TW252055B - - Google Patents

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TW252055B
TW252055B TW083101812A TW83101812A TW252055B TW 252055 B TW252055 B TW 252055B TW 083101812 A TW083101812 A TW 083101812A TW 83101812 A TW83101812 A TW 83101812A TW 252055 B TW252055 B TW 252055B
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coating
patent application
substrate
silazane
item
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TW083101812A
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Dow Corning
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    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
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    • H01L21/18Manufacture 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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    • C04B41/5024Silicates
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    • H01L21/02123Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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    • H01L21/02205Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
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    • H01L21/02323Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of oxygen
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    • H01L21/02337Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
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    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3105After-treatment
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
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  • Organic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Silicon Compounds (AREA)

Description

252055 A6 B6 經濟部中央櫺準局貝工消费合作社印製 五、發明説明(1 ) 本發明係闉於一種將含有麵矽酸蘧之塗層塗覆於電子基 板上之方法,其中雜矽氮烷聚合物係用作含有硼矽酸鹽塗 層之母質。 本技藝中已知有多種方法可於電子元件上施加陶瓷塗曆 。例如,各種氣相沈積去中K氣態母質產生二氧化矽,氮 化矽,氧氮化矽,碳化矽等之塗層。此等塗層為有效之保 護及介電層。 同樣地,以聚合物母質於霣子元件上沈横陶瓷塗靨亦為 本技藝所知。例如,美國專利第4,749,631號與第 4,756,977號Μ及亞邱格拉斯TM (ACCUgiassTM)產品文獻 揭示,二氧化矽塗層係以二氧化矽母質溶液塗覆於元件上 ’然後加熱經塗覆之元件將母霣轉換成二氧化矽而得。不 過,這些參考文獻並未掲示使用硼矽氮烷當作_矽酸鹽母 質。 使用聚矽氮烷於電子元件上塗覆含有矽,碳及氮之陶瓷 塗層亦為本技藝所知。例如,美國專利第4,756,977號及 第4,826,733號教示Μ含矽及氮之聚合物,如聚矽氮烷塗 曆塗覆於此類元件上•然後在一棰惰性氣氛中加热經塗覆 之元件Κ生成陶瓷塗層。彼等塗饜於惰性氣氛中加熱時氮 存留於聚合物中而生成氮化矽或碳氮化矽塗層。 美國專利第4,973,526號亦述及一種形成含有矽,氧及 硼塗曆之方法。此方法包含Μ矽倍半氧烷氫樹脂與一種氧 化砸母質混合•將此混合物塗覆於電子元件上並加熱經塗 覆之元件使之陶瓷化。此參考文獻亦未述及硼矽氮烷之使 本紙張尺度逋用中鼷Η家樣準(CNS)甲4规格(210x297公釐) 裝................:訂.....................線 {請先閲讀背面之注意事項再填寫本買) 252055 A6 B6 經濟部中央標準局貝工消费合作社印製 五、發明説明(2 ) 用0 最後,已知美圔專利第4,482,689號及第4,910,173號 與歐洲專利第0 364 323號及第〇 424 082號中揭示 矽氮烷形成塗層。不遇,此等參考文獻並未教示或建議使 用此類材料於電子學上而且由其衍生之塗層亦非硼矽酸蘧 〇 吾人已於研究中發現,含有硼矽酸鹽之塗層可由钃矽氮 焼聚合物衍生並且成功地塗覆於電子基板上。因為所得之 塗層厚而平坦且無缺陷遂可當作保護及介轚曆。 吾人提出申謫專利之發明中引入一種將含有钃矽酸鹽之 塗層沈積於電子基板上之方法。此方法包含先K含有钃砂 氮烷聚合物之塗層塗覆於電子基板上。然後將經塗覆之基 板於氧化氣氛中以足夠之溫度加熱使硼矽氮烷聚合物轉換 成含有硼矽酸鹽之塗曆。 在吾人研究之前,本技藝並不了解棚矽氮烷聚合物在電 子基板上是否能轉換成含有硼矽酸鹽之塗層而且不損害基 板並對其電性有良好之效應。 此處引用之措辭”綳矽酸鹽”係指含有Si-0及B-0鐽之 已熱解材料*其可能(也可能不)完全無殘留碳•氫及/ 或氮,但其他方面則具陶瓷之特徽。措辭”平坦之塗層” 係指塗層表面較塗覆塗層之前更規則。再者,措辭”電子 基板”包括矽基元件,砷化鎵基元件*焦面式陣列,光電 元件,光伏打電池》光學元件,平板顯示器以及位在晶片 及姐合级上之積體罨路。此類基板之特殊實例包含雷晶體 本紙張尺度逋用中Η國家標準(CNS)甲4规格(210X297公釐) 裝.....................................訂.............................線 {請先Μ讀背面之注意事項再填窝本頁) 經濟部t央樣準局貝工消费合作社印製 ^52055 A6 __B6 五、發明説明(5 ) 元件*電容器及類電容器元件*積層元件* 3— D元件*絕 緣體之矽元件及超晶格元件。 本發明使用之聚_矽氮烷(或確矽氮烷聚合物)一般為 本技藝中熟知而且其结構並無特別要求。此類聚合物之钃 含量一般同樣亦無嚴格要求而且變化範國很廣(例如, 〇 . - 5 0重量分率 >。一般言之,此類硼矽氮烷之構架包含
Si-B,Si-N及B— N鐽,此等原子剌餘之價數則各Μ埋自氳 原子,含1至20個碳原子之烷基·如甲基*乙基及丙基; 芳基•如笨基;及烯基如乙烯基填補。其中較佳之硼矽氮 烷聚合物,其重覆單元中不含碳(亦即,碳可能位於聚合 物之端基上>。 特別之矽氮烷實例包含美國專利第4,482,689號, 4,604,367號,4,910,173號· 5,030,744號及 5,169,908號 所述*歃洲專利申請某第0 364 323號及0 424 082號所 述;Μ及席佛斯(Seyferth)等人於美國陶瓷學會73, 2131 - 2133 ( 1990)中所述Μ及諾斯(Hoth)於無機化學Η 有機化學會報16(9) · 618-21· (1961)中所述。 製備此類化合物之方法同樣為本技«所知而且完全詳述 於口述參考文獻中。無論如何,此等方法之實例包含(1) Κ三鹵化_與矽氮烷寡聚物•如(RSMNiOnUS ((CH3)3Si)2NH反應,其中R係選自氫厚子*烴基及一種 络取代烴基而X為2至20之整數;(2) K —種有櫬氮哄 與一種有機聚矽烷反應;Μ及(3) Μ —種钃化合物•如一 種_烷錯合物,_喔星(boroxine)·晒烷氧化物及硼氮畊 本紙張尺度適用中國國家標準(CNS)甲4规格(210X297公釐) ......................................................................................裝..................::玎.....................線 {請先閲讀背面之注意事項再填寫本頁) 經濟部t央標準局貝工消费合作社印製 252055 A6 _____B6 五、發明説明(4 ) 與一種聚矽氮烷反廳。 一種特佳之聚合物包含美國専利第5,169,9〇8號之以硼 改良之氫聚矽氮烷聚合物。彼等聚合物係以包含將一種氣 矽氮烷聚合物與一種*烷錯合物或二钃烷反應之方法製得 。本發明之一種較佳具«實胞例採用之氫聚矽氮烷係以美 國專利第4,540,803號,上述提及,908號專利所述方法而 將三氯矽烷及六甲基二矽氮烷反應而得。 雖然上述特別提及數種聚合物,但是嫌乎任一種硼矽氮 烷皆可用於此處所述之方法中。 本發明之第一步嫌係將硼矽氮烷塗覆於基板上以形成一 種前陶瓷塗層。ΒΙ然任一習用技術皆可採用,但是Κ一種 含有溶劑及硼矽氮烷之溶液塗覆於基板上特佳。溶蜊可播 蒸發或類似技術去除Μ生成前陶瓷塗層。不遇其他等效之 方法例如熔融塗層•亦靨此處之考量。 若採用上述溶液法·則碥矽氮烷率先溶於溶劑中。各種 肋長方式•如攢拌及/或加热皆可促進溶解。可採用之溶 劑包含任何可將《矽氮烷溶解形成一種不影響塗層之溶液 或懸浮液者。此等溶劑可包括,例如芳香烴類,如二甲笨 ,苯或甲笨*烷類,如Π-庚烷,癸烷或十二烷*鬭類,酷 類,乙二酵醚類或環二甲基聚矽氧烷類,而添加最足將硼 矽氮烷溶解。一般言之,使用足量之上述溶劑可形成 0. 1-50重量分率之溶液。 若採用上述溶液法則Μ例如旋轉塗佈•浸漬塗佈,哦琪 塗佈或流動塗佈之技術塗覆塗層溶液。藉任何適當之方式 ......................................... .............................裝................:i ·玎........ ::.線 {請先閲讀背面之注意事項再填窝本頁} 本紙張尺度遑用中國國家標準(CNS)甲4规格(210X297公釐) 252055 A6 B6 經濟部中央揉準局貝工消费合作社印製 五、發明説明(5 ) ,如曝®於大氣環境中簡單風乾或抽真空或適溫加熱(如 低於50¾ )使溶劑蒸發而得到所須之先陶瓷塗曆。 然後將前陶瓷塗曆置於氧化環境中加熱使SiN及BN鐽水 解而失去氮以促使钃矽氮烷轉換成磡矽酸蘧。此外•矽及 /或硼上之其他官能基亦可於此種環境中去除。氧化瑁境 ,如含有空氣,02,奥氧,水氣,氧霣漿,氨,胺類及上 述之琨合物均可使用。 _矽氮烷置於反應環境及足K陶瓷化之溫度中。一般言 之,此溫度為20至1000 T:,端視反應氣氛而定。較佳之溫 度範園為50至800 Ό 。較高之溫度通常造成陶瓷化更快且 更完全,但是該溫度亦對不同溫度敏感之基板造成不良影 響。對溫度敏感之基板*如轚子元件,溫度範讀為1〇〇至 5 00C最佳。硼矽氮烷塗暦一般置於這些溫度持績一段時 間K使塗層陶瓷化*通常至多為6小時,較佳之時間範圃 為2 — 4小時。 加熱步驟可採用任一種熱源,如加热板,對流爐,快速 熱製程或輻射或微波能量。 藉上述方法可於基板上產生含有硼矽醴_之平坦塗層。 此塗層使各種基板之不規則面平滑並具優異之附著力。此 外,此塗層相當厚(例如•大於0.5微米)。此類塗層很 有用,例如可當作保護性塗層及中間介霣層。 砸矽酸鹽塗層亦可覆K其他塗層,如以一種額外之塗曆 塗覆其上,如Si〇2,Si〇2 /改良式陶瓷氧化物層,含矽塗 層•含碳化矽塗靥,含氮化矽塗暦*含碳氮化矽塗層及/ 本紙張尺度逋用中國國家標準(CNS)甲4规格(210X297公釐) < 裝..........................訂.....................線 {請先閲讀背面之注意事項再填寫本頁) 252055 A6 B6 五、發明説明(6 ) 或類讚石碳塗層。此種多靥塗覆之更詳细說明及教示述於 美圃專利第4,973,526號中。 凡熟悉本技藝者可«下列提出之非限制實例而輕易了解 本發明。 經濟部+央標準局貝工消费合作社印製 將含有1.5重量分率钃且數平均分子量(M„)為6000之硼 氫化聚矽氮烷(BHPZ>M美B專利第5, 169,908號之方法製 得。將5重量分率之BHPZ溶液於二甲苯/庚烷溶劑中,以 3000 rpie,進行20秒,旋轉塗覆於一 Η2·54公分(1英吋 )見方之矽晶Η及一個14011Β CMOS元件上。然後經塗覆 之基板置於4.2—4.3重量分率之臭氧中在175T:加熱3小時 。所得之塗層K FT IR分析顯示«矽酸鹽含有一些殘留之砂 烷醇。經塗覆之基板置於水性氨蒸氣中在175TC加熱3小時 Μ去除矽烷醇。FT IR光譜指出矽烷酵幾乎完全去除。 CMOS元件經轉換後顯示其功能。塗靥厚度為60奈米( 600埃)而折射率為1.456 ( 6328 2 )。 奮例 2 將10重量分率之BHPZ溶液(如實例1 >於甲苯溶劑中, Μ 3000 rpm·進行20秒,旋轉塗覆於一片2.54公分(1英 时 > 見方之矽晶片上。然後經塗覆之基板置於空氣中在 400 t:加熱4小時。所得之塗曆以FTIR顯示_矽酸驪僅含有 微量之SiH(約初值之3Χ )。塗層厚度為290奈米(2900 ................:::玎.....................線 {請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用十國國家樣準(CNS)甲4規格(210X297公釐) 252055 經濟部中央標準局貝工消费合作社印製 A6 B6_ 五、發明説明(7 ) 埃)而折射率為1.553 ( 8300 2 )。 奮例 將10重量分率之BHPZ溶液(如實例1 )於甲苯溶劑中, Μ 3000 rpm,進行20秒,旋轉塗覆於一片2.5 4公分(1英 时 >見方之矽晶Η上。然後經塗覆之基板置於水性氨蒸氣 中在400 1C加热3小時。所得之塗曆KFTIR顧示硼矽酸_ 塗曆僅含有微量之SiH (約初值之3« )。塗層厚度為 160奈米(1600埃)而折射率為 1.513 ( 6328 2 )。 g例4 將有30重量分率之BHPZ溶液(如實例1 )於二甲笨/庚 烷溶劑中,Μ 3000 rpin,進行20秒,旋轉塗覆於一片 2. 54公分(1英吋)見方之矽晶片及一塊2. 54公分< 1英 时)見方之氧化鋁基板上。然後經塗覆之基板置於空氣中 在800 C加熱1小時。所得之塗層MFTIR顯示幾乎完全轉 換成硼矽酸鹽。塗層厚度為560奈米(5600埃)而折射率 為1.466( 8300 2 >。塗層經1000倍放大檢視並無裂缝。 奮例 5 將30重量分率之BHPZ溶液(含有5重量分率之钃)於庚 烷/甲笨溶劑中,M3000 rpm,進行20秒,旋轉塗覆於一 H2.54公分(1英时)見方之矽晶片上。然後經塗覆之基 板置於空氣中在800t加熱1小時。所得之塗曆MFTIR顯 ................. h.........................裝..................i:訂 1:-:-:線 <請先閲讀背面之注意事項再填窝本頁) ~ 9 - 本紙張尺度適用中國國家备本(CNS)甲4規格(210X297公釐) A6 B6
五、發明説明(8 ^5^055 示幾乎完全縛換成_矽酸鹽。塗層厚度為930奈米( 9300埃)而折射率為1.461 ( 8300 2 )。 奮例 β 將30重量分率之ΒΗΡΖ溶液(含有10重量分率之珊)於庚 烷/甲笨溶劑中,W3000 rpm,進行20秒,旋轉塗覆於— H2.54公分(1英时 > 見方之矽晶片上。然後經塗覆之基 板置於空氣中在800C加熱1小時。所得之塗牖WFTIR顬 示幾乎完全轉換成硼矽酸鹽。塗層厚度為71〇奈米( 7104埃)而折射率為 1 . 457 ( 6328 2 >。 窗例 7 將10重量分率之BHPZ溶液(含有10重最分率之蘭)於庚 烷/甲苯溶爾中,M3000 rpm,進行20秒,旋轉塗覆於一 Η 2 . 54公分(1英时)見方之矽晶片上。然後經塗覆之基 板置於4.1 一 4.3重量分率之臭氧中在175Ό加熱3小時。 所得之塗靨M FT IR顯示轉換成之確矽酸鼸中殘留一些砂综 酵。塗層厚度為687奈米(6872埃)而折射率為1.447 ( 6328 λ ) 〇 裝................:....訂.....................線 (精先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 中 用 適 度 尺 張 紙 本 CN 標 家 祕 釐 公 7 9 2

Claims (1)

  1. A7 s 5^055 〇7 - D7 i、申請專利範圍 L —種將含有_矽酸鹽之塗層沈積於電子基板上之方法* 其包含: 將包含钃矽氮烷聚合物之塗曆塗覆於該基板上,κ及 將經塗覆之基板於氧化氣氛中在20至10001C之溫度加 熱使_矽氮烷聚合物轉換成含硼矽酸鹽之塗層。 2· 根據申請專利範圍第1項之方法*其中該塗層係Μ溶麵 將礙矽氮烷聚合物溶解成溶液,再Μ該溶液塗覆於基板 上•然後將溶劑蒸發之方法形成。 3_ 根據申請專利範圍第2項之方法,其中該溶劑係自芳香 烴類,烷類,酮類.酯類,乙二酵醚類及環二甲基聚矽 氧烷類,而且溶劑之量足使钃矽氮烷溶解形成0.1至50 重量分率之溶液。 < 根據申請專利範圃第1項之方法,其中該氧化氣氛係選 自空氣,氧,臭氧,水蒸氣,氧電漿,氨,胺類及上述 之混合物。 5· 根據申請專利範園第1項之方法,其中該經塗覆之基板 於50至800 C之溫度加熱,時間少於6小時。 Β- 根據申請專利範圍第1項之方法,其中該钃矽氮烷之聚 合物其重覆單元不含碳。 7- 根據申請專利範圃第1項之方法,其中該钃矽氮烷之構 架含有Si-B,Si-N及Β-Ν鐽,其剰餘之價數各Κ選自氫 (請先閲讀背面之注意事項再«寫本頁) 訂. .線. 經濟部中央樣準局R工消費合作杜印製 a 補 填 基 稀 及 基 芳 基 烷 之 子 原 碳 個 ο 2 至 11 有 含 子 原 含 所 烷 氮 矽 硼 該 中 其 法 方 之 項 1Λ 第 圍 範 利 專 請 申 據 根 1A 11 本紙張又度適用中國8家標準(CNS)甲4规格(210 X 297公# > η 520^5 Α7 Β7 C7 D7 六、申請專利範園 9. 之硼氫化聚矽氮烷係以三氯矽烷與六甲基二矽氮烷反應 •然後使該反應產物與硼烷反懕製得。 根據申請專利範画第1項之方法,其中該硼矽氮烷之棚 含量範圍介於0.1與50重量分率之間。 (請先閲讀背面之注意事項再塡寫本頁) -裝. 訂- 經濟部中央標準局β:1·消费合作钍印製 12 本紙張又度適用中B®家標準(CNS)甲4规格(210 X 297公* )
TW083101812A 1993-03-25 1994-03-02 TW252055B (zh)

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