發射極層設置並包括具有第二本徵材料晶格常數的第二材料，該第二本徵材料晶格常數與該第一本徵材料晶格常數相差大於1%；其中該窗口層是厚度為大於15nm至等於或小於60nm的基本完全應變的擬晶式層，並且該基本完全應變的擬晶式層已經基本為其整個層在垂直於磊晶生長方向的平面中建立了與該第一本徵材料晶格常數相對應的內部晶格常數。
  2. 如請求項1所述的光伏打電池，其中該第二本徵材料晶格常數大於該第一本徵材料晶格常數。
  3. 如請求項1所述的光伏打電池，其中該第二本徵材料晶格常數小於該第一本徵材料晶格常數。
  4. 如請求項3所述的光伏打電池，其中該第二材料選自由AlP、AlInP、InGaP、AlInGaP和GaP構成的群組。
  5. 如請求項1所述的光伏打電池，其中該光伏打電池生長於包括GaAs和Ge之一的一襯底上。
  6. 如請求項1所述的光伏打電池，其中該光伏打電池包括三個或更多個不同的子電池，每個子電池的基極層具有不同的帶隙。
  7. 如請求項1所述的光伏打電池，其中該第一材料是GaAs、InGaP和AlInGaP之一。
  8. 如請求項1所述的光伏打電池，其中該第一材料包括GaInP。
  9. 如請求項1所述的光伏打電池，其中該第二材料包括AlxIn1-xP。
  10. 如請求項9所述的光伏打電池，其中x>0.65。
  11. 如請求項1所述的光伏打電池，其中晶格失配至少為1.3%。
  12. 如請求項1所述的光伏打電池，其中晶格失配至少為1.5%。
  13. 如請求項1所述的光伏打電池，其中該窗口層的厚度至少為35nm。
  14. 如請求項1所述的光伏打電池，其中該窗口層的厚度至少為42nm。
  15. 如請求項1所述的光伏打電池，其中，晶格失配至少為1.3%；以及該窗口層的厚度至少為35nm。
  16. 如請求項15所述的光伏打電池，其中該第二材料包括AlxIn1-xP，其中x>0.65。
  17. 如請求項1所述的光伏打電池，其中該窗口層的特徵在於，相比於與鄰近的該發射極層具有基本相同的本徵材料晶格常數的窗口層，具有更高帶隙。
  18. 一種形成光伏打電池的子電池中與發射極相鄰的完全應變的窗口層的方法，包括：使用分子束磊晶以300攝氏溫度和550攝氏溫度之間的溫度並以至少0.1微米每小時的生長速率生長該窗口層；使用主要包括純度為至少99.9999%的元素鋁、元素銦、元素鎵以及分子磷的原材料；使用少於10-5托的背景壓力；其中，該發射極包括具有第一本徵材料晶格常數的第一材料；該窗口層包括具有第二本徵材料晶格常數的第二材料，該第二本徵材料晶格常數與該第一本徵材料晶格常數相差大於1%；其中該窗口層是厚度為大於15nm至等於或小於60nm的基本完全應變的擬晶式層，並且所述基本完全應變的擬晶式層已經基本為其整個層在垂直於磊晶生長方向的平面中建立了與該第一本徵材料晶格常數相對應的內部晶格常數；以及該窗口層選自由AlInP、AlInGaP和GaInP構成的群組。
  19. 如請求項18所述的方法， 其中該發射極選自由GaInP、AlInGaP和GaAs構成的群組。
  20. 如請求項19所述的方法，其中該窗口由AlxIn1-xP形成，其中x>0.65。
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