TWI501414B - 用於ｃｉｇｓ電池的氧化鋅膜方法和結構 - Google Patents

用於ｃｉｇｓ電池的氧化鋅膜方法和結構 Download PDF

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TWI501414B
TWI501414B TW099133467A TW99133467A TWI501414B TW I501414 B TWI501414 B TW I501414B TW 099133467 A TW099133467 A TW 099133467A TW 99133467 A TW99133467 A TW 99133467A TW I501414 B TWI501414 B TW I501414B
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Robert D Wieting
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Description

用於CIGS電池的氧化鋅膜方法和結構
本發明總體涉及光電材料及製造方法。更具體地，本發明提供了一種用於薄膜光電池的方法和結構。僅通過實例的方式，本發明的方法和結構提供了利用包含銅銦二硫化物物質的吸收材料的薄膜光電池。
從一開始，人類已致力於發現開發能源的方式。能源來源於如石油化學、水力發電、原子核、風、生物質、太陽的形式，以及更原始的形式如木材和煤來源。在過去的世紀中，現代文明已依賴石油化學能量作為重要的能源。石油化學能源包括氣體和油。氣體包括較輕形式如丁烷和丙烷，通常用於加熱住宅(取暖)和用作用於烹調的燃料。氣體還包括汽油、柴油、和噴氣燃料，通常用於運輸目的。在一些地方，較重形式的石油化學品也可以用於加熱住宅。不幸的是，石油化學燃料的供應是有限的，並且基於行星地球上可獲的量基本上是固定的。另外，隨著更多的人以增長的量利用石油產品，它將快速成為一種稀缺資源，其隨時間將最終變得耗竭。
最近，已期望環境清潔和可再生的能源。清潔能源的實例是水力發電能。水力發電能來源於由水壩如內華達州的Hoover Dam產生的水流驅動的發電機。產生的電能用於為加利福尼亞洛杉磯的大部分城市供電。清潔和可再生的能源還包括風、波浪、生物質等。也就是說，風車將風能轉化為更有用形式的能源如電能。清潔能源還有的其他類型包括太陽能。太陽能的具體細節可以在 整個本發明背景中並更具體地在下文中找到。
太陽能技術通常將來自太陽的電磁輻射轉化為其他有用的能量形式。這些其他能量形式包括熱能和電能。對於電能應用，通常使用太陽能電池。雖然太陽能是環境清潔的並在每一點上已經是成功的，但是在其變為在全世界廣泛使用之前仍然有許多限制有待解決。作為實例，一種類型的太陽能電池利用來源於半導體材料錠的結晶材料。這些結晶材料可以用於製造包括將電磁輻射轉化為電能的光伏器件和光電二極體器件的光電器件。然而，結晶材料通常是昂貴的並難以大規模製備。另外，由這樣的結晶材料製成的器件通常具有低能量轉化效率。其他類型的太陽能電池使用“薄膜”技術以形成感光材料的薄膜用於將電磁輻射轉化為電能。類似的限制存在於製造太陽能電池時薄膜技術的使用中。也就是說，效率通常較差。另外，膜可靠性通常較差並且在常規環境應用中不能用於較長的時期。通常，薄膜難以彼此機械地整合。這些常規技術的這些和其他限制可以在整個本發明說明書並更具體地在下文中找到。
根據上述，可以看出期望用於製造光電材料的改進的技術和得到的器件。
根據本發明的實施方式，提供了一種用於形成光電池的方法和結構。更具體地，本發明提供了一種用於形成薄膜串聯光電池的方法和結構。僅通過實例的方式，根據本發明的實施方式已經利用薄膜半導體材料實施。但是應當認識到根據本發明的實施方式可以具有更廣泛範圍的適用性。
在一個具體實施方式中，提供了一種用於製造薄膜光電池器件的方法。該方法包括提供基板。該基板包括吸收層和形成在吸收層上的覆蓋(疊置)窗口層。該方法包括將基板裝載到室中並使基板經受真空環境。在一個具體實施方式中，真空環境具有從0.1托到約0.02托範圍內的壓力。將來源於二乙基鋅物質和水物質的反應物物質的混合物和載氣引入到室中。該方法包括利用選擇的流速將乙硼烷物質引入到反應物物質的混合物中。利用選擇的流形成覆蓋在視窗層之上的氧化鋅(鋅氧化物)膜以限定透明導電氧化物以提供約2.5毫歐-cm和更小的電阻率和約3000到5000埃的平均粒徑。
在一個可替換的實施方式中，提供了一種用於形成薄膜光電器件的方法。該方法包括提供包括表面區的基板。該方法形成覆蓋在表面區之上的第一電極層、以及形成覆蓋在第一電極層之上的包含銅物質、銦物質、和硒化物物質的吸收材料。形成包含鎘硒化物(硒化鎘)物質的視窗層覆蓋在吸收材料之上。在一個具體實施方式中，該方法利用一種或多種前體氣體形成覆蓋在視窗層之上的氧化鋅層，該氧化鋅層特徵在於從約第一值到約第二值的範圍的粒徑。在一個具體實施方式中，一種或多種前體氣體包括鋅物質和氧物質以及載氣。在一個具體實施方式中，載氣包括至少氮物質。該方法在大於約200攝氏度的溫度下進行至少形成氧化鋅層的全部或一部分，同時保持包含鋅物質和氧物質的氣體混合物的選擇的流速。
通過根據本發明的實施方式，可以獲得許多益處。例如，可以利用對常規設備沒有實質改變的技術製造薄膜串聯光電池。另外，本發明的薄膜光電池與常規的光電池相比具有提高的轉換效率，並提供了一種將陽光轉換為電能的節約成本的方式。取決於實施方式，可以獲得一個或多個這些益處。通過整個本發明說明書以及特別是下面的內容更詳細地描述了這些和其他益處。
根據本發明的實施方式，提供了用於形成光電池的方法和結構。更具體地，根據本發明的實施方式提供了用於形成薄膜光電池的方法和結構。僅僅通過實例的方式，根據本發明的實施方式已經利用薄膜半導體材料實施。但是應當認識到，根據本發明的實施方式可以具有更廣泛範圍的適用性。
圖1為示出了根據本發明一個實施方式的形成光電池的方法的簡化工藝流程圖。如所示的，該方法起始於開始步驟(步驟102)。提供了透明的基板。在一個具體實施方式中，透明基板可以使用玻璃基板如鈉鈣玻璃。也可以使用其他透明基板材料。這些其他透明基板材料可以包括熔融石英(石英玻璃)、石英等。形成第一電極層覆蓋在透明基板的第一表面區之上(步驟106)。在一個具體實施方式中，可以利用鉬材料提供第一電極層。根據應用，也可以使用其他電極材料如透明導電氧化物材料、其他金屬材料。該方法包括形成覆蓋在第一電極層之上的吸收層(步驟108)、以及形成覆蓋在吸收層之上的視窗層(步驟110)。在一個具體實施方式中，吸收層包含CIGS材料或CIS材料，窗口層包含鎘硫化物材料。在一個具體實施方式中，該方法包括將具有形 成在基板上的吸收層和視窗層的基板(包括透明基板)裝載到室中(步驟112)。該方法使基板經受真空環境(步驟114)並引入來源於含鋅的物質和水物質的反應物物質的混合物和載氣(步驟116)。在一個具體實施方式中，含鋅的物質可以由二乙基鋅提供。在一個具體實施方式中，該方法利用選擇的流速將乙硼烷物質引入反應物物質的混合物中。在一個具體實施方式中，形成包含氧化鋅材料的透明導電氧化物材料(步驟118)覆蓋在視窗層之上。該方法進行其他步驟(步驟120)以完成光電池。該方法終止於結束(END)步驟(步驟122)。當然，可以存在其他改變、更改、和替換。
其中，所述二乙基鋅物質可以為二乙基鋅蒸氣，所述水物質可以為水蒸氣。其中，所述載氣包括氮氣或氬氣。
上面的步驟順序提供了一種根據本發明實施方式的形成光電器件的方法。如所示的，在一個具體實施方式中，該方法包括形成包含氧化鋅材料的透明導電氧化物層的步驟。氧化物材料優選特徵在於大於約99%的透光率和約2.5毫歐-cm和更小的電阻率。取決於實施方式，可以加入一個或多個步驟，可以去除一個或多個步驟，以及可以以不同的順序進行一個或多個步驟而不偏離本文的申請專利範圍。本領域技術人員應當認識到其他改變、更改、和替換。
圖2-6為示出了根據本發明實施方式的形成薄膜光電器件的方法的簡圖。這些圖僅是實例，不應當不適當地限制本文的申請專利範圍。本領域技術人員會認識到其他改變、更改、和替換。如圖2中所示，提供了包括表面區204的透明基板構件202。在 某一個實施方式中，基板構件可以為玻璃材料如鈉鈣玻璃。鈉鈣玻璃為用於透明基板構件的節約成本的選擇。也可以使用其他合適的透明基板如石英、熔融石英、太陽能玻璃(solar glass)。每個透明基板可以包括沉積在表面區上的阻擋層。在一個具體實施方式中，阻擋層可以防止鈉離子從玻璃材料擴散到光電材料區中。阻擋層可以為利用以下技術沉積的介電材料如矽氧化物(氧化矽)，如濺射工藝、化學氣相沉積工藝、包括等離子體增強工藝等。也可以使用其他阻擋材料。取決於實施方式，這些阻擋材料包括氧化鋁、氮化鈦、氮化矽、氧化鉭、氧化鋯。
參照圖3，該方法包括形成覆蓋在透明基板構件的表面區之上的第一電極層302，該透明基板構件可以具有形成在其上的阻擋層。可以利用透明導電氧化物(TCO)如氧化銦錫(通常稱為ITO)、摻雜氟的錫氧化物等提供第一電極層。在一些實施方式中，可以利用金屬材料提供第一電極層。在一個具體實施方式中，金屬材料可以為鉬材料。可以利用沉積技術如濺射、電鍍、物理氣相沉積(包括蒸發、昇華)、化學氣相沉積(包括等離子體增強工藝)，接著進行圖案化工藝來形成鉬材料。鉬材料對基於CIG或CIGS的薄膜光電池提供了優於其他電極材料的一些優勢。例如，鉬材料提供了對於CIGS膜來說低的接觸電阻和在隨後的工藝步驟中的穩定性。在一個具體實施方式中，通過沉積第一鉬層覆蓋在透明基板構件之上來形成鉬材料。在一個具體實施方式中，第一鉬層具有第一厚度和抗拉特性。形成具有壓縮特徵和第二厚度的第二鉬層覆蓋在第一鉬層之上。在一個具體實施方式中，如所示的，可以進一步圖案化包含鉬材料的第一電極層。 鉬材料的沉積和圖案化的進一步的細節可以至少在共同轉讓的於2008年9月30日提交的美國臨時申請號61/101,646(代理人檔案號：026335-003800US)和於2008年9月30日提交的美國臨時申請號61/101,650(代理人檔案號：026335-003900US)中找到，將其通過引用的方式併入本文中。當然，可以存在其他改變、更改、和替換。
如圖4所示，該方法包括形成覆蓋在第一電極層的表面區之上的吸收層402。在一個具體實施方式中，吸收層可以為薄膜半導體材料。在一個具體實施方式中，取決於應用，薄膜半導體材料為由銅銦二硫化物材料、或銅銦鎵二硫化物材料、或銅銦二硒化物材料、或銅銦鎵二硒化物材料、這些的任何組合等提供的p型半導體材料。典型地，p型特徵可以利用摻雜劑如硼或鋁物質提供。吸收層可以通過如濺射、電鍍、蒸發(包括硫化或硒化步驟)的技術沉積。形成吸收材料的進一步的細節可以在共同轉讓的標題為“High Efficiency Photovoltaic Cell and Manufacturing Method”的臨時美國專利申請號61/059,253中找到，將其通過引用的方式併入本文中。
在一個具體實施方式中，該方法形成覆蓋在吸收層的表面區之上的視窗層502以形成光電膜堆疊從而為光電池提供pn結。在一個具體實施方式中，通常利用用於p型吸收層的廣帶隙n型半導體材料來提供視窗層。在一個優選的實施方式中，對於利用CIGS、CIS和相關材料作為吸收層的光電池，視窗層利用鎘硫化物材料。視窗層可以利用如濺射、真空蒸發、化學浴沉積等的技術來沉積。
參照圖6，該方法包括提供基板602。該基板包括透明基板構件，該透明基板構件具有覆蓋在透明基板構件之上的第一電極層。薄膜吸收層覆蓋在第一電極層之上，而視窗層覆蓋在薄膜吸收層之上。如所示的，將基板裝載到室604中。該室包括內容積606。該室還包括泵送系統608以提供合適的真空水準。如所示的，在一個具體實施方式中，該室包括一個或多個氣體管線610和多個輔助件以引入一種或多種前體物質用於形成覆蓋在視窗層之上的透明導電氧化物材料614。該室包括一個或多個加熱裝置612以提供用於透明導電材料沉積的的合適的反應溫度。在一個優選的實施方式中，透明導電氧化物包括氧化鋅材料。當然，可以存在其他改變、更改、和替換。
再次參照圖6，該方法包括將基板裝載到室中。在一個具體實施方式中，向下抽吸該室與基板以使壓力在從約0.1托到約0.02托的範圍。利用一個或多個氣體管線，將反應物或前體物質的混合物引入到室中。在一個具體實施方式中，對於氧化鋅材料，反應物物質的混合物可以包括利用載氣提供的二乙基鋅材料和含氧的物質。在一個具體實施方式中，含氧的物質可以為水。取決於實施方式，二乙基鋅材料可以以半導體級、或催化劑級提供。在一個具體實施方式中，水與二乙基鋅比率大於約1到約4。在另一個實施方式中，水與二乙基鋅比率為約1。在一個具體實施方式中，載氣可以為惰性氣體如氮、氬、氦等。在某一個實施方式中，來源於乙硼烷物質的含硼的物質也可以以選擇的流速與反應物的混合物一起引入以形成摻雜硼的氧化鋅材料。取決於應用，也可以使用其他含硼的物質如硼鹵化物(例如，三氯化硼、 三氟化硼、三溴化硼)、或硼氫鹵化物。可以以0%至約5%的乙硼烷與二乙基鋅比率提供乙硼烷物質。在一個具體實施方式中，乙硼烷比率與二乙基鋅比率為約1%。取決於實施方式，在氧化鋅材料沉積期間，該室可以處於約0.5托到約1托的壓力下。在一個具體實施方式中，為了氧化鋅材料的沉積，將基板保持在從約130攝氏度到約190攝氏度範圍內的溫度。在一個可替換的實施方式中，可以將基板保持在約200攝氏度的溫度，並且可以更高。含硼的物質可以降低氧化鋅材料的電阻率特性。取決於氧化鋅材料中含硼的物質的水準，氧化鋅材料可以具有約2.5毫歐-cm和更小的電阻率。此外，取決於含硼的物質的水準，氧化鋅材料可以具有從約3000埃到約5000埃範圍內的粒徑以對於在從約800納米到約1200納米範圍內的波長範圍中的電磁輻射提供80%或更大並優選為90%和更大的透射比。在一個具體實施方式中，氧化鋅材料可以具有模糊的(hazy)外觀。當然，可以存在其他改變、更改、和替換。
雖然已經利用具體的實施方式描述了本發明，但應當理解可以實施對本發明中所用的方法的多種改變、更改、和變換而沒有偏離如所附的權利要求中限定的本發明的精神和範圍。例如，可以利用硼作為摻雜劑物質示出氧化鋅材料。也可以使用其他摻雜劑如氫、鋁、銦、鎵等。此外，雖然上面已經就CIS和/或CIGS薄膜電池的具體結構進行了一般描述，但也可以使用其他具體CIS和/或CIGS構造，如在美國專利號4,612,411和美國專利號4,611,091中提及的那些構造，將其通過引用方式併入本文中，而沒有偏離通過本文的申請專利範圍描述的本發明。此外，根據本 發明的實施方式可以用於其他薄膜構造如由金屬氧化物材料、金屬硫化物材料或金屬硒化物材料提供的那些構造。本領域的普通技術人員會認識到其他改變、更改、和替換。
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202‧‧‧透明基板構件
204‧‧‧表面區
302‧‧‧第一電極層
402‧‧‧吸收層
502‧‧‧視窗層
602‧‧‧基板
604‧‧‧室
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608‧‧‧泵送系統
610‧‧‧氣體管線
612‧‧‧加熱裝置
614‧‧‧透明導電氧化物材料
圖1為示出了根據本發明一個實施方式的製造薄膜光電器件的方法的簡化工藝流程圖。
圖2至圖6為示出了根據本發明實施方式的製造薄膜光電器件的方法的簡化圖。
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Claims (21)

  1. 一種用於製造薄膜光電器件的方法，所述方法包括：提供一基板，該基板包括一吸收層及一覆蓋在所述吸收層之上的視窗層；將所述基板裝載到室中；使所述基板經受從0.1托到約0.02托範圍內的真空環境，並將所述基板保持在介於約130攝氏度到約190攝氏度的溫度；引入來源於二乙基鋅物質和水物質的反應物物質的混合物和載氣；利用選擇的流速將乙硼烷物質引入到所述反應物物質的混合物中，所述乙硼烷物質與二乙基鋅的比值小於5%；利用所述選擇的流速形成覆蓋在所述視窗層之上的氧化鋅膜以形成一透明導電氧化物，該透明導電氧化物具有約2.5毫歐-cm和更小的電阻率和約3000埃到約5000埃的平均粒徑。
  2. 如申請專利範圍第1項所述之方法，其中，所述二乙基鋅物質為二乙基鋅蒸氣。
  3. 如申請專利範圍第1項所述之方法，其中，所述水物質為水蒸氣。
  4. 如申請專利範圍第1項所述之方法，其中，所述載氣包括氮氣或氬氣。
  5. 如申請專利範圍第1項所述之方法，其中，所述水與二乙基鋅比率為大於約1到約4
  6. 如申請專利範圍第1項所述之方法，其中，所述水與二乙基鋅比率為約1。
  7. 如申請專利範圍第1項所述之方法，其中，所述乙硼烷與二乙基鋅比率為1%。
  8. 如申請專利範圍第1項所述之方法，其中，將所述基板保持在大於約200攝氏度的溫度。
  9. 如申請專利範圍第1項所述之方法，其中，所述氧化鋅膜是模糊的。
  10. 如申請專利範圍第1項所述之方法，其中，所述氧化鋅膜具有90%和更大的透光比。
  11. 如申請專利範圍第1項所述之方法，其中，所述氧化鋅膜對於具有約800納米到約1200納米的波長的電磁輻射具有80%和更大的透射比。
  12. 如申請專利範圍第1項所述之方法，其中，所述引入將所述室的壓力增大到約0.5到1托。
  13. 如申請專利範圍第1項所述之方法，其中，所述二乙基鋅為半導體級。
  14. 如申請專利範圍第1項所述之方法，其中，所述二乙基鋅為催化劑級。
  15. 如申請專利範圍第1項所述之方法，其中，所述吸收層包含CIGS材料或CIG材料。
  16. 如申請專利範圍第1項所述之方法，其中，所述視窗層包含鎘硫化物材料。
  17. 一種用於形成薄膜光電器件的方法，所述方法包括：提供包括表面區的基板； 形成覆蓋在所述表面區之上的第一電極層；形成覆蓋在所述第一電極層之上的包含銅物質、銦物質、和硒化物物質的吸收材料；形成覆蓋在所述吸收材料之上的包含鎘硒化物物質的視窗層；使所述基板經受從0.1托到約0.02托範圍內的真空環境；利用包含鋅物質和氧物質的一種或多種前體氣體和包含至少一氮物質的載氣，在大於約200攝氏度的溫度下形成覆蓋在所述視窗層之上的氧化鋅層，所述氧化鋅層的特徵在於具有從約3000埃到約5000埃範圍內的粒徑，所述氧化鋅層形成一具有小於約2.5毫歐-cm的電阻率的透明導電氧化物層。
  18. 如申請專利範圍第17項所述之方法，其中，含氧的物質來源於水蒸氣。
  19. 如申請專利範圍第17項所述之方法，其中，所述鋅物質來源於二乙基鋅。
  20. 如申請專利範圍第17項所述之方法，其中，所述氮物質為氮氣。
  21. 如申請專利範圍第17項所述之方法，其中，所述氧化鋅層的特徵在於99%和更大的透光比。
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