TW201543694A - 以硫化氫反應性退火降低奈米粒子－衍生薄膜中之碳 - Google Patents
以硫化氫反應性退火降低奈米粒子－衍生薄膜中之碳 Download PDFInfo
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Abstract
本發明係關於一種使用CIGS奈米粒子在基板上製造CIGS吸收劑層之方法，該方法包括一或多個退火步驟，該等退火步驟涉及加熱該(等)CIGS奈米粒子薄膜以乾燥該薄膜及可能使該等CIGS奈米粒子熔合在一起以形成CIGS晶體。通常，至少該最終退火步驟將誘導粒子熔合以形成CIGS晶體。已發現反應性氣體退火有助於在所得CIGS吸收劑層中生長較大顆粒並改善彼等層之光伏打性能。懷疑CIGS奈米粒子薄膜中存在碳會阻礙可在退火時在CIGS薄膜中獲得之晶體之顆粒生長及限制其大小。已發現將該等CIGS奈米粒子薄膜曝露於含有硫之反應性氛圍下可降低薄膜中之碳量，從而導致退火時生長較大CIGS晶體。
Description
[相關申請案之交叉參考]
本申請案主張2014年1月31日申請之美國臨時專利申請案第61/934,495號之權利。
關於聯邦贊助研究或開發之聲明：不適用
本發明大體上係關於薄膜光伏打裝置。更特定言之，本發明係關於基於銅銦鎵二硒化物/二硫化物(CIGS)之薄膜光伏打裝置。
相關技術之包含於37 CFR 1.97及1.98下所揭示之資訊之說明
光伏打電池提供產生自化石燃料之能量之最具前景的替代品中之一。為實現商業可行性，光伏打電池必須使用低成本材料以廉價方式來製造並展示光電轉換之中高效率。此外，為使裝置製造方法在商業上獲得成功，該等用於合成材料之方法必須係可擴充。
用於現代光伏打裝置中之最普遍材料係矽。然而，矽係非撓性、昂貴，且相對差之光吸收劑。因此，已提出許多薄膜塊狀半導體材料作為矽之潛在替代物，例如，碲化鎘、銅銦鎵硫化物(硒化物)及非晶矽。在此等材料之間，廣泛認為銅銦鎵硫化物(硒化物)(CuXInYGaZSASeB)(通常亦被稱為CIGS)係一種可作為光伏打裝置中之光敏感吸收劑之具有前景的矽替代品。
目前，大多數用於製造CIGS之技術涉及諸如蒸發或濺射之高真空技術。此等技術對高通量操作而言不理想，因為其等涉及具有尺寸限制且難以用高通量方式實施之高真空室。因此，使用彼等技術難以於大基板上及/或在形狀奇怪之基板上製造CIGS膜。
一種用於生產CIGS薄層之具有前景之替換方法係藉由奈米粒子燒結。此技術涉及自CIGS前驅物材料之奈米粒子製造溶液或墨水及使用多種成膜技術中之一者於基板上沉積該墨水之層。然後退火該等經沉積之層以自該等薄膜中移除溶劑及其他墨水組分及使奈米粒子熔合在一起以產出CIGS半導體層。
CIGS墨水之奈米粒子組分包含CIGS前驅物-銅、銦及/或鎵及硫及/或硒之奈米粒子。奈米粒子可包含呈單一奈米粒子之組分中之一或多者。例如，奈米粒子包含Cu、In及Se以提供CuInSe2層。或者，該墨水可含有若干不同類型之奈米粒子，其等經組合以提供所需組分。例如，該墨水可含有Cu與In之奈米粒子及Cu與Se之其他奈米粒子，當將其等組合時提供CuInSe2。
對可作為用於光伏打薄膜之初始材料的CIGS奈米粒子而言，其等應具有許多性質。第一，該等奈米粒子必須小-理想上直徑約幾奈米至幾百奈米。此類小粒子緊密堆積在一起，使得其等在熔合時可更易聚結。第二，窄尺寸分佈有利於確保所有奈米粒子在近似相同之溫度下熔合，從而確保所得薄膜係均勻及具有高品質。第三，較佳地，奈米粒子係以揮發性有機封端劑封端。通常需要此類封端劑以助於在用於在基板上沉積奈米粒子之有機溶液中增溶該等奈米粒子。較佳地，該等封端配位基具有高揮發性，使得在退火薄膜時可將其等有效移除。最後，該等奈米粒子之熔合溫度應低於相應之塊材，容許使用較低之處理溫度。
目前有許多技術可用於製造CIGS奈米粒子。可使用膠體法、溶
劑熱法、聲化學法及塊狀硒化銅之球磨製造奈米粒子。
本文所揭示之方法可以使用任何方法製得之CIGS奈米粒子實施。然而，膠體法尤其具有前景。膠體法通常涉及形成經氧化三辛膦(TOPO)或胺類封端之奈米粒子之高溫(>250℃)合成，諸如「熱注射」技術。熱注射依賴於在高溫下將少量前驅物注射至大量溶劑中。高溫引起前驅物分解，引發奈米粒子之成核作用。接著降低該反應混合物之溫度以支持一定時間內之奈米粒子生長，接著以合適之有機溶劑淬火。在美國專利公開案第2009/0139574 A1號及美國專利案第8,563,348號中揭示膠體奈米粒子合成之其他方法。
奈米粒子一經製備及分離，可將其等調配成可施加於基板以形成薄膜之墨水。此類墨水通常係奈米粒子在有機溶劑(諸如甲苯、異佛爾酮、丙醇等)中之溶液或懸浮液。奈米粒子上之表面結合之配位基有助於奈米粒子分散/懸浮於墨水中及防止奈米粒子聚結。該等墨水亦可含有其他組分，諸如防腐劑、流動或黏度增強劑及類似物。
可使用諸如印刷或噴塗方法、旋塗法、刮刀塗佈法及類似方法之各種成膜技術於基板上形成CIGS墨水之薄膜。一經形成該等薄膜，通常加熱其等以排出薄膜之有機組分並燒結奈米粒子，提供CIGS半導體層。
已觀測到自薄膜中移除有機組分對於獲得高性能CIGS半導體層而言係重要。咸信在燒結過程中膜內存在有機組分會限制半導體顆粒的生長。較小顆粒增加所得半導體層內之晶界數且對薄膜之性能具有不良影響。因此，此項技術中需要在燒結期間移除CIGS薄膜之有機組分之經改良的方法及系統。
本發明提供藉由沉積及退火CIGS奈米粒子前驅物之薄膜以製造用於光伏打裝置之CIGS吸收劑層的系統及方法。該等所揭示之方法
的優點係其等增強自薄膜中移除碳組分及提供更佳之裝置性能。該等所揭示之方法涉及在反應性H2S氛圍中及/或在含有H2S與H2Se之混合物之氛圍中退火經沉積之CIGS奈米粒子薄膜。
100‧‧‧製備CIGS吸收劑層之一般方法
101‧‧‧基板
102‧‧‧CIGS奈米粒子墨水
103‧‧‧印表機
104‧‧‧退火階段/退火步驟
105‧‧‧CIGS層
106‧‧‧CIGS奈米粒子墨水
107‧‧‧印表機
108‧‧‧雙層薄膜
109‧‧‧印表機
110‧‧‧CIGS奈米粒子墨水
111‧‧‧退火階段/退火步驟
112‧‧‧吸收劑層
113‧‧‧第二退火階段/退火步驟
圖1係沉積及退火CIGS奈米粒子之薄膜以提供CIGS半導體層之方法的示意說明圖。
圖2係藉由沉積CIGS奈米粒子及在H2S氛圍中退火薄膜所製得之光伏打裝置的I-V曲線。
圖3係藉由沉積CIGS奈米粒子及在H2S及H2Se氛圍中退火薄膜所製得之光伏打裝置的I-V曲線。
圖4顯示用於形成圖2及圖3之I-V曲線之裝置之CIGS層的XRD光譜。
圖5係用於形成圖3之I-V曲線之裝置之CIGS層的SEM影像。
如本文所使用，術語CIGS係指含有第11族、第13族及第16族之元素的材料。通常，CIGS材料具有式Cu(In,Ga)(S,Se)2。請注意該化學計量可變化。亦請注意「CIGS」可係指此類即使無Ga之材料，例如，CuInS2。如本文所使用，術語CIGS奈米粒子墨水係指含有提供CIGS材料之組分之奈米粒子的墨水。
圖1示意地繪示使用CIGS奈米粒子在基板101上製備CIGS吸收劑層之一般方法100。熟習此項技術者將瞭解可使用許多類型之基板以製造光伏打電池。基板之一個實例係此項技術中已知的塗覆鉬之玻璃。
使用印表機103在基板101上印刷第一CIGS奈米粒子墨水102。
CIGS奈米粒子墨水102通常係含有奈米粒子CIGS前驅物之有機溶劑懸浮液，即，含有至少一第13族之材料(通常係銦及/或鎵)、第11族之材
料(通常係銅)及第16族之材料(通常係硫及/或硒)。可以奈米粒子之單一物質提供所有CIGS前驅物，即，呈具有通式Cu(In,Ga)(S,Se)2之奈米粒子。或者，可提供CIGS前驅物作為兩種或更多種類型之奈米粒子之組分，每種提供一或多種CIGS組分。一實例係含有CuSe2及InSe2奈米粒子以提供CuInSe2 CIGS層之組分的墨水。
本文描述之方法可用於形成以許多方法中之任意方法製造之CIGS奈米粒子之薄膜。美國專利公開案第2009/0139574 A1號，及美國專利案第8,563,348號中揭示形成具有相同尺寸及確定之化學計量之CIGS奈米粒子的方法，兩個案件之全部內容以引用之方式併入本文中。
該等奈米粒子分散於墨水中，此容許精確、可定製化及高效印刷材料之薄層。該墨水通常包含多種有機化合物中之一者，諸如芳族化合物、脂族化合物及/或硒醇或硫醇化合物。通常，該墨水包含甲苯及十二烷。根據某些實施例，該所得之墨水調配物可包含多達約50% w/v之奈米粒子，然而該w/v百分比可調整。此外，可向墨水中添加彈性體或黏合劑以影響材料之塗層性質。
印表機103可係任何此項技術中已知的可適用於分散CIGS奈米粒子墨水之印表機。實例包含點矩陣式印表機、噴墨印表機及類似物。
此外，雖然在圖1中印刷階段1繪示為使用印表機，可使用其他施加薄膜之技術。此類技術之實例包含旋塗、蒸發塗佈、刮刀塗佈、液滴塗佈及任何其他此項技術中已知的用於施加有機薄膜之技術。
薄膜沉積後，在退火階段104中退火該經沉積之CIGS奈米粒子薄膜以產生CIGS層105。退火步驟104通常涉及加熱該等CIGS奈米粒子薄膜至足以乾燥該薄膜之溫度及時間。退火步驟104亦可導致奈米粒子熔合以形成CIGS晶體。下文將更詳細描述該等退火階段。但應注意本方法通常含有至少一個熔合該等奈米粒子以形成晶體之退火步
驟。
接著，在印刷階段2中使用印表機107施加CIGS奈米粒子墨水106。印表機107可係相同印表機103，其可簡單重複利用於印刷階段2中，或印表機107可係一種不同設備。同樣地，CIGS奈米粒子墨水106可係與102相同之墨水調配物或可係不同調配物。可以多層方式施加該相同調配物以提供較厚之薄膜。或者，墨水調配物102及106可相異，以便提供組成隨吸收劑層內之位置而變化之吸收劑層。例如，美國專利案第8,563,348號描述使用多個CIGS層以提供吸收劑層，其中In對Ga之比率隨在吸收劑層內之深度而變化。
印刷階段2後，在第二退火階段113中退火該薄膜以形成雙層薄膜108。注意薄膜108描述為具有兩個不同層之薄膜僅用於說明；實際上，可能沒有(及通常較佳將無)層邊界。
方法100可包含額外印刷階段3，其使用印表機109施加附加CIGS奈米粒子墨水110之層以及額外退火階段111。圖1繪示三階段方法，但該階段之數量可係一至大體上任何數，此取決於所需成品之厚度及組成。方法100之最終產品係吸收劑層112。
該所揭示之方法係關於一或多個在圖1中繪示之退火步驟104、113及111。可根據現在欲討論之方法實踐該等退火步驟中之一或多者。如上所述，退火涉及加熱該(等)CIGS奈米粒子薄膜以乾燥該薄膜及可能使CIGS奈米粒子熔合在一起以形成CIGS晶體。通常，至少該最終退火步驟將引起粒子熔合以形成CIGS晶體。
可使用任何合適之熱源例如烘箱、真空烘箱、爐、IR燈、雷射或熱板加熱該薄膜。退火時間及溫度可取決於奈米粒子大小及組成及墨水組成。無需過度實驗即可獲得此類參數。退火溫度通常高於200℃。可根據溫度斜坡控制退火溫度，藉此該溫度以給定之變化速率從第一溫度變化至第二溫度，維持該第二溫度達較長一段時間及然
後變化至第三溫度等。美國專利公開案第2009/0139574號中揭示溫度斜坡之實例。
可在靜態或動態氛圍下進行退火。根據一個實例，在所選氣體之流動氛圍下使用管形爐進行退火。
美國專利公開案第2009/0139574號描述在靜態及動態惰性氛圍(諸如氮氣)下之退火。然而，亦可使用反應性氛圍。例如，在退火期間易於從膜中排出Se。因此可在諸如H2Se之含有Se之氛圍下退火含有Se之薄膜以維持或調整膜內之Se濃度。亦可在退火期間藉由在含有Se之氛圍下退火含有S之薄膜而使Se代替膜內的S。已經發現使用含有Se之氛圍退火含有S之薄膜有助於在薄膜內形成大顆粒，因為當Se取代S原子時，薄膜體積膨脹。體積膨脹之範圍係約14%。
已發現反應性氣體退火促進在所得CIGS吸收劑層內生長較大顆粒及改善彼等層之光伏打性質。據懷疑在CIGS奈米粒子膜內存在碳會阻礙可在退火時於CIGS薄膜中獲得之晶體之顆粒生長並限制其尺寸。此類碳之潛在來源係用於形成CIGS奈米粒子墨水之溶劑，該墨水中之其他組分，諸如彈性體、黏合劑、黏度調節劑及類似物，以及結合至該等奈米粒子之表面之配位基。
發明者已發現使CIGS奈米粒子薄膜曝露於含硫之反應性氛圍下可降低膜內之碳數量，從而導致在退火時生長較大之CIGS晶體。根據一個實施例，可在諸如H2S之含有硫之反應性氛圍下，進行圖1中所繪示之退火步驟中之一或多者。該CIGS奈米粒薄膜通常含有一或多種類型之提供總組成Cu(In及/或Ga)(S及/或Se)2的奈米粒子。注意在含有S之氛圍下退火含有S或含有Se之薄膜不合常理(counterintuitive)。
更典型的是在Se氛圍下退火彼等類型之薄膜。在反應性含S之氛圍下退火後，在含有Se之氛圍中退火該等薄膜。
自CIGS奈米粒子薄膜中反應性地移除碳可提供較大之CIGS晶體
且其退火溫度低於在含有碳之薄膜中形成晶體所需之溫度。該退火溫度可低於500℃、低於480℃或低於460℃。較低溫度處理具有若干優點。例如，在較低溫度下，可在諸如聚合物之可撓性基板上生長CIGS吸收劑層，該等基板無法經受較高溫度處理。較低溫度處理亦防止形成充當失效模式之諸如MoSe的物質。
應瞭解，該反應性硫退火可作為圖1中所繪示之退火步驟中之任何一者的部分來實施。換而言之，可在反應性硫之存在下退火一或多個層及/或完整之CIGS吸收劑層。
根據另一個實施例，可在含S氣體及含Se氣體之混合物中進行一或多個退火階段。依序使用H2Se及H2S之反應性退火導致開路電壓(Voc)之增加及短路電流(Jsc)之同時減小。在薄膜內之H2S及H2Se之混合物中之反應性退火增大薄膜的填充係數及功率轉化效率(PCE)。
圖2顯示使用藉由以CIGS奈米粒子墨水沉積薄膜及在H2Se氛圍中退火該薄膜所形成之吸收劑層的裝置的電流-電壓圖。該裝置展示0.46V之Voc、32.4mA/cm2之Jsc、53之填充係數及8.1%之PCE。
圖3顯示除在H2S及H2Se之混合物中退火薄膜外，以相似方式製造之裝置的圖。圖3之裝置展示0.48V之Voc、35.7mA/cm2之Jsc、61.1之填充係數及10.6%之PCE。相較於基線裝置，Jsc已從32.4mA/cm2增加至35.7mA/cm2及FF已從53顯著增加至61.1，導致裝置具有10.6%之PCE。
表1顯示用於形成圖3中所繪示之圖之裝置之裝置單分的數據。該表顯示填充係數(FF)隨著裝置表面積減小而增加。當該裝置經單分(藉由減小入射之表面積)時，FF增加至68.3及效率係11.0%。該等值與針對使用真空方法所製得之裝置之文獻中引用的值相當。
圖4顯示在H2Se(A)及在H2S/H2Se(B)中退火之薄膜的XRD光譜。
該等薄膜之組成十分相似及主要對應於CuInSe2。該等薄膜之相似性指示FF之增加並非該薄膜之化學組成所導致的結果，而是與該薄膜之品質有關。H2S/H2Se退火之薄膜的SEM影像指示顯著顆粒生長。圖5中展示該薄膜之SEM影像實例。
較佳實施例及其他實施例之前述說明無意限制或約束由本申請者所設想之發明概念的範圍及適用性。應瞭解本發明之益處：上述根據本發明所揭示之標的物的任何實施例或態樣之特徵可單獨利用或與本發明所揭示之標的物之任何其他實施例或態樣中之任何其他所述特徵組合使用。雖然已展示並描述本發明之特定實施例，但是其等無意限制本專利所涵蓋之範圍。熟習此項技術者應瞭解可對本發明作出各種變動及修改而未背離藉由以下申請專利範圍所字面上及等效地涵蓋之本發明的範圍。
100‧‧‧製備CIGS吸收劑層之一般方法
101‧‧‧基板
102‧‧‧CIGS奈米粒子墨水
103‧‧‧印表機
104‧‧‧退火階段/退火步驟
105‧‧‧CIGS層
106‧‧‧CIGS奈米粒子墨水
107‧‧‧印表機
108‧‧‧雙層薄膜
109‧‧‧印表機
110‧‧‧CIGS奈米粒子墨水
111‧‧‧退火階段/退火步驟
112‧‧‧吸收劑層
113‧‧‧第二退火階段/退火步驟
Claims (20)
- 一種用於製造含有銅銦鎵硫化物(硒化物)[CIGS]奈米粒子之薄膜之方法，其包括：在基板上沉積CIGS前驅物之溶液或懸浮液以形成薄膜；在含有硫之反應性氛圍下退火該薄膜。
- 如請求項1之方法，其中該含有硫之反應性氛圍包括硫化氫氣體(H2S)。
- 如請求項1之方法，其中該含有硫之反應性氛圍進一步包括硒。
- 如請求項3之方法，其中該硒係呈硒化氫氣體(H2Se)之形式。
- 如請求項1之方法，其中該等CIGS前驅物包括銅、銦及/或鎵，及硫及/或硒。
- 如請求項1之方法，其中該基板包括玻璃。
- 如請求項6之方法，其中該玻璃係塗覆鉬之玻璃。
- 如請求項1之方法，其中該退火係在大於約200℃之溫度下進行。
- 如請求項1之方法，其中該退火溫度在退火過程中變化。
- 如請求項9之方法，其中該退火溫度係以選定之變化速率自第一溫度變化至第二溫度。
- 如請求項10之方法，其進一步包括在該第二溫度下保持該退火溫度一段選定之時間及然後改變該退火溫度至第三溫度。
- 如請求項1之方法，其中該含有硫之氛圍係靜態氛圍。
- 如請求項1之方法，其中該含有硫之氛圍係動態氛圍。
- 如請求項1之方法，其中該退火之時間及溫度係足以誘導粒子熔合以形成CIGS晶體。
- 如請求項1之方法，其進一步包括在含有硫之反應性氛圍中退火 後接著在含有硒之氛圍中退火該薄膜。
- 如請求項1之方法，其中該退火係在管形爐中進行。
- 如請求項1之方法，其中該基板係聚合物及該退火溫度係低於約500℃。
- 如請求項17之方法，其中該基板係聚合物及該退火溫度係低於約460℃。
- 如請求項1之方法，其進一步包括額外沉積及退火步驟以形成多層薄膜。
- 如請求項19之方法，其中該多層薄膜中銦對鎵之比率隨在該膜內之深度而變化。
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| US6127202A (en) * | 1998-07-02 | 2000-10-03 | International Solar Electronic Technology, Inc. | Oxide-based method of making compound semiconductor films and making related electronic devices |
| US8563348B2 (en) * | 2007-04-18 | 2013-10-22 | Nanoco Technologies Ltd. | Fabrication of electrically active films based on multiple layers |
| KR101144807B1 (ko) * | 2007-09-18 | 2012-05-11 | 엘지전자 주식회사 | 태양전지 박막조성용 잉크와 그 제조방법, 이를 이용한ｃｉｇｓ 박막형 태양전지, 및 그 제조 방법 |
| WO2009068878A2 (en) * | 2007-11-30 | 2009-06-04 | Nanoco Technologies Limited | Preparation of nanoparticle material |
| US8784701B2 (en) | 2007-11-30 | 2014-07-22 | Nanoco Technologies Ltd. | Preparation of nanoparticle material |
| US8802977B2 (en) * | 2008-05-09 | 2014-08-12 | International Business Machines Corporation | Techniques for enhancing performance of photovoltaic devices |
| US8889469B2 (en) * | 2009-12-28 | 2014-11-18 | Aeris Capital Sustainable Ip Ltd. | Multi-nary group IB and VIA based semiconductor |
| US7998789B1 (en) * | 2010-04-16 | 2011-08-16 | Jenn Feng New Energy Co., Ltd. | Method and system for forming copper indium gallium sulfur selenide absorption layer and cadmium sulfide buffer layer under non-vacuum condition |
| WO2013033729A1 (en) * | 2011-09-02 | 2013-03-07 | Alliance For Sustainable Energy, Llc | Electrodepostion of gallium for photovoltaics |
| US8551802B2 (en) * | 2011-09-12 | 2013-10-08 | Intermolecular, Inc. | Laser annealing for thin film solar cells |
| US20130157407A1 (en) | 2011-12-20 | 2013-06-20 | Intermolecular, Inc. | APPARATUS FOR INLINE PROCESSING OF Cu(In,Ga)(Se,S)2 EMPLOYING A CHALCOGEN SOLUTION COATING MECHANISM |
| US9018032B2 (en) * | 2012-04-13 | 2015-04-28 | Tsmc Solar Ltd. | CIGS solar cell structure and method for fabricating the same |
| US9243340B2 (en) * | 2013-03-07 | 2016-01-26 | Nano And Advanced Materials Institute Limited | Non-vacuum method of manufacturing light-absorbing materials for solar cell application |
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| CN105940500A (zh) | 2016-09-14 |
| KR101822147B1 (ko) | 2018-01-25 |
| US20150221795A1 (en) | 2015-08-06 |
| JP2018197188A (ja) | 2018-12-13 |
| US9887304B2 (en) | 2018-02-06 |
| TWI560891B (en) | 2016-12-01 |
| EP3100306A1 (en) | 2016-12-07 |
| WO2015114356A1 (en) | 2015-08-06 |
| JP2017511782A (ja) | 2017-04-27 |
| KR20160103077A (ko) | 2016-08-31 |
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