TWI550077B - Silicon wafer processing fluid and silicon wafer processing method - Google Patents

Silicon wafer processing fluid and silicon wafer processing method Download PDF

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TWI550077B
TWI550077B TW100130151A TW100130151A TWI550077B TW I550077 B TWI550077 B TW I550077B TW 100130151 A TW100130151 A TW 100130151A TW 100130151 A TW100130151 A TW 100130151A TW I550077 B TWI550077 B TW I550077B
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wafer processing
processing liquid
nitrogen
containing compound
water
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TW201217505A (en
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Tomohiko Kitamura
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Idemitsu Kosan Co
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    • C10M173/00—Lubricating compositions containing more than 10% water
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/02008—Multistep processes
    • H01L21/0201—Specific process step
    • H01L21/02024—Mirror polishing
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    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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Description

矽晶圓加工液及矽晶圓加工方法 發明領域
本發明係有關於矽晶圓加工液及矽晶圓加工方法。
 發明背景
於製造矽晶圓時會實施切斷矽鑄錠或研磨矽晶圓等之加工。例如切斷矽鑄錠係邊將加工液加注至導線邊實施。於此，切斷矽鑄錠有游離研磨粒及固定研磨粒兩種方式，游離研磨粒方式係以將研磨粒分散至加工液之狀態切斷矽鑄錠；而固定研磨粒方式係以事先將研磨粒固定於導線表面之狀態切斷矽鑄錠。
用於游離研磨粒方式之加工液係使用例如含摩擦係數降低劑及防鏽助劑等的水溶性加工液。此加工液所含之摩擦係數降低劑係使用不飽和脂肪酸，而防鏽助劑係使用苯并三唑(請參照文獻1：特開平8-57848號公報)。
用於固定研磨粒方式之加工液係使用例如含二醇類、羧酸、醇胺等的水溶性加工液。(請參照文獻2：特開2003-82334號公報)
於此，如文獻1之游離研磨粒方式，若導線太粗，則因切量變大而會產生很多切粉，進行切斷矽鑄錠之成品率會變差。另一方面，因導線會隨使用而被削掉，則將導線本身弄細係有界限。因此，於製造期待今後能大量增產之太陽能電池用等之矽晶圓上，以游離研磨粒方式而言，生產性並未達到要求程度，而不甚佳。
而，根據如文獻2之固定研磨粒方式，因事先將研磨粒固定於導線，而可弄細導線也可減少切粉。但，即使是此種固定研磨粒方式，隨著導線的使用研磨粒也會磨耗、脫落。結果，因導線會斷線、加工效率或切斷精度會降低，而會有成品率降低之問題。又，亦有切粉與水反應產生氫、加工液溢流出加工液槽等之問題。
 發明概要
而，本發明之目的係提供可抑制研磨粒的磨耗及氫的產生之矽晶圓加工液及矽晶圓加工方法。
為解決前述課題，本發明係提供如下之矽晶圓加工液及矽晶圓加工方法。
(1)一種矽晶圓加工液，係調配含有含氮化合物之摩擦調整劑而成者，其特徵在於前述含氮化合物與水的質量比(前述含氮化合物/前述水)為1/99時，pH為2以上且8以下。
(2)前述本發明之矽晶圓加工液中，其特徵在於前述含氮化合物為雜環化合物。
(3)前述本發明之矽晶圓加工液中，其特徵在於前述雜環化合物係苯并三唑、3,4-二氫-3-羥-4-側氧-1,2,3-苯并三、吲唑、苯并咪唑及其等之衍生物當中之至少一種雜環化合物。
(4)前述本發明之矽晶圓加工液中，其特徵在於該矽晶圓加工液的pH為3以上且9以下。
(5)前述本發明之矽晶圓加工液中，其特徵在於以加工液總量基準計，前述含氮化合物的含量為0.05質量%以上且10質量%以下。
(6)前述本發明之矽晶圓加工液中，其特徵在於以加工液總量基準計，該矽晶圓加工液係含50質量%以上且99.95質量%以下的水。
(7)前述本發明之矽晶圓加工液中，其特徵在於係用於矽晶圓加工，該矽晶圓加工係藉由固定有研磨粒之導線所行者。
(8)一種矽晶圓加工法，係使用調配含有含氮化合物之摩擦調整劑而成之矽晶圓加工液，並藉由固定有研磨粒之導線加工矽晶圓者，其特徵在於前述含氮化合物與水的質量比(前述含氮化合物/前述水)為1/99時，pH為2以上且8以下。
依據本發明係提供可抑制研磨粒的磨耗及氫的產生之矽晶圓加工液及矽晶圓加工方法。
 用以實施發明之形態
本發明之矽晶圓加工液(以下，會有略寫成「加工液」的情況。)係用於藉由導線加工矽晶圓之時。於此，係說明本發明之加工液藉由固定研磨粒方式用於切斷矽鑄錠時的情況，不過其也可用於游離研磨粒方式的情況。
本發明之加工液係調配摩擦調整劑而成者。摩擦調整劑係含有含氮化合物，此含氮化合物與水的質量比(含氮化合物/水)為1/99時，pH為2以上且8以下。
若pH小於2，則導線、線鋸、矽等恐有被腐蝕之虞。另一方面，若pH大於8，則切斷矽鑄錠時的摩擦係數會增加，且摩擦會變大。因此，pH宜為3以上且7以下，又以4以上且6以下為佳。
做為具有此樣特定pH之含氮化合物有例如雜環化合物，具體可舉苯并三唑、3,4-二氫-3-羥-4-側氧-1,2,3-苯并三、吲唑、苯并咪唑及其等之衍生物等。其中以苯并三唑及3,4-二氫-3-羥-4-側氧-1,2,3-苯并三為佳。
藉由本發明之含氮化合物，導線能有良好的潤滑性，且能抑制固定於導線的研磨粒的磨耗，又可防止研磨粒從導線脫落。因此，因可防止導線斷線且可提升加工效率或切斷精度，而可提升成品率。又，藉由此樣含氮化合物係可抑制矽鑄錠的切粉與水反應產生氫。因此，亦可抑制加工液溢流出加工液槽。
又，本發明之加工液的pH宜為3以上且9以下，又以5以上且7以下為佳。因pH係於中程度的酸性至弱鹼性的範圍內，則更可抑制氫的產生。進一步地亦可抑制導線、矽等的腐蝕。
而，以加工液總量基準計，本發明之含氮化合物的含量以0.05質量%以上且10質量%以下為佳，又以0.1質量%以上且5質量%以下為佳。以含量為0.05質量%以上，更能抑制研磨粒的磨耗及氫的產生，且可防止導線、矽等的腐蝕。另一方面，以含量為10質量%以下，可抑制成本。
本發明之加工液係含水，其中水並無限制，自來水、純化水皆可。水的含量以50質量%以上且99.95質量%以下為佳，又以60質量%以上且95質量%以下為佳。以50質量%以上，與用以作為習知主成分之乙二醇相比，可減小環境負荷。又，因是以水作為主成分，而可降低引燃性。
接著，將針對本發明之矽晶圓加工方法進行說明。
本發明之矽晶圓加工方法，例如為固定研磨粒方式，其係事先將研磨粒固定於導線上。
於實施本發明之矽晶圓加工方法時，係將矽鑄錠導入已佈滿導線之線鋸的加工室內。
然後邊將本發明之加工液加注於導線，並邊切斷矽鑄錠。
本發明之加工液因含有具特定pH之含氮化合物，而可防止研磨粒的磨耗。又，雖矽鑄錠會產生切粉，但藉由本發明之含氮化合物，可抑制切粉與水產生反應。
又，本發明之加工液以不違反本發明目的之範圍可含公知的添加劑，如摩擦調整劑、消泡劑、金屬減活化劑、殺菌劑(防腐劑)、黏度調整劑、pH調整劑、增黏劑、分散劑等。
摩擦調整劑係用於抑制研磨粒的磨耗。作為摩擦調整劑係可使用各種介面活性劑、水溶性高分子。作為介面活性劑可舉二醇類等之非離子介面性活劑。而作為水溶性高分子可舉聚丙烯酸等的羧酸系高分子化合物、聚乙二醇等的伸烷基二醇系高分子化合物。
消泡劑係用於防止加工液溢流出設於加工室內的加工液槽。作為消泡劑例如可舉聚矽氧油、氟聚矽氧油、氟烷醚油等。
作為金屬減活化劑可舉咪唑啉、嘧啶衍生物、噻二唑、苯并三唑等。
殺菌劑(防腐劑)係用於防止導線等的腐蝕。作為殺菌劑(防腐劑)可舉對羥苯甲酸酯類(paraben類)、苯甲酸、柳酸、山梨酸、去氫醋酸、對甲苯磺酸及其等之鹽類、苯氧基乙醇等。
pH調整劑係用於調整本發明之加工液的pH在3以上且9以下之範圍。pH調整劑可分為酸性調整劑與鹼性調整劑。作為酸性調整劑可舉聚丙烯酸、異壬酸等的酸性化合物。而作為鹼性調整劑可舉N-甲基二乙醇胺、環己基二乙醇胺等的鹼性化合物。
增黏劑係用於提升本發明之加工液的黏度及對導線的附著性。藉此可抑制研磨粒的磨耗。作為增黏劑可舉與摩擦調整劑相同之羧酸系高分子化合物、伸烷基二醇系高分子化合物等。
分散劑係用於抑制切粉往線鋸的堆積。作為分散劑可舉與上述摩擦調整劑相同之各種介面活性劑、水溶系高分子等。
此等之添加劑的含量雖依目的適當設定即可，但以加工液總量作為基準，此等之添加劑的合計量通常為0.01質量%以上且30質量%左右。
又，雖顯示了本發明之加工液係用於切斷矽晶圓時之構成，但也可用於研磨矽晶圓。
又，本發明之加工液的製造方法並無特別限定。從搬運、販賣的便利性來看，例如亦可調製含水量少而呈濃縮狀態的加工液，再於使用前加水調整濃度。
而，雖說明了本發明之加工液係以水為主成分之構成，但也可以二醇作為主成分。
[實施例]
接著，將更加詳細地說明本發明之實施例，但本發明不限於這些範例。
[實施例為1至3，比較例為1至5]
調製於表1所示組成之加工液，實施各種實驗並進行了評價。以下為加工液所含之成分及各種實驗項目。評價結果及加工液的pH亦一併於表1顯示。
＜加工液的成分＞
(1)水：自來水
(2)丙二醇
(3)含氮化合物：苯并三唑(Zypro化成(股)製CEATECBT)
(4)含氮化合物：3,4-二氫-3-羥-4-側氧-1,2,3-苯并三
(5)含氮化合物：咪唑啉
(6)含氮化合物：3,4-二氫-2H-吡哆(1,2-a)嘧啶-2-酮
(7)含氮化合物：N-甲基二乙醇胺(日本乳化劑(股)製胺醇MDA)
(8)十二烷二酸(INVISTA(Japan)(股)製　註冊商標Corfree M1)
＜實驗項目＞
(1)往復摩擦實驗
1.評價方法
依據下述實驗條件，藉由測定摩擦係數進行了評價。
2.實驗條件
實驗機：(股)Orientec製F-2100
球：3/16英吋SUJ2
實驗板：多晶矽
滑動速度：20mm/s
滑動距離：2cm
荷重：200g
(2)氫產生實驗
1.評價方法
邊將1600g加工液加注至Ni電鍍鑽石導線(原線徑為0.12mm，粒度為12μm以上且25μm以下)，藉由下述切斷條件切斷了多晶矽(□156mm)。將加工液循環使用並實施了4次切斷。藉此，製備了含有活性矽的切粉之加工液。將含切粉之加工液100g靜置，以水上置換法將產生的氣體回收至量筒，藉由下述實驗條件進行了定量。又，以比較例1、2而言，因摩擦係數太大而無進行實驗。
2.切斷條件
線鋸：DWT公司製CS810(單線鋸)
導線使用量：30m(藉由往復運動重複使用)
導線運行速度：平均值340m/min
導線撓曲設定：5°
3.實驗條件
實驗時間：3天
靜置之加工液量：100g
量筒容量：200ml
(3)省資源性實驗
1.評價方法
依據下述評價基準，藉由加工液所含之水的含量對加工液進行了評價。
2.評價基準
水的含量80%以上：A
水的含量70%以上少於80%：B
水的含量60%以上少於70%：C
水的含量少於60%：D
(評價結果)
藉由於表1之實施例1至3的結果，本發明之加工液因含有預定的含氮化合物而可減少摩擦係數。因此可知係可抑制研磨粒的磨耗且可防止研磨粒的脫落。又，可知本發明之加工液可減少氫的產生量，且可防止加工液溢流出加工槽。進一步地，因本發明的主成分為水，故環境的負荷小，且擁有優異的省資源性。
另一方面，比較例1至5因無含於本發明視為所需之具有預定pH之含氮化合物來作為摩擦調整劑，而無法共同抑制摩擦係數及氫產生量的增加。又，比較例4因主成分為丙二醇，則環境負荷大，且缺乏省資源性。

Claims (7)

  1. 一種矽晶圓加工液，係調配含有含氮化合物之摩擦調整劑而成者，其特徵在於：前述含氮化合物在與水的質量比(前述含氮化合物/前述水)為1/99時，pH為3以上且7以下，該矽晶圓加工液的pH為5以上且7以下。
  2. 如申請專利範圍第1項之矽晶圓加工液，其中前述含氮化合物為雜環化合物。
  3. 如申請專利範圍第2項之矽晶圓加工液，其中前述雜環化合物係苯并三唑、3,4-二氫-3-羥-4-側氧-1,2,3-苯并三、吲唑、苯并咪唑及其等之衍生物當中之至少一種雜環化合物。
  4. 如申請專利範圍第1至3項中任一項之矽晶圓加工液，其中以加工液總量基準計，前述含氮化合物的含量為0.05質量%以上且10質量%以下。
  5. 如申請專利範圍第1至3項中任一項之矽晶圓加工液，其中以加工液總量基準計，該矽晶圓加工液係含50質量%以上且99.95質量%以下的水。
  6. 如申請專利範圍第1至3項中任一項之矽晶圓加工液，其係用於矽晶圓加工，該矽晶圓加工係藉由固定有研磨粒之導線所行者。
  7. 一種矽晶圓加工方法，係使用調配含有含氮化合物之摩擦調整劑而成之矽晶圓加工液，並藉由固定有研磨粒之導線加工矽晶圓者，其特徵在於：前述含氮化合物在與水的質量比(前述含氮化合物/前 述水)為1/99時，pH為3以上且7以下，該矽晶圓加工液的pH為5以上且7以下。
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