TWI540202B - Polishing pad and manufacturing method thereof - Google Patents
Polishing pad and manufacturing method thereof Download PDFInfo
- Publication number
- TWI540202B TWI540202B TW104102699A TW104102699A TWI540202B TW I540202 B TWI540202 B TW I540202B TW 104102699 A TW104102699 A TW 104102699A TW 104102699 A TW104102699 A TW 104102699A TW I540202 B TWI540202 B TW I540202B
- Authority
- TW
- Taiwan
- Prior art keywords
- isocyanate
- component
- polishing
- polishing pad
- polyurethane resin
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims description 135
- 238000004519 manufacturing process Methods 0.000 title claims description 19
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- 239000012948 isocyanate Substances 0.000 claims description 50
- 150000002513 isocyanates Chemical class 0.000 claims description 39
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- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- 239000004970 Chain extender Substances 0.000 claims description 16
- -1 alkoxyalkyl isocyanate Chemical class 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 229920002635 polyurethane Polymers 0.000 claims description 11
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Description
本發明係有關於研磨墊,其可對透鏡、反射鏡等光學材料或矽晶圓、硬碟用玻璃基板、鋁基板、及一般經金屬研磨加工等之要求高度表面平面性之材料穩定且高研磨效率地進行平面化加工。本發明之研磨墊尤其適合使用於在矽晶圓及其上形成有氧化物層、金屬層等之元件上欲進一步積層‧形成此等氧化物層或金屬層之前所進行之平面化步驟。
作為要求高度表面平面性之材料的代表性者,係可舉出製造半導體積體電路(IC、LSI)之被稱為矽晶圓的單結晶矽圓盤。矽晶圓在IC、LSI等的製造步驟中,在用以形成電路形成所使用各種薄膜之可信賴的半導體接合,而進行積層‧形成氧化物層或金屬層的各步驟中,被要求將表面以高精度修整為平面。在如此之研磨修整步驟中,一般而言研磨墊被黏附在被稱為平臺(platen)之可旋轉的支撐圓盤,半導體晶圓等加工物被黏附在研磨頭。然後藉由雙方
的運動,使平臺與研磨頭之間產生相對速度,進一步藉由將含有研磨粒之研磨漿體連續供給至研磨墊上,使研磨操作被實行。
作為研磨墊之研磨特性,係要求研磨對象物之平面性(planarity)及面內均勻性優良,研磨速度快。關於研磨對象物之平面性、面內均勻性可藉由使研磨層高彈性率化的方式得到一定程度的改善。此外,關於研磨速度,可藉由使用為發泡體之研磨層而使漿體的保持量變多,或者使用親水性之研磨層提高保持漿體能力的方式提升。
例如,在專利文獻1中,用以提升研磨墊之水的可濕性,提案一種研磨墊用組成物,其特徵係含有(A)交聯彈性體、(B)具有選自於羧基、胺基、羥基、環氧基、磺酸基及磷酸基所構成之群中至少1種官能基的物質、及水溶性物質,且,上述(A)交聯彈性體為使1,2-聚丁二烯交聯的聚合物。
此外,在專利文獻2,用以使漿體容易與研磨墊融合,提案有一種研磨墊,含有具有親水性基之化合物進行共聚合而成的胺酯樹脂,且以含有親水性基之聚胺酯組成物構成,其中該親水劑係選自於2,4,7,9-四甲基-5-癸炔-4,7-二醇-二聚氧乙烯醚、及2,4,7,9-四甲基-5-癸炔-4,7-二醇所構成之群中至少一種,具有該親水性基之化合物為環氧乙烷單體。
此外,在專利文獻3,用以獲得平面性、面內均勻性、研磨速度良好、研磨速度之變化少,且壽限特性優
良之研磨墊,提案作為聚胺酯樹脂發泡體的原料成分之1種,使用原料成分含有具有25重量%以上環氧乙烷單位(-CH2CH2O-)之數量平均分子量500以上的親水性高分子量多元醇成分與異氰酸酯成分的親水性異氰酸酯末端預聚物(B)。
此外,在專利文獻4,提案有用以提升研磨層之親水性,含有為可溶於可溶解構成研磨層之樹脂之有機溶劑,且難溶於或不溶於水之部分醯化多醣類成分的研磨層。
但,若使研磨層為親水性,雖然研磨速度會變快,但有研磨對象物之平面性會變差的問題。
專利文獻1:日本專利第3826702號說明書
專利文獻2:日本專利第3851135號說明書
專利文獻3:日本專利第4189963號說明書
專利文獻4:日本專利第5189440號說明書
本發明之目的在於提供一種研磨速度快且平面特性優良之研磨墊及其製造方法。
本發明人等為解決前述課題不斷努力檢討的結果,發現藉由下述研磨墊可解決前述課題,而得以完成本
發明。
本發明乃有關一種研磨墊,係具有由聚胺酯樹脂發泡體構成之研磨層者,其特徵在於前述聚胺酯樹脂發泡體之形成材料的聚胺酯樹脂,於側鏈具有下述通式(1)所示之烷氧基矽基。
(式中,X為OR1或OH,R1各自獨立為碳數1~4的烷基。)
如上述,本發明之特徵在將前述烷氧基矽基導入至聚胺酯樹脂的側鏈。存在於研磨層表面之前述烷氧基矽基,會於研磨中因漿體中的水被水解,而在研磨層表面產生矽醇基。該矽醇基為親水性因此會提升研磨層表面的親水性。其結果,可提高漿體的保持能力,而可使研磨速度變快。
另一方面,由於烷氧基矽基被導入至聚胺酯樹脂的側鏈,故聚胺酯樹脂難以因漿體而澎潤。此外,存在於研磨層內部之前述烷氧基矽基因難以與漿體中的水接觸,所以難以被水解。因此,僅研磨層表面可被親水化,而可抑制研磨層整體之硬度的降低。其結果,研磨墊之平面化特性難以降低。
前述聚胺酯樹脂宜為含有含烷氧基矽基異氰酸酯末端預聚物及鏈伸長劑之聚胺酯原料組成物的反應硬化
體,該含烷氧基矽基異氰酸酯末端預聚物為含有異氰酸酯成分與含3官能以上多元醇之多元醇成分的預聚物原料組成物之反應物,且該異氰酸酯成分包含下述通式(2)所示之含烷氧基矽基異氰酸酯。
(式中,X為OR1或OH,R1各自獨立為碳數1~4的烷基,R2為碳數1~6的伸烷基。)
前述含烷氧基矽基異氰酸酯宜為3-異氰酸酯丙基三乙氧基矽烷。
此外,前述含烷氧基矽基異氰酸酯的含量,宜於聚胺酯原料組成物中佔1~10重量%。由於烷氧基矽基被導入至聚胺酯樹脂的側鏈,所以因少量烷氧基矽基的導入而表現親水性。在含烷氧基矽基異氰酸酯的含量未達1重量%的情況下,難以引發研磨層表面的親水化,若超過10重量%則有製作研磨特性優良之研磨層變困難的傾向。
此外本發明並有關一種研磨墊之製造方法,係包含一將含有異氰酸酯末端預聚物之第1成分與含有鏈伸長劑之第2成分混合,並進行硬化來製作聚胺酯樹脂發泡體的步驟,其特徵在於:前述步驟係將聚矽氧系界面活性劑以相對於第1成分及第2成分之合計重量為0.05~10重量%的方式添加至第1成
分中,再將前述第1成分與非反應性氣體攪拌而調製出使前述非反應性氣體成氣泡分散之氣泡分散液後,於前述氣泡分散液混合含有鏈伸長劑之第2成分,並進行硬化來製作聚胺酯樹脂發泡體的步驟,其中前述第1成分含有含烷氧基矽基異氰酸酯末端預聚物,該含烷氧基矽基異氰酸酯末端預聚物為含有異氰酸酯成分與含3官能以上多元醇之多元醇成分的預聚物原料組成物之反應物,且該異氰酸酯成分包含下述通式(2)所示之含烷氧基矽基異氰酸酯。
(式中,X為OR1或OH,R1各自獨立為碳數1~4的烷基,R2為碳數1~6的伸烷基。)
前述含烷氧基矽基異氰酸酯宜為3-異氰酸酯丙基三乙氧基矽烷。
前述含烷氧基矽基異氰酸酯的含量宜在前述第1成分及前述第2成分之合計重量中佔1~10重量%。
此外,本發明並有關一種半導體元件之製造方法,其包含一使用前述研磨墊研磨半導體晶圓表面的步驟。
本發明之研磨墊其研磨速度快,且平面特性優良。此外,本發明之研磨墊在研磨操作時研磨層表面會因漿體而變成親水性,因此漿體中之研磨粒不易產生凝集,
可有效抑制在研磨對象物產生刮痕的情形。
1‧‧‧研磨墊(研磨層)
2‧‧‧研磨定盤
3‧‧‧研磨劑(漿體)
4‧‧‧研磨對象物(半導體晶圓)
5‧‧‧支撐臺(研磨頭)
6、7‧‧‧旋轉軸
圖1係表示在化學機械(CMP)研磨所使用研磨裝置之一例的概略構成圖。
本發明之研磨墊可為僅以聚胺酯樹脂發泡體構成之研磨層,亦可為研磨層與其他層(例如緩衝層等)的積層體。
作為聚胺酯樹脂發泡體之形成材料的聚胺酯樹脂,係於側鏈具有下述通式(1)所示之烷氧基矽基。X以OR1為佳。此外,R1以甲基或乙基為佳。
(式中,X為OR1或OH,R1各自獨立為碳數1~4的烷基。)
作為聚胺酯樹脂的原料,係與異氰酸酯成分、多元醇成分(高分子量多元醇、低分子量多元醇)、及鏈伸長劑一起使用用以將上述通式(1)所示之烷氧基矽基導入至聚胺酯樹脂之側鏈的含烷氧基矽基化合物。將烷氧基矽基導入至聚胺酯樹脂之側鏈的方法無特別限制,例如可舉出1)使3官能以上之多元醇成分與含烷氧基矽基異氰酸酯進行反應的方法、2)使3官能以上之異氰酸酯成分與含烷氧基矽基醇或含烷氧基矽基胺進行反應的方法、3)使含烷氧
基矽基異氰酸酯在聚胺酯樹脂進行反應的方法(脲甲酸酯反應或縮二脲反應)等。
在本發明,聚胺酯樹脂宜為含有含烷氧基矽基異氰酸酯末端預聚物及鏈伸長劑之聚胺酯原料組成物的反應硬化體,該含烷氧基矽基異氰酸酯末端預聚物為含有異氰酸酯成分與含3官能以上多元醇之多元醇成分的預聚物原料組成物之反應物,且該異氰酸酯成分包含下述通式(2)所示之含烷氧基矽基異氰酸酯。
(式中,X為OR1或OH,R1各自獨立為碳數1~4的烷基,R2為碳數1~6的伸烷基。)
上述通式(2)所示之含烷氧基矽基異氰酸酯,宜使用3-異氰酸酯丙基乙氧基矽烷。
作為前述含烷氧基矽基異氰酸酯以外的異氰酸酯成分,可使用聚胺酯領域中公知之化合物而無特別限制。例如可舉出2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、2,2’-二苯甲烷二異氰酸酯、2,4’-二苯甲烷二異氰酸酯、4,4’-二苯甲烷二異氰酸酯、1,5-萘二異氰酸酯、對苯二異氰酸酯、間苯二異氰酸酯、對伸茬基二異氰酸酯、間伸茬基二異氰酸酯等芳族二異氰酸酯;伸乙基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、1,6-六亞甲基二異
氰酸酯等脂肪族二異氰酸酯;1,4-環己烷二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、異佛酮二異氰酸酯、降莰烷二異氰酸酯等脂環式二異氰酸酯等。此等係可單獨使用,亦可將2種以上併用。
作為前述3官能以上的多元醇(具有3個以上羥基的多元醇),例如可舉出聚己內酯三醇等官能基數為3的高分子量多元醇、聚己內酯四醇等官能基數為4的高分子量多元醇、三羥甲基丙烷、甘油、二甘油、1,2,6-己三醇、三乙醇胺、新戊四醇、四羥甲基環己烷、甲基葡萄糖苷、及此等之氧化烯(EO、PO等)加成物等。此等可單獨使用,亦可將2種以上併用。此等之中,以使用聚己內酯三醇為佳。
前述3官能以上之多元醇以外的多元醇成分,可舉如一般在聚胺酯樹脂之技術領域中所使用的高分子量多元醇。例如可舉出以聚四亞甲基醚乙二醇、聚乙二醇等為代表的聚醚多元醇;以聚己二酸二丁酯為代表的聚酯多元醇;聚己內酯多元醇、如聚己內酯之聚酯乙二醇與碳酸伸烷酯之反應物等所例示的聚酯聚碳酸酯多元醇;將乙烯碳酸酯與多元醇進行反應,接著將所獲得的反應混合物與有機二羧酸進行反應的聚酯聚碳酸酯多元醇;藉由聚羥基化合物與芳基碳酸酯進行轉酯化所獲得的聚碳酸酯多元醇等。此等可單獨使用,亦可將2種以上併用。
高分子量多元醇的重量平均分子量係無特別限定,但從可獲得的聚胺酯樹脂之彈性特性等觀點來看,以
500~3000為佳。若重量平均分子量未達500,則使用此所獲得之聚胺酯樹脂不具有充分的彈性特性,容易成為易碎的聚合物,此聚胺酯樹脂構成的研磨墊會有太硬,成為研磨對象物表面刮痕之產生原因的情況。此外,由於容易磨損,從研磨墊壽命的觀點來看亦為不佳。另一方面,若重量平均分子量超過3000,則使用此所獲得之聚胺酯樹脂構成的研磨墊會變軟,變得難以獲得令人充分滿足的平面性。
除上述之高分子量多元醇之外,亦可併用乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、1,4-環己烷二甲醇、3-甲基-1,5-戊烷二醇、二乙二醇、三乙二醇、1,4-雙(2-羥基乙氧基)苯、二乙醇胺、及N-甲基二乙醇胺等低分子量多元醇。此外,亦可併用乙烯二胺、甲苯二胺、二苯甲烷二胺、及二乙烯三胺等低分子量多胺。此外,亦可併用單乙醇胺、2-(2-胺基乙基胺基)乙醇、及單丙醇胺等醇胺。此等低分子量多元醇、低分子量多胺等可單獨使用,亦可將2種以上併用。
前述含烷氧基矽基異氰酸酯末端預聚物,係使用前述異氰酸酯成分及多元醇成分等,以異氰酸酯基(NCO)與活性氫(H*)之等值比(NCO/H*)在1.2~8的範圍,宜為在1.5~3的範圍進行加熱反應而製造。在未達1.2的情況下,在製造預聚物時有容易膠化的傾向。另一方面,在超過8的情況下,在與鏈伸長劑反應時發熱量會變大,有難
以獲得均勻之研磨墊的傾向。
亦可與前述含烷氧基矽基異氰酸酯末端預聚物,同時併用不含烷氧基矽基的異氰酸酯末端預聚物。
在前述異氰酸酯末端預聚物之硬化係使用鏈伸長劑。鏈伸長劑係至少具有2個以上之活性氫基的有機化合物,作為活性氫,可例示羥基、一級或二級胺基、硫醇基(SH)等。具體而言可舉出4,4’-亞甲基雙(鄰氯苯胺)(MOCA)、2,6-二氯-對苯二胺、4,4’-亞甲基雙(2,3-二氯苯胺)、3,5-雙(甲基硫醇基)-2,4-甲苯二胺、3,5-雙(甲基硫醇基)-2,6-甲苯二胺、3,5-二乙基甲苯-2,4-二胺、3,5-二乙基甲苯-2,6-二胺、1,3-丙二醇-二-對胺苯甲酸酯、1,2-雙(2-胺基苯基硫基)乙烷、4,4’-二胺基-3,3’-二乙基-5,5’-二甲基二苯甲烷、N,N’-二-二級丁基-4,4’-二胺基二苯甲烷、3,3’-二乙基-4,4’-二胺基二苯甲烷、間伸茬基二胺、N,N’-二-二級丁基-對苯二胺、間苯二胺、及對伸茬基二胺等所例示之多胺類;或者,上述之低分子量多元醇或低分子量多胺。其等可使用1種,或將2種以上混合亦無妨。
前述含烷氧基矽基異氰酸酯的含量,宜在聚胺酯樹脂原料組成物中佔1~10重量%,且1~8重量%較佳,1~5重量%更佳。
聚胺酯樹脂發泡體,係可應用熔融法、溶液法等公知之胺酯化技術進行製造,但在考慮到成本、作業環境的情況下,以使用熔融法製造為佳。
聚胺酯樹脂發泡體的製造,係預聚物法、單塞
法之任一者皆為可能。在預聚物法的情況下,相對於鏈伸長劑之活性氫基(羥基、胺基)數之前述預聚物的異氰酸酯基數,以0.9~1.2為佳。
作為聚胺酯樹脂發泡體之製造方法,係可舉出添加中空珠之方法、機械性發泡法(包含機械泡沫法)、化學性發泡法等。
尤其以使用聚矽氧系界面活性劑的機械性發泡法為佳,其中聚矽氧系界面活性劑係聚烷基矽氧烷與聚醚的共聚物。作為聚矽氧系界面活性劑,例示有SH-192及L-5340(Dow Corning Toray公司製)、B8443、B8465(Goldschmidt公司製)等適合的化合物。聚矽氧系界面活性劑宜以在聚胺酯原料組成物中佔0.05~10重量%的方式添加,且0.1~5重量%較佳。
因應必要,亦可在聚胺酯原料組成物中,添加抗氧化劑等穩定劑、潤滑劑、顏料、填充劑、抗靜電劑、其他添加劑。
聚胺酯樹脂發泡體可為獨立氣泡類型,亦可為連續氣泡類型,但為了防止漿體侵入研磨層內部,及防止存在於研磨層內部之烷氧基矽基的水解,以獨立氣泡類型為佳。
於以下說明關於製造構成研磨墊(研磨層)之微細氣泡類型聚胺酯樹脂發泡體之方法實例。這樣的聚胺酯樹脂之製造方法,係具有以下步驟。
1)製造含烷氧基矽基異氰酸酯末端預聚物之氣泡
分散液的發泡步驟
將聚矽氧系界面活性劑添加至含烷氧基矽基異氰酸酯末端預聚物(第1成分)中,且在非反應性氣體的存在下進行攪拌,使非反應性氣體成氣泡分散而做成氣泡分散液。在前述預聚物於常溫為固體的情況下,預熱至適當溫度,經熔融後使用。
2)鏈伸長劑的混合步驟
於上述氣泡分散液中添加鏈伸長劑(第2成分)並經混合、攪拌而做成發泡反應液。
3)鑄件步驟
將上述發泡反應液倒入至模具。
4)硬化步驟
將倒入至模具的發泡反應液加熱,且使其反應硬化。
作為用以形成氣泡所使用的非反應性氣體,係以非可燃性者為佳,具體而言例示有氮、氧、碳酸氣、氫或氬等惰性氣體或此等之混合氣體,使用經乾燥除去水分的空氣在成本上為尤佳。
作為使非反應性氣體成氣泡狀被分散至含有聚矽氧系界面活性劑之第1成分的攪拌裝置,係可使用公知的攪拌裝置而無特別限制,具體而言例示有均質機、溶解器、2軸行星式混合器(planetary mixer)等。攪拌裝置之攪拌翼的形狀亦無特別限定,但使用籠型攪拌翼可獲得微細氣泡而為佳。
另外,使用不同攪拌裝置進行發泡步驟中製作
氣泡分散液的攪拌、與混合步驟中添加鏈伸長劑加以混合的攪拌,亦為適宜的態樣。尤其在混合步驟之攪拌亦可為非形成氣泡之攪拌,以使用不會捲入大氣泡的攪拌裝置為佳。作為如此之攪拌裝置,以行星式混合器為適宜。發泡步驟與混合步驟之攪拌裝置使用相同的攪拌裝置亦無妨,在使用時因應必要進行調整攪拌翼之旋轉速度等攪拌條件之調整亦為適宜。
在聚胺酯樹脂發泡體之製造方法中,對將發泡反應液倒入模具反應至不會流動為止的發泡體進行加熱、後硬化的操作,係有提升發泡體之物理特性的效果,非常適宜。以將發泡反應液倒入模具後立刻放入加熱烤箱作為進行後硬化的條件亦可,由於即使在如此條件下熱亦不會馬上傳導至反應成分,因此氣泡徑不會變大。為使氣泡形狀穩定,硬化反應宜在常溫下進行。
聚胺酯樹脂發泡體,係使用三級胺系等公知之促進聚胺酯反應的觸媒也沒關係。觸媒的種類、添加量係考慮在混合步驟後,倒入預定形狀之模具的流動時間來進行選擇。
聚胺酯樹脂發泡體的製造,係可為秤量各成分投入至容器,並進行攪拌的批次方式,此外亦可為將各成分與非反應性氣體連續供給至攪拌裝置進行攪拌,並送出氣泡分散液製造成形品的連續生產方式。
此外,將聚胺酯樹脂發泡體原料的預聚物放入反應容器內,然後投入鏈伸長劑,在攪拌後倒入預定大小
的鑄件製造鑄塊,並使用鉋狀、或者手鋸狀的切片機切片的方法,或者在前述之鑄件的階段,製成薄片狀亦可。
聚胺酯樹脂發泡體的平均氣泡徑係以30~200μm為佳。在逸脫此範圍的情況下,有研磨後之研磨對象物的平面性降低的傾向。
聚胺酯樹脂發泡體的硬度,宜經ASKER D硬度計顯示為40~70度。在ASKER D硬度未達40的情況下,研磨對象物的平面度會降低,另一方面,在超過70度的情況下,平面度雖然良好,但會有研磨對象物之均勻性(uniformity)降低的傾向。
聚胺酯樹脂發泡體的比重,係以0.5~1.3為佳。在比重未達0.5的情況下,有研磨層之表面強度降低,且研磨對象物之平面性降低的傾向。此外,在較1.3大的情況下,有研磨層表面的氣泡數變少,平面性雖然良好,但研磨速度降低的傾向。
在本發明之研磨墊(研磨層)與研磨對象物接觸的研磨表面,宜具有可保持‧更新漿體的表面形狀。由發泡體構成的研磨層,於研磨表面具有許多開口,擁有保持‧更新漿體的作用,但為了更有效率進行更進一步的漿體保持性與漿體之更新,此外亦為了防止因吸附研磨對象物造成研磨對象物的破壞,以在研磨表面具有凹凸構造為佳。凹凸構造只要為可保持‧更新漿體的形狀便無特別限定,例如可舉出XY格子溝、同心圓狀溝、貫通孔、未貫通孔、多角柱、圓柱、螺旋狀溝、偏心圓狀溝、放射狀
溝、及將此等之溝組合者。此外,此等之凹凸構造一般為具有規則性者,但為了讓漿體之保持‧更新性更符合期望,亦可讓間距、溝寬、溝深等分別在一定範圍內變化。
前述凹凸構造之製作方法係非被特別限定者,例如可舉出使用預定尺寸之如鑽頭的治具進行機械切削的方法;藉由將樹脂倒入具有預定之表面形狀的模具,使其硬化而進行製作的方法;以具有預定之表面形狀的壓板壓製樹脂進行製作的方法;使用光學微影法製作的方法;使用印刷手法製作的方法;使用二氧化碳雷射等雷射光進行製作的方法等。
本發明之研磨墊亦可為將前述研磨層與緩衝片貼合者。
前述緩衝片(緩衝層),係補足研磨層之特性者。緩衝片係在化學機械研磨(CMP)中,用以兼顧為互償關係之平面性與均勻性兩者之所必須。所謂平面性係指在研磨具有於圖案形成時產生之微小凹凸的研磨對象物時,其圖案部的平面性,所謂均勻性係指研磨對象物整體的均勻性。根據研磨層的特性會改善平面性,而根據緩衝片的特性會改善均勻性。在本發明之研磨墊,緩衝片宜使用較研磨層柔軟者。
作為前述緩衝片,係例如可舉出聚酯不織布、尼龍不織布、丙烯酸不織布等纖維不織布或如經含浸聚胺酯之聚酯不織布的樹脂含浸不織布;聚胺酯發泡體、聚乙烯發泡體等高分子樹脂發泡體;丁二烯橡膠、異戊二烯橡
膠等橡膠性樹脂;感光性樹脂等。
作為將研磨層與緩衝片貼合的手段,係例如可舉出將研磨層與緩衝片以雙面膠帶夾住壓製的方法。
前述雙面膠帶係具有於不織布或薄膜等基材的兩面設置有接著層之一般構造者。若考慮到防止漿體對緩衝片的浸透,則宜於基材使用薄膜。此外,接著層的組成,例如可舉出橡膠系接著劑或丙烯酸系接著劑等。若考慮到金屬離子的含量,則丙烯酸系接著劑因金屬離子含量少而為佳。此外,也有研磨層與緩衝片的組成不同的情形,因此亦可使雙面膠帶之各接著層的組成不同,調整各層之接著力。
本發明之研磨墊,亦可為在與平臺接著的面設置雙面膠帶。作為該雙面膠帶,可使用具有與上述相同於基材的兩面設置有接著層之一般構造者。作為基材,例如可舉出不織布或薄膜等。若考慮到研磨墊在使用後要自平臺剝離,宜於基材使用薄膜。此外,作為接著層的組成,例如可舉出橡膠系接著劑或丙烯酸系接著劑等。若考慮到金屬離子的含量,則丙烯酸系接著劑因金屬離子含量少而為佳。
半導體元件之製造係經使用前述研磨墊研磨半導體晶圓表面的步驟。所謂半導體晶圓,一般係指於矽晶圓上積層配線金屬及氧化膜者。半導體晶圓之研磨方法,在研磨裝置並無特別限制,例如在進行時使用如圖1所示具備支撐研磨墊(研磨層)1之研磨定盤2,與支撐半導體晶
圓4之支撐臺(研磨頭)5與用以對晶圓均勻加壓之包裝材,與研磨劑3之供給機構的研磨裝置等。研磨墊1係例如藉由以雙面膠帶貼附,裝著於研磨定盤2。研磨定盤2與支撐臺5,被以各自支撐之研磨墊1與半導體晶圓4成為對向的方式進行配置,分別具備旋轉軸6、7。此外,在支撐臺5方,設置有用以將半導體晶圓4頂至研磨墊1的加壓機構。在研磨之際,一邊使研磨定盤2與支撐臺5旋轉一邊將半導體晶圓4頂至研磨墊1,並在供給漿體的同時進行研磨。漿體的流量、研磨荷重、研磨定盤旋轉數、及晶圓旋轉數並無特別限制,在適當調整下進行。
藉此使半導體晶圓4之表面突出的部分被除去而被研磨成平面狀。之後,藉由切割、接合、封裝等製造半導體元件。半導體元件係被使用於執行單元或記憶體等。
以下,藉由實施例說明本發明,但本發明非受此等實施例所限定者。
[測定、評價方法]
(平均氣泡徑之測定)
將用薄片切片機把製造之聚胺酯樹脂發泡體以1mm以下盡可能薄的厚度平行切出者作為測定用試料。使用掃描式電子顯微鏡(Hitachi ScienceSystems公司製,S-3500N)以100倍攝影試料表面。然後,使用圖像解析軟體(MITANI CORPORATION公司製,WIN-ROOF),測定任意範圍之全氣泡的圓當量直徑,並從其測定值算出平均氣泡徑。
(比重之測定)
以JIS Z8807-1976為基準進行。比重測定用試料使用將製造之聚胺酯樹脂發泡體切成4cm×8.5cm之長方形(厚度:任意)者,於溫度23℃±2℃、濕度50%±5%的環境靜置16小時。測定使用比重計(Sartorius公司製)來測定比重。
(硬度之測定)
以JIS K6253-1997為基準進行。硬度測定用試料使用將製造之聚胺酯樹脂發泡體切成2cm×2cm(厚度:任意)之大小者,於溫度23℃±2℃、濕度50%±5%的環境靜置16小時。測定時將試料重疊,使厚度成為6mm以上。使用硬度計(高分子計器公司製,ASKER D型硬度計)測定硬度。此外,將試料浸漬於水48小時,然後取出試料稍微擦去表面的水分,再以相同的方法測定硬度。
(研磨特性之評價)
研磨裝置使用MAT-ARW-8C1A(MAT(股)製),並使用製造之研磨墊,進行研磨特性之評價。研磨速度係根據將於8吋矽晶圓製膜1μm熱氧化膜者研磨60秒時的研磨量算出。氧化膜之膜厚測定使用光干涉式膜厚測定裝置(Nanometrics公司製,裝置名:Nanospec)。作為研磨條件,係將矽石漿體(SS12,Cabot公司製)作為漿體在研磨中以流量120ml/min的方式添加。研磨荷重為4.5psi、研磨定盤旋轉數為93rpm,晶圓旋轉數為90rpm。
平面化特性係根據摩耗量進行評價。將熱氧化膜堆積0.5μm至8吋矽晶圓後,在進行預定之圖案化後,於
p-TEOS堆積1μm氧化膜,製作初期落差0.5μm之附圖案晶圓。將此晶圓在前述條件下進行研磨,研磨後測定各落差算出磨耗量。所謂摩耗量,係指在寬270μm之線以30μm之空格並排的圖案與寬30μm之線以270μm之空格並排的圖案,前述2種圖案之線上部的落差在2000Å以下時之270μm空格的摩耗量。在270μm空格之摩耗量少的情況下,表示不想摩耗之部分的磨耗量少,平面性高。
刮痕之評價係藉由以下方式進行,在前述條件下研磨3片8吋測試晶圓,之後將堆積有厚度10000Å之熱氧化膜的8吋晶圓研磨1分鐘,然後使用KLA-Tencor公司製之缺陷檢測裝置(Surfscan SP1),測定在研磨後之晶圓上有多少0.19μm以上的條痕。
實施例1
在反應容器內,加入3異氰酸酯丙基三乙氧基矽烷(信越化學股份有限公司製,KBE-9007)10.2重量份、甲苯二異氰酸酯(2,4-體/2,6-體=80/20的混合物,TDI-80)37.8重量份、聚己內酯三醇(Daicel chemical公司製,PCL305,羥值:305mgKOH/g,官能基數:3)22.6重量份、數量平均分子量650之聚四亞甲基醚乙二醇(PTMG650)26.5重量份、及二乙二醇(DEG)2.9重量份(NCO Index:1.9),以75℃反應3小時而獲得含烷氧基矽基異氰酸酯末端預聚物(NCO重量%:9.12重量%,以下稱為Si-預聚物)。
在反應容器內加入聚醚系預聚物(Uniroyal公司製,Adiprene L-325)75重量份、製造之Si-預聚物25重量
份、及聚矽氧系界面活性劑(Goldschmidt公司製,B8465)3重量份進行混合,調整至70℃進行減壓脫泡。之後,使用攪拌翼以旋轉數900rpm激烈攪拌約4分鐘,將氣泡拌入反應系統內。之後,於反應容器內添加預先以120℃熔融之4,4’-亞甲基雙(鄰氯苯胺)(以下稱為MOCA)26.4重量份(NCO Index:1.1)。將該混合液攪拌約70秒後,倒入至麵包型敞模(鑄件容器)。在此混合液喪失流動性的階段放入烤箱內,於100℃進行16小時後硬化,獲得聚胺酯樹脂發泡體。
使用切片機(Amitec公司製,VGW-125)將加熱至約80℃之前述聚胺酯樹脂發泡體塊切片,獲得聚胺酯樹脂發泡體片。接著,使用拋光機(Amitec公司製)對該片之表面進行拋光處理至厚度成為1.27mm為止,成為厚度精度良好的片。以直徑61cm的大小貫穿此經拋光處理的片,使用溝加工機(Techno公司製)於表面進行溝寬0.25mm、溝間隔1.50mm、溝深0.40mm之同心圓狀的溝加工,獲得研磨層。對此研磨層之溝加工面與反向的面使用貼合機貼上雙面膠帶(積水化學工業公司製,Double tack tape)。並且,將經電暈處理之緩衝片(Toray公司製,聚乙烯發泡體,TORAYPEF,厚度0.8mm)的表面進行拋光處理,使用貼合機將其貼合至前述雙面膠帶。並且,在緩衝片之其他面使用貼合機貼上雙面膠帶製作研磨墊。
實施例2~8、比較例1~3
除了採用記載於表1之配方以外以與實施例1相同的方
法製作研磨墊。另外,表1中之親水性預聚物係以下述方法製作。
在反應容器內加入聚乙二醇(PEG,第一工業製藥公司製,數量平均分子量1000)40重量份、聚乙二醇(PEG,第一工業製藥公司製,數量平均分子量600)12.8重量份、DEG 6重量份,在攪拌的同時進行減壓脫水1~2小時。接著,將氮導入可分離燒瓶內,且於氮氣沖洗後添加TDI-80(41.2重量份)。在將反應系統內溫度維持在70℃左右的同時攪拌到反應結束為止。反應之結束係定為在NCO%幾乎沒有變化的階段(NCO重量%:9.96重量%)。之後,進行約2小時的減壓脫泡,獲得親水性預聚物。
[表1]
實施例1~8之研磨墊,其研磨速度快,且平面化特性優良。此外,可有效抑制於晶圓產生刮痕的情形。另一方面,比較例1~3之研磨墊,在研磨速度及平面化特性都不充分。此外,比較例1及比較例2之研磨墊,無法抑制於晶圓產生刮痕的情形。
本發明之研磨墊可對鏡片、反射鏡等光學材料或矽晶圓、鋁基板、及一般經金屬研磨加工等之要求高度表面平面性之材料穩定且高研磨效率地進行平面化加工。本發明之研磨墊尤其適合使用於在矽晶圓及其上形成有氧化物層、金屬層等之元件上欲進一步積層‧形成此等氧化物層或金屬層之前所進行之平面化步驟。
1‧‧‧研磨墊(研磨層)
2‧‧‧研磨定盤
3‧‧‧研磨劑(漿體)
4‧‧‧研磨對象物(半導體晶圓)
5‧‧‧支撐臺(研磨頭)
6、7‧‧‧旋轉軸
Claims (8)
- 一種研磨墊,係具有由聚胺酯樹脂發泡體構成之研磨層(但,排除含有布帛之研磨層)者,其特徵在於前述聚胺酯樹脂發泡體之形成材料的聚胺酯樹脂,於側鏈具有下述通式(1)所示之烷氧基矽基;
- 如請求項1之研磨墊,其中前述聚胺酯樹脂係含有含烷氧基矽基異氰酸酯末端預聚物及鏈伸長劑之聚胺酯原料組成物的反應硬化體,該含烷氧基矽基異氰酸酯末端預聚物為含有異氰酸酯成分與含3官能以上多元醇之多元醇成分的預聚物原料組成物之反應物,且該異氰酸酯成分包含下述通式(2)所示之含烷氧基矽基異氰酸酯;
- 如請求項2之研磨墊,其中前述含烷氧基矽基異氰酸酯 係3-異氰酸酯丙基三乙氧基矽烷。
- 如請求項2或3之研磨墊,其中前述含烷氧基矽基異氰酸酯的含量係於聚胺酯原料組成物中佔1~10重量%。
- 一種研磨墊之製造方法,係包含一將含有異氰酸酯末端預聚物之第1成分與含有鏈伸長劑之第2成分混合,並進行硬化來製作聚胺酯樹脂發泡體的步驟,其特徵在於:前述步驟係將聚矽氧系界面活性劑以相對於第1成分及第2成分之合計重量為0.05~10重量%的方式添加至第1成分中,再將前述第1成分與非反應性氣體攪拌而調製出使前述非反應性氣體成氣泡分散之氣泡分散液後,於前述氣泡分散液混合含有鏈伸長劑之第2成分,並進行硬化來製作聚胺酯樹脂發泡體的步驟,其中前述第1成分含有含烷氧基矽基異氰酸酯末端預聚物,該含烷氧基矽基異氰酸酯末端預聚物為含有異氰酸酯成分與含3官能以上多元醇之多元醇成分的預聚物原料組成物之反應物,且該異氰酸酯成分包含下述通式(2)所示之含烷氧基矽基異氰酸酯;
- 如請求項5之研磨墊之製造方法,其中前述含烷氧基矽 基異氰酸酯係3-異氰酸酯丙基三乙氧基矽烷。
- 如請求項5或6之研磨墊之製造方法,其中前述含烷氧基矽基異氰酸酯的含量,係在前述第1成分及前述第2成分合計重量中佔1~10重量%。
- 一種半導體元件之製造方法,係包含一使用如請求項1至4中任一項之研磨墊研磨半導體晶圓表面的步驟。
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