TWI550717B - 熱處理方法及其所製得之產物 - Google Patents

熱處理方法及其所製得之產物 Download PDF

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TWI550717B
TWI550717B TW103129205A TW103129205A TWI550717B TW I550717 B TWI550717 B TW I550717B TW 103129205 A TW103129205 A TW 103129205A TW 103129205 A TW103129205 A TW 103129205A TW I550717 B TWI550717 B TW I550717B
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substrate
precursor
heat treatment
protective layer
heating chamber
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TW103129205A
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TW201608638A (zh
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侯惟仁
李昇翰
陳梓斌
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新能光電科技股份有限公司
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Priority to TW103129205A priority Critical patent/TWI550717B/zh
Priority to US14/832,385 priority patent/US10053364B2/en
Priority to EP15182194.9A priority patent/EP2991122A1/en
Priority to CN201510526900.4A priority patent/CN105390393A/zh
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Description

熱處理方法及其所製得之產物
本發明係關於一種熱處理方法，尤其是一種透過於前驅物上直接覆蓋保護層，維持基板上各處熱處理條件之一致性及提升產品良率之熱處理方法。
熱處理係一種普遍應用於各種領域中，用於生長、合成或改良材料之關鍵製程，其主要透過加熱方式，使前驅物中之元素或化合物進行鍵結、擴散、結晶、再結晶、解離與揮發等各種物理或化學反應。藉由調整熱處理過程之操作條件，例如升溫梯度、持溫時間、降溫速率、環境氣體種類、氣壓、氣流及熱流等參數，改變所得產物之物理化學性質。熱處理製程中各操作條件係影響產物性質之重要因素，於大規模量化生產之商業應用上，其更是影響產品品質一致性或良率的關鍵性因素。
為探知適合所欲獲得材料之熱處理條件，往往需要大量且長時間之反覆實驗測試，而在後續商業上大規模量化生產時，更需要投入高成本之設備控制或維持所欲達之操作條件，以求製程產品品質穩定性與一致性。尤其是在廣為使用熱處理製程生產大尺寸基板之應用領域中，例如太陽能面板領域，如何維持大尺寸基板上各處熱處理條件之一致性及提升產品良率係該領域中從業人士的首要目標。
在維持熱處理條件一致性、增進產品良率及提高成本效益等前提下，各界提出不同的技術手段，例如美國專利公開US 2011/0088768 A1中針對目標產物，揭露其最佳之熱處理溫度。美國專利公開US 2010/0203668 A1中針對金屬前驅物之熱處理方式，提出最佳之製程溫度曲線、壓力與環境氣體種類。中華民國新型專利TW M413213，透過設計新型退火爐，達到熱處理時最佳化之氣體流場分布。
然而，先前技術所採之手段均係由調整熱處理參數為基礎，其往往需搭配大幅度調整製程設備，本發明提出一種有別於先前技術之熱處理參數調整手段，僅透過於前驅物上直接覆蓋保護層，達到大尺寸產品量產所欲之高穩定性及高良率。
為達前述之目的，本發明之方法包含：(1)提供基板；(2)將前驅物施加至該基板表面上；(3)將保護層覆蓋於經施加該前驅物之基板上，使其與該前驅物直接接觸；(4)將步驟(3)所得之基板之整體置於加熱腔體中，進行熱處理；及(5)移除該保護層。本發明亦提供一種以該熱處理方法製得之產物，其可為硒化銅銦鎵系列、硒化銅鋅錫系列，或碲化鎘系列之化合物。
C‧‧‧加熱腔體
11‧‧‧基板
12‧‧‧前驅物
21‧‧‧基板
22‧‧‧前驅物
23‧‧‧保護層
圖1為實施先前技術之熱處理製程示意圖。
圖2為實施本發明之熱處理方法示意圖。
本發明提供一種熱處理方法，其包含：(1)提供基板；(2)將前驅物施加至該基板表面上；(3)將保護層覆蓋於經施加該前驅物之基板上，使其與該前驅物直接接觸；(4)將步驟(3)所得之基板之整體置於加熱腔體中，進行熱處理；及(5)移除該保護層。該基板之整體可以 任意方式放置於加熱腔體中，較佳係以該保護層面向加熱腔體頂部之方式放置，更佳係以該保護面與加熱腔體頂部平行之方式放置。根據本發明之一實施態樣，在施加前驅物前可額外施加金屬層，例如鉬金屬層以增加基板導電度。
根據本發明之一具體實施態樣，本發明之方法可在前述步驟(4)之熱處理後，移除該保護層，獲得形成於該基板上之產物。根據本發明之另一具體實施態樣，可視情況重複步驟(2)至(4)或步驟(2)至(5)，使形成於該基板上之產物進行多次熱處理或進一步於已形成於該基板上之產物上施加相同或不同前驅物。
根據本發明之一具體實施態樣，該前驅物包含一或多種具有選自於以下元素組成之群：Cu、In、Zn、Sn、Ga及Cd，及具有至少一種VIA族元素之元素(包括O、S、Se及Te等)前驅物。該一或多種元素前驅物可以以下方式施加於該基板上：以複數個含有單一元素之層之形式逐次施加、以複數個含有兩種以上之元素之層之形式逐次施加於該基板上、以含有多種元素之單一層形式施加於該基板上或其組合。該施加可以磁控直流濺鍍法、磁控射頻濺鍍法、熱蒸鍍法、共蒸鍍法、濺鍍法、化學氣相沉積法或塗佈法進行。
根據本發明之一具體實施態樣，本發明之熱處理係在室溫至1200℃之操作溫度下進行，較佳係在300℃至1100℃，更佳係在400℃至1000℃。本發明之熱處理包含在前述溫度下所進行之升溫、持溫、降溫、退火、淬火或回火等習知技藝人士熟知之操作手段。本發明之熱處理可在如氮氣或惰性氣體之非反應性氣體下進行，亦可在低壓進行。
根據本發明之一具體實施態樣，該保護層係具有耐高溫且熱傳導性佳之特性，較佳可為由碳元素構成之材料、石英玻璃或陶瓷材料。該由碳元素構成之材料可包含(但不限於)，碳纖維、碳布、碳 管、碳球、中空奈米碳球、奈米碳膠囊等。該石英玻璃可為熔融石英玻璃或合成石英玻璃等習知技藝人士熟知之種類。該陶瓷材料可為由SiO2、Al2O3、B2O3、MgO、CaO、Li2O、K2O、Na2O以及類似物等習知技藝人士熟知之種類。
根據本發明之一具體實施態樣，本發明之熱處理方法製得之產物可為硒化銅銦鎵系列、硒化銅鋅錫系列、碲化鎘系列或其類似系列之化合物。
如圖1所示，在先前技術之熱處理方法中，經施加前驅物(12)之基板(11)係以直接裸露於腔體氣體中之方式置放於腔體(C)中。如圖2所示，本發明藉由在施加於基板(21)上之前驅物(22)上直接覆蓋保護層(23)之熱處理方法，以避免熱處理過程中加熱腔體(C)內氣流或熱流流場影響，維持所得之產物性質或品質之一致性。該基板可以該保護層面向加熱腔體頂部之方式放置於加熱腔體中
以下提供之實施例主要敘述本發明中保護層之使用方式，但不侷限前驅物種類、厚度或形成方法，亦不限定熱處理使用之溫度、壓力、氣流等參數。本發明所涵蓋之權力範圍，當以後附之專利權範圍為基準。本文中所使用術語「約」意指包含如由一般熟習此項技術者所測定之特定值的可接受誤差，其部分地視如何量測或測定該值而定。
實施例1
於1公尺見方、3mm厚之玻璃基板上，濺鍍上約500nm厚度之金屬鉬層，接著以直流濺鍍法依序鍍上約300nm厚之銅、約100nm厚之鎵、約500nm厚之銦等三層金屬，以及熱蒸鍍法於前述複數金屬層上鍍上一層約1000nm之硒元素，作為成長硒化銅銦鎵(CIGSe)材料之前驅物。將一片約2mm厚及具有與該玻璃基板相同大小之石英玻璃覆蓋於經施加前驅物之玻璃基板上作為保護層後，獲得樣品1。將樣品1 傳送至加熱爐內進行熱處理製程，加熱腔體內全程通入流量50slm之氮氣，以每分鐘50℃至70℃之升溫速率由室溫升至500℃後，在該溫度下持溫10分鐘後，再以每分鐘50℃至100℃之降溫速率使腔體溫度自500℃降至室溫後取出樣品1。將該石英玻璃移除後，即可於該玻璃基板上得到一層均勻且結晶品質良好之硒化銅銦鎵薄膜。
實施例2
於20公分見方、1mm厚之聚醯亞胺(polyimide)基板上，濺鍍上約500nm厚度之金屬鉬層，接著以共蒸鍍法同時鍍上銅、鋅、錫及硒四種元素之混合物層約1000nm，作為成長硒化銅鋅錫(CZTSe)材料之前驅物。將一片約0.2mm厚及略大於該玻璃基板之石墨紙覆蓋在經施加前驅物之聚醯亞胺基板上作為保護層，獲得樣品2。將樣品2直接置放於已預熱至380℃之加熱板上，該加熱板放置於充滿氮氣之環境以防止反應物氧化，經過10分鐘後取下樣品2。將該石墨紙移除後，即可於基板上得到一層均勻且結晶品質良好之硒化銅鋅錫薄膜。
實施例3
於30公分見方、3mm厚之玻璃基板上，濺鍍上約500nm厚度之鋁摻雜氧化鋅層，接著以濺鍍法於其上形成約2000nm厚之非晶相或微晶相碲化鎘(CdTe)薄膜作為前驅物。將一片約2mm厚及具有與該玻璃基板相同大小之氧化鋁陶瓷薄片覆蓋於經施加前驅物之玻璃基板上作為保護層，獲得樣品3。將樣品3傳送至加熱爐內進行再結晶之熱處理製程。加熱腔體內全程通入流量20slm之氮氣，以每分鐘50℃至70℃之升溫速率由室溫升至450℃後，於在該溫度下持溫30分鐘，再以每分鐘50℃至100℃之降溫速率，使腔體溫度自450℃降至室溫後取出樣品3。將該氧化鋁陶瓷薄片後移除，即可於該玻璃基板上得到一層均勻且結晶品質良好之碲化鎘薄膜。
C‧‧‧加熱腔體
21‧‧‧基板
22‧‧‧前驅物
23‧‧‧保護層

Claims (7)

  1. 一種熱處理方法，其包含：(1)提供基板；(2)將前驅物施加至該基板表面上；(3)將經個別預先形成之保護層覆蓋於經施加該前驅物之基板上，使其與該前驅物直接接觸；(4)將步驟(3)所得之基板置於加熱腔體中，進行熱處理；及(5)移除該保護層；其中，該保護層係與該前驅物直接接觸，以避免熱處理過程中該加熱腔體內氣流或熱流流場對該前驅物造成之影響；及其中，該保護層係具有耐高溫且熱傳導性佳之特性，及該保護層係可為由碳元素構成之材料、石英玻璃或陶瓷材料。
  2. 如請求項1之方法，其可視情況重複步驟(2)至(4)或(2)至(5)。
  3. 如請求項1之方法，該步驟(3)所得之基板以任意方式置於加熱腔體中。
  4. 如請求項1之方法，其中該熱處理係在室溫至1200℃之操作溫度下進行。
  5. 如請求項1至4中任一項之方法，其中該前驅物包含一或多種具有選自於以下元素組成之群：Cu、In、Zn、Sn、Ga及Cd，及具有至少一種VIA族元素之元素前驅物。
  6. 如請求項5之方法，其中該一或多種元素前驅物可以以下方式施加於該基板上：以複數個含有單一元素之層之形式逐次 施加、以複數個含有兩種以上之元素之層之形式逐次施加於該基板上、以含有多種元素之單一層形式施加於該基板上或其組合。
  7. 一種以請求項1至6中任一項之方法所製得之產物，該產物可為硒化銅銦鎵系列、硒化銅鋅錫系列，或碲化鎘系列之化合物。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100218814A1 (en) * 2009-09-09 2010-09-02 International Business Machines Corporation Method of controlling the composition of a photovoltaic thin film
US20130217176A1 (en) * 2012-02-21 2013-08-22 Aqt Solar, Inc. Closed-Space Annealing of Chalcogenide Thin-Films with Volatile Species

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100218814A1 (en) * 2009-09-09 2010-09-02 International Business Machines Corporation Method of controlling the composition of a photovoltaic thin film
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