TW388099B - Integrated circuit dielectrics - Google Patents

Integrated circuit dielectrics Download PDF

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Publication number
TW388099B
TW388099B TW86119030A TW86119030A TW388099B TW 388099 B TW388099 B TW 388099B TW 86119030 A TW86119030 A TW 86119030A TW 86119030 A TW86119030 A TW 86119030A TW 388099 B TW388099 B TW 388099B
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Taiwan
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xerogel
dielectric
metal
integrated circuit
ministry
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TW86119030A
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English (en)
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Changming Jin
Stacey Yamanaka
R Scott List
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Texas Instruments Inc
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  • Engineering & Computer Science (AREA)
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  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
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Description

五、發明説明（ A7 B7 發明之背景 本發明係關於電子裝置’尤指積體電路絕緣材料及製造方 法。 南密度積體電路之性能，由於金屬線之電阻率及相鄰線間之電 容耦合，而受金屬互相連接層次RC延遲所支配。電容耦合可藉 減少相鄰線間之介電質(絕緣趙)之相對介電係數(介電質常數)予以 減少。 人們曾建議各種介電質材料’供使用於發積體電路；亦即， 二氧化矽(目前之主要介電質材料’具有相對介電係數約為4〇)， 無機材料諸如氟化二氧化矽(相對介電係數約為3 〇_4 〇)，有機材 料諸如聚醢亞胺，聚對苯二甲基，無定形鐵氟龍(相對介電係數約 為1.9-3.9)，及多孔介電質諸如二氧化矽乾凝膠(相對介電係數依 孔大小及密度而定，一般為1.3-3.0)。的確，二氧化矽乾凝膠中 之孔大小通常遠小於積體電路特色大小；請見Smith等人， preparation of Low-Density Xerogel at Ambient Pressure f〇r k Dielectrics, 381 Mat.Res.Soc.Symp.Proc.261 (1995) 〇 孑匕隙度可高達 99%。 冋 供積體電路介電質之薄膜二氧化矽乾凝膠可藉⑴先質製備， (2)旋塗，（3)老化，（4)溶劑交換，及⑶乾燥等普通步驟製造。酸 驗溶膠凝膠反應可如下： 在溶劑中水解醇鹽： 經濟部中央樣準局貝工消费合作社印製
,0' o V -ν ο ο ----------裝------訂------線-------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297兮釐） TT 86642 五、發明说明（） 溶劑可方便為乙醇 然後冷凝： Kr 、，^ C SI + ，0 0、H H，(
CxHr ο Ηχ〇 Ό,
Cj.H^ 〔此 經濟部中央標準局貝工消費合作社印製 冷凝將予以控制，以便在部份冷凝至適當粘性後發生旋塗。 溶劑交換步驟藉低表面張力溶劑替代存在於冷凝網絡之細孔 内之原始溶劑，以在乾燥時減少毛細管壓力，並使最少細孔之皺 縮。美國專利USP5,561，318號揭示該方法之種種變化。 然而’目前尚未能製造多孔二氧化矽。 Shea 等人之 arylsilseSqui〇xane Gd 咖 reiate(i 恤㈤也， New Hybrids of Organic and Inorganic Network, 114 LAmfhem.S〇C.67〇〇(i992) ’說明自單體諸如有二乙氧基甲矽烷 基之苯水缺練卿紅郷；郷f予健，並且大孔隙聚 合物網絡敏縮，產生一種大孔隙聚石夕倍半環氧乙烧乾凝膠。 發明之概述 本發明提供乡減合體有機二氧化·㈣路介電質。吾人 發現’纽二氧切有包料雜級裂之問題；並且這限 =現有之處理倾。而且m氫，及純結合，較之二 ί切之界驗合，—麵較不可極化，目衫獄合體介電質 之可相比多孔二氧切具有更低之介電健^ ' (請先閲讀背面之注意事項再填寫本頁) -裝. » i m · -4 - 冰織適用中' X 297公釐） 經濟部中央梯準局貝工消费合作社印製 A7 B7 五、發明説明（） 多孔混合體有機二氧化矽具有優於多孔二氧化矽之優點，包 括既定乾凝膠密度之更低介電係數及增加之材料可撓性，以限制 積體電路製造時之易碎性問題。 附圖之簡要說明 為求明晰，圖式為略圖。 圖1以剖面正視圖示第一較佳實施例金屬間層次介電質。 囷2a-c以剖面正視圖例示一較佳實施例製造方法。 囷3a-f示替代性較佳實施例介電質結構。 較佳實施例之說明
-A 多孔混合體有機二氧化>6夕介電質係得自一舨形式(R〇)3Si(〇R)3 之單體，其中R為任何合宜之烷基及A表示一有機橋連基；此 與先前技藝單體Si(OR)4明顯不同。例如，a可為甲撐，苯撐， 聯本撐’苯撐二曱基等等如較佳實施例中所例示。單體之水解及 冷凝提供與先前技藝類似之凝膠：
(RO>3Si-A-Si(OR㈣0^〇)3Si-A-Si(OR)2-aSi(OR)2-A-Si(O 在A缺少可極化結合，有助更低之介電係數，並且氟取代提供 另外之較佳實施例，由於碳-氟結合之穩定性而具有較高溫度容限 之另外優點。 圖1以剖面圖較佳實施例示乾凝膠110加二氧化矽120之金 屬間層次介電質(IMDS)及一反應障壁(純化層)ί06。金屬線104具 有約0.25-0.5微米之寬度，約0.7微米之高度，以及也具有約0.25 微米之最小間距。預金屬層次介電質（premetal level dielectric，簡 本紙張纽適用中困®家標準（CNS)八4胁（別x297公羡） 赛------IT-------^ (請先聞讀背面之注意事項再填寫本頁)
A7 B7 五、發明説明（） 稱PMD)覆蓋電晶體。 胂基橋連基hybrid xerogel介電質 第一較佳實施例介電質有單體1,4_雙(三乙氧基甲矽烷基)-笨’其在70°C藉下列反應回流1-2小時(單體，乙二醇，乙醇， 水’及硝酸之克分子比為1 : 3 : I.5 : ι·5 : 〇·〇42)，藉以在乙二醇， 乙醇’水，及1ΜΗΝ03之溶液中水解，諸如： 〇 卜⑤ 5/、〇\收 +H2〇3 认丨 〇 t 0 \
+ C^HcrOH 溫和酸性狀況催化水解，並且較高溫度(例如70°c)增加反應 速率’但乙醇在約78充沸騰。可發生每單體替代二或更多乙氧基； 然而，羥基之對抗性冷凝以形成Si-0-Si結合二聚物，三聚物， 藉下列反應消除羥基，諸如： -6- 本紙張从賴中目目轉準（CNS ) A4· ( 2lQx297公楚） 參------tT------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央梯準局貝工消費合作社印裝 五、發明説明（） ί V Η站 2-\ , c/ol^ /^
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S ο ^ ^ 經濟部中央標準局貝工消費合作杜印製 水解加冷凝反應使單體緩慢轉換為不同大小之齊聚物，並且 溶液之粘性增加。達到適當聚合度時，溶液予以冷卻至室溫，並 以乙醇稀釋(咼達300%)’其產生數月或更長之儲存期限。一般為， 平均齊聚物將以3-10單體作成，並有大多數其乙氧基由羥基或矽 氧炫結合所替代。在冷凝時，齊聚物由於在每一齊聚物上之大量 經基地點而可能交聯。 一種鹼諸如氩氧化銨(ΝΗ40Η)催化齊聚物之進一步冷凝；可 恰好在旋塗前將0·25 MNH4OH(以容積計10%)加至齊聚物溶液。 要不然，可使用齊聚物溶液而不添加鹼。8吋直徑晶圓約需3毫 升溶液，以提供約1克平均厚度之塗層。1000-5000轉/分旋轉速 度約10-15秒，一般便足夠。各種旋轉速度可在旋塗過程予以設 定程式，以控制薄膜斑紋，並且背面清洗及邊緣卷緣去除也可予 ----------#------,tx------0 (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） A7 B7 經濟部中央梯率扃貝工消费合作社印製 五、發明説明（） 以合併’以除去邊緣及背面沉積物。也可使用嘴塗或浸塗。冷凝 反應使齊聚物進一步聚合，並藉以與一種矽倍半環氧乙烷聚合物 網絡形成溶劑飽和薄膜凝膠約如： 0^
在塗布後，使薄膜凝膠老化以繼續冷凝及網絡形成。藉乙二 醇之飽和大氣使凝膠中之溶劑保持在晶圓上。12(rc之老化溫度 2-4分鐘便完成冷凝；可將一種鹼催化劑導入大氣。更低之溫度 老化將需要較長之老化時間。 在老化時之溶劑蒸發，可能導致凝膠之過早乾燥及實際收 縮，其增加薄膜密度及介電係數，並引起薄膜龜裂。因此，控制 晶圓上之大氣，或使用較少揮發性溶劑，諸如甘油代替乙醇，藉 以限制溶劑蒸發。 - --. 總趙水解/冷凝將原始乙氧基梦R-0-Si結合之大約70%轉換 成矽氧燒Si_G_Si齡，並將魏&氧基雜合轉触主要為石夕 烧醇Si-O-H結合。表面Si_〇-H基具有作用性及親水性，但在網 Ί — ~Μ 11^I—1Τ-------.^ (請先閲讀背面之注項再填寫本X)
A7 B7 經濟部中央揉準局貞工消费合作社印裝 - 五、發明説明（ 絡予以隔離，並且不另外冷凝。 網絡有微孔，直徑少於ίο毫微米^請察知，圖1中之相鄰 金屬線間之250毫微米最小間距大為超過孔大小，並且金屬線幾 何結構很少影響凝膠形成。 在老化後’在一旋轉器以乙醇清洗晶圓,以替代細孔中之高表 面張力溶劑乙二醇’在隨後乾燥時減少毛細管壓力。由於小孔大 小(小曲率半徑）’在溶劑蒸發時(亦即細孔表面部份沾濕因而液體 表面張力非對稱時），存在高毛細管虔力，並可能導致聚合物網絡 皺縮’產生較濃密之薄膜。 而且，細孔表面Si-O-H基呈現一親水性表面，其可能吸附 水分’运將會增加細介電係數，並脑相鄰金屬表面^在乾燥 時所可能之SiOH紅進-步精反應也可能導致驅之永久收 縮。 ®此， 以六甲基二矽氮烷 (HMDS)(CH3)3Si-NH-Si(CH3)3清洗晶，以疏水性並且也無法進一 步冷凝之Si-0-Si(CH3)3基替代Si姻基，藉以修改細孔表面。 其次，以庚烧或己烧清洗晶圓，以在凝膝乾燥時使毛細管 壓力更為降低。最後’將晶圓置於—在3〇〇 35〇<>c之熱板上約 秒’藉以使錢寒。這留下-有雜之細 物網絡）。 如果聚合物網絡足夠堅固，經得起在乾燥時之毛細管壓力， 也可在乾燥後進行HMDS或其他表面修改。 2下-節綱在製造圖丨之咖層之—時，使用上述乾凝 膠方法。 -9- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ----------^------1T------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央揉準局員工消費合作社印裝 A7 B7 五、發明説明（） IMD製造 圖2a-c例示較佳實施例乾凝膠imd結構之製造步驟，其也 包含一供乾凝膠之鈍化(反應障壁)層。特別是，圖2a示寬度0.25-0.6 微米，高度0.7微米’及線間最小間距0.25微米之包覆鋁線204。 在金屬線204上及在介電質下面之共形鈍化層206提供一供金属 線204之化學反應障壁’保護其以防腐蝕。鈍化層2〇6可為二氧 化矽，有10-50毫微米之厚度，並可藉(等離子增強)CVD予以敷 著。 圖2b示旋著形成薄膜凝膠208之齊聚物溶液。這使用先前 所說明之齊聚物溶液’並藉冷凝催化劑之旋著。儘管其〇.7微米 之深度，厚度0.3-0.5微米之平均薄膜208填滿在最小間距；在金 屬線204上之薄膜厚度僅約為0.1微米。 如先前所說明處理凝膠(老化，替代溶劑，修改細孔表面，及 乾燥），以形成乾凝膠210。然後敷著上面之氧化矽220，並藉諸 如化學機械拋光(CMP)平面化，以產生一如圖2c中所示之平面表 面。通路形成及填滿產生如在圖1中所之下IMD層。 旋著以形成凝膠208，提供一合理平面之表面，上面妙氧化 物之CMP因而可予省略。 單體製備 首先在300毫升四氫。夬喃(THF)添加一少量碘結晶體至15克 鎂旋屑及450毫升TEOS之混合物，並在氮大氣下使混合物回 流，可藉以製備第一較佳實施例之單體。其次，在2小時時間將 100毫升THF中之48克1，4-二漠苯之溶液一滴一滴添加至回流 之混合物。在起始添加之30分鐘以内，反應變成溫和放熱。在 -10- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -----------裂-- C請先閲讀背面之注意Ϋ項再填寫本頁} -訂 線 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明（） 完成添加二溴化物後，保持反應混合物回流1小時。冷卻灰綠色 混合物至室溫’然後在真空除去THF。添加己烷以使任何餘留之 鎮鹽在溶液中沉澱，並在氮下過濾混合物，以產生—種清澈，淺 稼色溶液。在真空除去己烷，並在真空蒸餾除掉其餘之TE〇s， 留下一種棕色油。蒸餾棕色油(130-1351C在200毫托），以產生一 種清澈無色油單體》 氟化混合體乾凝膠 第二實施例乾凝膠IMD為第一較佳實施例之氟化型。特別 疋，乾凝勝有氟取代在笨環橋連基之氫。所有四個氫’或僅有些’ 可以氟予以取代；所有其他參數保持固定氟時，含量愈大，溫度 容限愈佳，並且介電係數愈低。 氟化乾凝膠可藉相同處理步驟自氟化單體作成，或可在乾凝 膠製成後’在低壓暴露至F2 ’藉以予以1化。在製成後之氟化， 由於氟原子之大小大於氫，應該使乾凝膠膨脹，但膨脹應該僅減 少孔隙度。氟化也使HF演變’在各向異性蝕刻後氟化之情形， 其必須予以抽吸去除，以避免金屬或氧化物蝕刻。藉HMDS之 表面修改以替代矽烧醇基，也可以氟化型予 以替代.. 熱穩定性 積想電路製造通常包括非常高溫度初始處理步驟，但在一般 為結基之金屬線形成後’由於銘低熔點，處理之溫度峰值約在450 °C(鋁之燒結溫度）。因之，IMD材料在惰性大氣應該為熱穩定， -11 - 本紙張尺度通用中國國家標準（CNS ) A4規格（210X297公釐） ----------装— (請先閲讀背面之注意Ϋ項再填寫本頁) 訂 線 A7 B7 五、發明説明（） 直到約為意c »前輕連基實狀_結合敎倾供乾凝踢 之此種熱穩定性；的確，使贱苯基代替f基之細孔表面修改， 增強熱穩定性。亦即，以_0_si(c6H5)3基替代細孔表面基冬 Si(CH3)3。 同樣，（部份)氟化一般增加熱穩定性，因而前述諸如讲〇)3沿_ C6F4_Si(OR)3單體或表面修改基諸如办si(CF3)3或_〇Si(C6FA之(部 份)氟化型增強熱穩定性。 替代性橋連基 另外之較佳實施例與第一較佳實施例相似，但在單體及乾凝 膠使用不同之橋連基。特別是’橋連基可由鏈烷，分枝鏈烷，鏈 稀’分枝鏈烯，炔’分枝炔，環烷，及如下列單體所例證之粗砂 所構成： aj} 經濟部中央揉準局員工消费合作社印製 {請先W讀背面之注意事項再填寫本頁) (K0)3 C〇^3 cH3 ch3 -12- 本紙張尺度適用中國國家梯準（CNS) A4規格（210><297公釐） 五、發明説明（ LK〇)^i -csc-s< C〇^h CK〇hsc 5t (r〇)3 5t： -〇〇 A7 B7 p^ 5 1 C〇R)3fe
5i ⑽3 (請先閲讀背面之注意事項再填寫本頁) st C〇K) '3 (RD)_3 义 •OcCr 經濟部中央揉準局貝工消費合作社印製 (m3 5(- 0
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Si (〇R) 3 13 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2!0X297公釐） 經濟部中央揉準局員工消费合作社印裝 A7 B7 五、發明説明（） 鍵炫，鏈烯’及炔鏈可有1至12碳原子；超過12碳原子， 聚合物網絡便開始與聚乙烯相似。同樣，相似長度之鏈烯及炔鏈 提供約略相似之乾凝膠。可使用具有3至8碳環之環烷〃如果石夕 原子間之碳原子之声短路徑不超過12，可使用熔合或鍵接苯或其 他環。 橋連基之選擇依希望之乾凝膠熱穩定性及可撓性而定。特別 是’熱穩定性自鏈烧至可相比之鏈烯.，至可相比之快，至可相比 之環烷，至可相比之粗砂增加。反之，可撓性以相反順序增加： 粗砂為最少撓性，而鏈烷為最多撓性。 利用所有此等橋連基，氟化增加熱穩定性。氟化之缺點為來 自氟之可能之金屬腐钱。 也可使用二或更多上述單體之共聚物以具有中間特徵。 替代性IMD結構 如圖3a-f在剖面圖中所試探性例證，較佳實施例乾凝膠可使 用於替代性較佳實施例IMD結構。特別是，圖3a示乾凝膠有覆 蓋之氧化物及通路在金屬線上面；此為與圖2c加通路並省略鈍 化層相同。 圖3b示乾凝膠在金屬線之最小間距，並在離開自最小間距 之開放場。此乾凝膠結構係如圖2b申所例示得自向後姓刻向下 至原始旋著乾郷之金屬線。-覆蓋氧化物軒敷著在向後侧 之乾凝膠，以完成IMD。向後蝕刻之乾凝膝具有使乾凝膠保留 在最小間距’但在開㈣減少厚度，並目此減讀械強度需求之 優點。其在通路蝕刻時也防止乾凝膠爆裂。的確，原始旋著乾凝膠 -14- 本紙張尺度適用中國鬮家棣準（CNS ) A4規格（2丨0Χ297公釐） I 1-— I裝— —訂 I I線 (請先閏讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作杜印策 A7 B7 五'發明説明（） 愈為共形’在開放場向後蚀刻之乾凝勝愈薄，同時保持乾凝膠填 滿之最小間距》 圖3c示金屬線及乾凝膠上之氧化物掩模僅在最小間距；隨 後氧化物之沉積及平面化完成IMD層。圖3c之結構可方便首先 使用氧化物掩模供金屬蝕刻以形成圖示之金屬線，其次旋著乾凝 膠填滿最小間距加開放場，並覆蓋氧化物掩模，然後向後蚀刻以 清除開放場’但留下最小間距填滿至少至金屬線之高度，而予以 製造。這不同於圖3b之向後姓刻’因為氧化物掩模基本上垂直 延伸最小間距，因而向後蚀刻可在除去金屬線間之乾凝膠前除去 開放場乾凝膠。例如’如果金屬線為0.7微米高，氧化物掩模為 0.34微米高’及乾凝膠厚度在開放場上面為〇 5微米，及在氧化 物掩模上面為0.2微米，則向後姓刻〇.5微米將會恰好清除開放 場，但在最小間距留出0.7微米》當然，在金屬線之外側壁所留下 之乾凝膠將無危害；不論各向同性或各向異性向後姓刻工作。 圖3d僅在最小間開金屬線之姓刻縫隙有乾凝膠，這允許乾 凝膠在金屬線上面及下面延伸(藉縫隙蝕刻至下面之介電質），並 且也藉以提供低介電係數材料至邊緣電場。此IMD結構之製造 藉敷著一種金屬，後隨沉積一種氧化物，掩蔽並蝕刻氧化物以及 金屬沉積一鈍化層，旋著及使將會填滿最小間距加覆蓋氧化物之 乾凝膝乾燥’及最後向後蚀刻’以自氧化物頂部除圭乾凝膠，僅 將其留在缝隙等步驟所進行。 圖3e示一使用乾凝膠之波紋結構。特別是，首先形成乾凝 膠(在金屬線之前），其次在乾凝膠各向異性蝕刻溝槽(加可能之通 •15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 111^—·—— — — ;^— I __ —訂 I I I I I I 線 (請先聞讀背面之注意事項再填寫本頁) 經濟部中央揉準局貝工消费合作社印製 A7 ______B7____ 五、發明説明（）. 路至下面導體），然後大片敷著填滿溝槽及覆蓋乾凝膠之金屬，並 且最後CMP ’以除去在上乾凝膠表面之金屬，但將金屬留在溝 槽，以形成金屬線。 圖3f示一非常厚之乾凝膠，其提供整個IMD(除了可能之鈍 化層）。 圖3a-b，e-f之結構需要來自乾凝膠之機械強度，特別是圖3e· f之結構。對照而言’囷3c-d之結構僅使用乾凝膠在最小間距。 機械強度依乾凝膠密度而定。較佳實施例混合體乾凝膠較之可相 比密度之二氧化矽乾凝膠具有更低介電係數；此對於所需要之介 電係數，混合體乾凝朦可為較滚濃密，從而較之二氧化梦乾凝膠 更堅固。 IMD應用 金屬（或其他導電)線間之上述乾凝膠可應用於各種積體電路 型式。例如記憶體(DRAM,SRAM，快閃EPROM等)具有很多組長 平行導電線諸如位元線，字線’條’位址及資料匯流排等等，並 且乾凝膠在平行線之此專台階填滿最小間距，減少電容柄合及關 聯之相互影響。 修改 較佳實施例可以很多方式予以變化，同時在使用積體電路介 電質之二氧化矽乾凝膠保有有機橋連基之一種或多種特色。例 如，乾凝膠可使用在積體電路内之各位置作為介電質，諸‘在多 晶矽或多化物閘與字線之間及微波電路元件周圍。 較佳實施例結構之尺寸可予以改變’諸如導電線間之最小間 -16- 本紙張尺度適用中國國家標準（CNS ) A4規210X 297公釐' " ----------^------II------.ii {請先閲讀背面之注意事項再填寫本頁} A7 B7 58S099 五、發明説明（） 距為0.18或0.1微米或更少，金屬線高度可改變，並且金屬為銅 或鎢或合金，或矽化物諸如TiSi2或CoSi2，或氮化物諸如TiN或 _，並且氧化物介電質可為氟化氧化物(SiOxFy)或一種羥基氮 化物或一種多層疊層，其純化層可予以省略，或者使用發氮化物 或羥基氮化物等等。 ------^----^------1T------0 (請先閲讀背面之注$項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 -適 尺 準 I標 I家 一国 i釐 9 -2

Claims (1)

  1. 388099 Bs8 申請專利範ΐ " "- L一種積體電路介電質，包含： ⑷乾凝谬’填滿第—與第二導體間之空間之至少一部份，該乾 凝膠3有聚合物網絡，該聚合物網路包括有機橋連基β 2·根據申請專利範圍第1項之介電質，其中： (a)該聚合物網絡之橋連基為選擇自鏈烷 ’鏈稀’块，粗砂，及 環烧之類組，越過橋連基之碳原子之最短路徑為至多12。 ---------^------，訂------^ (請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 8- TT 86642 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）
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