TW202033694A - 具有增強的缺陷抑制的酸性拋光組成物和拋光襯底之方法 - Google Patents
具有增強的缺陷抑制的酸性拋光組成物和拋光襯底之方法 Download PDFInfo
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- TW202033694A TW202033694A TW109102840A TW109102840A TW202033694A TW 202033694 A TW202033694 A TW 202033694A TW 109102840 A TW109102840 A TW 109102840A TW 109102840 A TW109102840 A TW 109102840A TW 202033694 A TW202033694 A TW 202033694A
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- Prior art keywords
- succinic anhydride
- chemical mechanical
- mechanical polishing
- polishing composition
- substrate
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
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Abstract
揭露了一種酸性化學機械拋光組成物,其包含具有正ζ電勢的膠體二氧化矽磨料顆粒以及選擇的烷氧基矽烷琥珀酸酐化合物以增強減少諸如二氧化矽和氮化矽的襯底的介電材料上的缺陷。還揭露了用於用該酸性化學機械拋光組成物拋光襯底以移除諸如二氧化矽和氮化矽的該介電材料的一些之方法。
Description
本發明關於具有增強的缺陷減少與良好的電介質移除速率的酸性拋光組成物和拋光襯底之方法。更具體地,本發明關於具有增強的缺陷減少與良好的電介質移除速率的酸性拋光組成物和拋光襯底之方法,其中該酸性拋光組成物包含具有正ζ電勢的膠體二氧化矽磨料顆粒以及選擇的烷氧基矽烷琥珀酸酐化合物以增強減少襯底上的缺陷,該襯底包括二氧化矽和氮化矽的電介質,並且其中從該襯底上移除該電介質中的至少一些。
在積體電路以及其他電子裝置的製造中,將多層導電材料、半導電材料以及介電材料沈積在半導體晶圓的表面上或從半導體晶圓的表面上移除。可以藉由若干種沈積技術來沈積導電材料、半導電材料以及介電材料的薄層。在現代加工中常見的沈積技術包括物理氣相沈積(PVD)(也稱為濺射)、化學氣相沈積(CVD)、電漿增強的化學氣相沈積(PECVD)、以及電化學電鍍(ECP)。
隨著材料層被依次地沈積和移除,晶圓的最上表面變成非平面的。因為後續的半導體加工(例如金屬化)要求晶圓具有平坦的表面,所以需要對晶圓進行平坦化。平坦化可用於移除不希望的表面形貌和表面缺陷,諸如粗糙表面、附聚的材料、晶格損傷、劃痕、以及被污染的層或材料。
化學機械平坦化、或化學機械拋光(CMP)係用於將襯底(諸如半導體晶圓)平坦化的常見技術。在常規的CMP中,晶圓被安裝在托架組件上並且被定位成與CMP設備中的拋光墊接觸。托架組件向晶圓提供可控的壓力,從而將晶圓壓靠在拋光墊上。該墊藉由外部驅動力相對於晶圓移動(例如旋轉)。與此同時,在晶圓與拋光墊之間提供拋光組成物(「漿料」)或其他拋光液。因此,藉由墊表面和漿料的化學和機械作用將晶圓表面拋光並且使其成為平面。
某些先進裝置設計要求在較低的使用點(POU)磨料wt%下提供良好的二氧化矽和氮化矽移除效率以及減少的劃痕缺陷以改進整個拋光方法和產物產率%的拋光組成物。隨著半導體裝置上結構大小不斷縮小,曾經可接受用於平坦化和減少拋光介電材料的缺陷的性能標準變得越來越難以接受。曾經被認為係可接受的劃痕現今成為產率限制。
因此,需要展現出所希望的平坦化效率、均勻性和電介質移除速率同時最小化諸如劃痕的缺陷的拋光組成物和拋光方法。
本發明提供一種酸性化學機械拋光組成物,其包含以下項作為初始組分:水;
具有正ζ電勢的膠體二氧化矽磨料顆粒;
具有式 (I) 之烷氧基矽烷琥珀酸酐化合物:(I)
其中當n係1或2時R1
選自(C1
-C4
)烷基;R2
係甲氧基、乙氧基、或甲氧基伸乙基氧基;並且n可以是0、1或2;
pH > 7;以及
視需要選自pH調節劑、季銨化合物和殺生物劑的一種或多種添加劑。
本發明還提供一種酸性化學機械拋光組成物,其包含以下項作為初始組分:
水;
0.1至40 wt%的具有正ζ電勢的膠體二氧化矽磨料;
0.0001至0.1 wt%的具有式 (I) 之烷氧基矽烷琥珀酸酐化合物:(I),
其中當n係1或2時R1
選自(C1
-C4
)烷基;R2
係甲氧基、乙氧基、或甲氧基伸乙基氧基;並且n可以是0、1或2;
2至6.5的pH;以及
視需要選自pH調節劑、季銨化合物和殺生物劑的一種或多種添加劑。
本發明進一步提供一種用於對襯底進行化學機械拋光之方法,該方法包括:
提供襯底,其中該襯底包括二氧化矽、氮化矽或其組合的介電材料;
提供酸性化學機械拋光組成物,其包含以下項作為初始組分:
水;
具有正ζ電勢的膠體二氧化矽磨料顆粒;
具有式 (I) 之烷氧基矽烷琥珀酸酐化合物:(I)
其中當n係1或2時R1
選自(C1
-C4
)烷基;R2
係甲氧基、乙氧基、或甲氧基伸乙基氧基;並且n可以是0、1或2:pH > 7;以及
視需要選自pH調節劑、季銨化合物和殺生物劑的一種或多種添加劑;
提供具有拋光表面的化學機械拋光墊;
用0.69至34.5 kPa的下壓力在該化學機械拋光墊的拋光表面與該襯底之間的介面處產生動態接觸;以及
在該酸性化學機械拋光墊與該襯底之間的介面處或介面附近將該酸性化學機械拋光組成物分配到該化學機械拋光墊上;並且其中該襯底被拋光並且該介電材料的一些被拋光掉。
本發明的酸性化學機械拋光組成物和方法使增強的缺陷減少以及良好的二氧化矽和氮化矽移除速率成為可能。
如本說明書通篇所使用的,除非上下文另外指示,否則以下縮寫具有以下含義:°C = 攝氏度;g = 克;L = 升;mL = 毫升;µ = µm = 微米;kPa = 千帕;Å = 埃;mm = 毫米;cm = 釐米;nm = 奈米;min = 分鐘;rpm = 每分鐘轉數;lbs = 磅;kg = 千克;wt% = 重量百分比;RR = 移除速率;Si = 矽;Si3
N4
= 氮化矽;DEAMS = (N,N-二乙基胺基甲基)三乙氧基矽烷,98%(賓夕法尼亞州莫里斯維爾Gelest公司(Gelest Inc.));TMOS = 原矽酸四甲酯;TMAH = 氫氧化四甲基銨;TEA = 四乙基銨;以及EDA = 乙二胺;PS = 本發明的拋光漿料;CS = 對比拋光漿料。
術語「化學機械拋光」或「CMP」係指單獨地憑藉化學和機械力來拋光襯底的製程,並且其區別於其中向襯底施加電偏壓的電化學-機械拋光(ECMP)。術語「TEOS」意指由原矽酸四乙酯(Si(OC2
H5
)4
)分解而形成的氧化矽。在通篇說明書中,術語「組成物」和「漿料」可互換使用。術語「伸烷基」與有機基團的更通用化學術語-「烷二基」同義。術語「鹵離子」意指氯離子、溴離子、氟離子和碘離子。術語「一個/種(a/an)」係指單數和複數二者。除非另外指出,否則所有百分比均為按重量計的。所有數值範圍都是包含端值的,並且可按任何順序組合,除了此數值範圍被限制為加起來最高達100%係合乎邏輯的情況之外。
本發明的酸性化學機械拋光組成物和方法可用於拋光包括介電材料的襯底並且對介電材料具有改進的拋光缺陷率性能,該介電材料包括二氧化矽、氮化矽或其組合。本發明的酸性化學機械拋光組成物含有以下項(較佳的是由以下項組成):水;減少介電材料上的缺陷和劃痕的具有式 (I) 之烷氧基矽烷琥珀酸酐化合物:(I)
其中當變數n係1或2時,R1
選自(C1
-C4
)烷基,諸如甲基、乙基、丙基或丁基,較佳的是甲基或乙基,更較佳的是甲基;R2
係甲氧基、乙氧基、或甲氧基伸乙基氧基,較佳的是甲氧基和乙氧基,更較佳的是乙氧基;並且變數n可以是0、1或2;其中R1
和R2
與Si共價鍵合;並且當n = 0時,僅R2
與Si共價鍵合;pH > 7;以及視需要選自pH調節劑、季銨化合物和殺生物劑的一種或多種添加劑。
本文和所附申請專利範圍中用於描述藉由將具有式 (I) 之烷氧基矽烷琥珀酸酐化合物包含在用於本發明的酸性化學機械拋光方法的酸性化學機械拋光組成物中而獲得的缺陷率性能的術語「改進的拋光缺陷率性能」意指滿足至少以下運算式:
X > X0
(方程式I),
其中X係如在實例中陳述的拋光條件下測量的含有本發明方法中使用的物質的酸性化學機械拋光組成物的缺陷率(即,後CMP/氟化氫(HF)劃痕);並且X0
係在相同條件下僅用存在的具有(+)正ζ電勢的二氧化矽磨料獲得的缺陷率(即,後CMP/氟化氫劃痕)。
示例性較佳的具有式 (I) 之烷氧基矽烷琥珀酸酐化合物由以下項組成:
3-三甲氧基矽基丙基琥珀酸酐(R2
= 甲氧基並且n = 0);
3-甲基二甲氧基矽基丙基琥珀酸酐(R1
= 甲基,R2
= 甲氧基並且n = 1);
3-二甲基甲氧基矽基丙基琥珀酸酐(R1
= 甲基,R2
= 甲氧基並且n = 2);
3-三乙氧基矽基丙基琥珀酸酐(R2
= 乙氧基並且n = 0);
3-甲基二乙氧基矽基丙基琥珀酸酐(R1
= 甲基,R2
= 乙氧基並且n =1);
3-二甲基乙氧基矽基丙基琥珀酸酐(R1
= 甲基,R2
=乙氧基並且n = 2);
3-三-(甲氧基伸乙氧基)-矽基丙基琥珀酸酐(R2
= 甲氧基伸乙氧基並且n = 0);
3-甲基雙-(甲氧基伸乙氧基)-矽基丙基琥珀酸酐(R1
= 甲基,R2
= 甲氧基伸乙氧基並且n = 1);以及
3-二甲基甲氧基伸乙氧基矽基丙基琥珀酸酐(R1
= 甲基,R2
= 甲氧基伸乙氧基並且n = 2)。
在本發明的酸性化學機械拋光方法中使用的酸性化學機械拋光組成物含有0.0001至0.1 wt%的具有式 (I) 或式 (II) 之烷氧基矽烷琥珀酸酐,較佳的是0.00075至0.006 wt%、更較佳的是0.003至0.006 wt%的具有式 (I) 或式 (II) 之烷氧基矽烷琥珀酸酐作為初始組分。
在本發明的化學機械拋光方法中使用的化學機械拋光組成物中含有的水較佳的是係去離子水和蒸餾水中的至少一種,以限制附帶的雜質。
在本發明的酸性化學機械拋光方法中使用的酸性化學機械拋光組成物含有0.1至40 wt%的具有淨正ζ電勢的膠體二氧化矽磨料;較佳的是1至25 wt%、更較佳的是1至12 wt%、最較佳的是1至3 wt%的具有淨正ζ電勢的膠體二氧化矽磨料。具有淨正ζ電勢的膠體二氧化矽磨料較佳的是具有 > 200 nm;更較佳的是75至150 nm;最較佳的是100至150 nm的平均粒度,如藉由動態光散射技術(DLS)測量的。
在本發明的酸性化學機械拋光組成物中,所提供的酸性化學機械拋光組成物含有具有正ζ電勢的膠體二氧化矽磨料顆粒作為初始組分,其中該膠體二氧化矽磨料顆粒包括含氮化合物。此類含氮化合物可以摻入膠體二氧化矽磨料顆粒內,或者可以摻入膠體二氧化矽磨料顆粒的表面上,或者本發明的化學機械拋光組成物可以含有具有組合的膠體二氧化矽磨料顆粒作為初始組分,其中含氮化合物摻入具有正ζ電勢的膠體二氧化矽磨料顆粒內,並且其中,含氮化合物摻入膠體二氧化矽磨料顆粒的表面上。
包括含氮化合物的膠體二氧化矽磨料顆粒係可商購的,或者可以如化學和膠體二氧化矽磨料顆粒文獻中描述的由熟悉該項技術者製備。可商購的包括含氮化合物的膠體二氧化矽顆粒的實例係KLEBOSOL™ 1598-B25表面改性的膠體二氧化矽顆粒(由AZ電子材料公司(AZ Electronics Materials)製造,從密西根州米德蘭陶氏化學公司(Dow Chemical company)可獲得);以及FUSO™ BS-3(日本大阪扶桑化學工業株式會社(Fuso Chemical Co., Ltd.))。此類膠體二氧化矽磨料顆粒較佳的是藉由熟悉該項技術者眾所周知的Stober方法製備。
本發明的酸性化學機械拋光組成物可具有與沒有含氮化合物的膠體二氧化矽磨料顆粒混合的包括含氮化合物的具有正ζ電勢的膠體二氧化矽磨料顆粒。適合於實踐本發明的磨料包括但不限於DEAMS表面改性的FUSO BS-3™磨料漿料(80 ppm DEAMS至1 wt%的二氧化矽)以及KLEBOSOL™ 1598-B25漿料(由AZ電子材料公司製造,從陶氏化學公司可獲得)。也可以使用此類磨料的混合物。
較佳的是,本發明的具有正ζ電勢的膠體二氧化矽磨料顆粒包括(在膠體二氧化矽磨料顆粒的表面上、在膠體二氧化矽磨料顆粒內、或其組合)含氮化合物,該含氮化合物包括但不限於具有以下通式的銨化合物:
R3
R4
R5
R6
N+
(III)
其中R3
、R4
、R5
和R6
獨立地選自氫、(C1
-C6
)烷基、(C7
-C12
)芳基烷基和(C6
-C10
)芳基。此類基團可以被一個或多個羥基取代。可以由本領域或文獻中已知的方法製備含有銨化合物的此類膠體二氧化矽磨料。
此類含氮銨化合物的實例係四甲基銨、四乙基銨、四丙基銨、四丁基銨、四戊基銨、乙基三甲基銨和二乙基二甲基銨。
含氮化合物還可包括但不限於具有胺基的化合物,諸如一級胺、二級胺、三級胺或季胺。此類含氮化合物還可包括具有一至八個碳原子的胺基酸,諸如離胺酸、麩醯胺酸、甘胺酸、亞胺基二乙酸、丙胺酸、纈胺酸、白胺酸、異白胺酸、絲胺酸和蘇胺酸。
在各種實施方式中,在本發明的膠體二氧化矽磨料顆粒中化學物質與二氧化矽的莫耳比較佳的是大於0.1%且小於10%。
胺基矽烷化合物係最較佳的摻入本發明的化學機械拋光組成物的膠體二氧化矽磨料顆粒的表面上或膠體二氧化矽磨料顆粒內的含氮化合物。此類胺基矽烷化合物包括但不限於一級胺基矽烷、二級胺基矽烷、三級胺基矽烷、季胺基矽烷和多足的(例如,二足的)胺基矽烷。胺基矽烷化合物可以包括基本上任何合適的胺基矽烷。可以用於實踐本發明的胺基矽烷的實例係雙(2-羥乙基)-3-胺基丙基三烷氧基矽烷、二乙基胺基甲基三烷氧基矽烷、(N,N-二乙基-3-胺基丙基)三烷氧基矽烷)、3-(N-苯乙烯基甲基-2-胺基乙基胺基丙基三烷氧基矽烷)、胺基丙基三烷氧基矽烷、(2-N-苄基胺基乙基)-3-胺基丙基三烷氧基矽烷)、三烷氧基矽基丙基-N,N,N-三甲基銨、N-(三烷氧基矽基乙基)苄基-N,N,N-三甲基銨、(雙(甲基二烷氧基矽基丙基)-N-甲基胺、雙(三烷氧基矽基丙基)脲、雙(3-(三烷氧基矽基)丙基)-乙二胺、雙(三烷氧基矽基丙基)胺、雙(三烷氧基矽基丙基)胺、3-胺基丙基三烷氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二烷氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三烷氧基矽烷、3-胺基丙基甲基二烷氧基矽烷、3-胺基丙基三烷氧基矽烷、3-胺基丙基三乙氧基矽烷、(N-三烷氧基矽基丙基)聚乙烯亞胺、三烷氧基矽基丙基二伸乙基三胺、N-苯基-3-胺基丙基三烷氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三烷氧基矽烷、4-胺基丁基-三烷氧基矽烷、(N,N-二乙基胺基甲基)三乙氧基矽烷、以及其混合物。熟悉該項技術者容易理解,胺基矽烷化合物通常在水性介質中水解(或部分水解)。因此,藉由列舉胺基矽烷化合物,應理解,可以將胺基矽烷或其水解的(或部分水解的)物質或縮合的物質摻入膠體二氧化矽磨料顆粒中。
在各種實施方式中,在膠體二氧化矽磨料顆粒中胺基矽烷物質與二氧化矽的莫耳比較佳的是大於0.1%且小於10%。
包括摻入膠體二氧化矽磨料顆粒內的含氮化合物的膠體二氧化矽磨料顆粒較佳的是藉由Stober方法製備,其中有機烷氧基矽烷諸如TMOS和TEOS用作二氧化矽合成的先質,並且含氮化合物用作催化劑。TMOS和TEOS作為先質在水性鹼性環境中經受水解和縮合。用於維持鹼性pH的催化劑係含氮物質,諸如但不限於氨、TMAH、TEA和EDA。作為抗衡離子,該等含氮化合物在顆粒生長期間不可避免地被捕獲在膠體二氧化矽磨料顆粒內部,因此導致包括內部摻入到膠體二氧化矽磨料顆粒內的含氮化合物的膠體二氧化矽磨料顆粒。包括摻入顆粒內的含氮化合物的可商購的膠體二氧化矽磨料顆粒的實例係從FUSO™可獲得的顆粒,諸如FUSO BS-3™膠體二氧化矽磨料顆粒。
視需要,所提供的酸性化學機械拋光組成物含有pH調節劑作為初始組分。此類pH調節劑包括二羧酸,其中該二羧酸包括但不限於丙二酸、草酸、琥珀酸、己二酸、馬來酸、蘋果酸、戊二酸、酒石酸、其鹽或其混合物。更較佳的是,所提供的酸性化學機械拋光組成物含有二羧酸作為初始組分,其中該二羧酸選自由以下項組成之群組:丙二酸、草酸、琥珀酸、酒石酸、其鹽以及其混合物。還更較佳的是,所提供的酸性化學機械拋光組成物含有二羧酸作為初始組分,其中該二羧酸選自由以下項組成之群組:丙二酸、草酸、琥珀酸、其鹽以及其混合物。最較佳的是,所提供的酸性化學機械拋光組成物含有二羧酸、琥珀酸或其鹽作為初始組分。此類二羧酸包含在酸性化學機械拋光組成物中以維持所希望的酸性pH。
用於本發明的酸性化學機械拋光方法中的酸性化學機械拋光組成物具有 > 7、較佳的是2至6.5、更較佳的是3至6、最較佳的是4至5的pH。將酸性化學機械拋光組成物維持在所希望的酸性pH範圍下的最較佳的pH調節劑係琥珀酸。
視需要,本發明的酸性化學機械拋光組成物包含一種或多種季銨化合物。此類季銨化合物包括但不限於具有通式 (IV) 之化合物:(IV),
其中R7
選自飽和或不飽和的(C1
-C15
)烷基、(C6
-C15
)芳基、以及(C6
-C15
)芳烷基,較佳的是(C2
-C10
)烷基,更較佳的是(C2
-C6
)烷基,還更較佳的是-(CH2
)6
-和-(CH2
)4
-,最較佳的是-(CH2
)4
-;其中R8
、R9
、R10
、R11
、R12
和R13
各自獨立地選自氫、飽和或不飽和的(C1
-C15
)烷基、(C6
-C15
)芳基、(C6
-C15
)芳烷基、以及(C6
-C15
)烷芳基,較佳的是氫和(C1
-C6
)烷基,更較佳的是氫和丁基,最較佳的是丁基;並且,其中陰離子係用於中和陽離子的(2+)電荷的抗衡陰離子,其中該陰離子係氫氧根、鹵離子、硝酸根、碳酸根、硫酸根、磷酸根或乙酸根,較佳的是,該陰離子係氫氧根或鹵離子,更較佳的是該陰離子係氫氧根。本發明的酸性化學機械拋光組成物視需要包含0.001至1 wt%、更較佳的是0.1至1 wt%、最較佳的是0.1至0.3 wt%的具有式 (I) 之化合物作為初始組分。最較佳的是,具有式 (IV) 之化合物係N,N,N,N’,N’,N’-六丁基-1,4-丁烷二銨二氫氧化物。
視需要,酸性化學機械拋光組成物可以含有殺生物劑,諸如KORDEX™ MLX(9.5% - 9.9%的甲基-4-異噻唑啉-3-酮、89.1% - 89.5%的水以及 ≤ 1.0%的相關反應產物)或含有活性成分2-甲基-4-異噻唑啉-3-酮和5-氯-2-甲基-4-異噻唑啉-3-酮的KATHON™ ICP III,每個均由陶氏化學公司(KATHON™和KORDEX™係陶氏化學公司的商標)製造。此類殺生物劑可以以如熟悉該項技術者已知的常規量包含在本發明的酸性化學機械拋光組成物中。
在本發明的酸性化學機械拋光方法中被拋光的襯底包括二氧化矽。襯底中的二氧化矽包括但不限於原矽酸四乙酯(TEOS)、硼磷矽酸鹽玻璃(BPSG)、電漿蝕刻的原矽酸四乙酯(PETEOS)、熱氧化物、未摻雜的矽酸鹽玻璃、高密度電漿(HDP)氧化物。
視需要,在本發明的酸性化學機械拋光方法中被拋光的襯底進一步包括氮化矽。如果存在的話,襯底中的氮化矽包括但不限於氮化矽材料,諸如Si3
N4
。
較佳的是,在本發明的拋光襯底的方法中,所提供的化學機械拋光墊可以是本領域已知的任何合適的拋光墊。熟悉該項技術者知道選擇用在本發明方法中適當的化學機械拋光墊。更較佳的是,在本發明的拋光襯底的方法中,所提供的化學機械拋光墊選自織造拋光墊和非織造拋光墊。還更較佳的是,在本發明的拋光襯底的方法中,所提供的化學機械拋光墊包括聚胺酯拋光層。最較佳的是,在本發明的拋光襯底的方法中,所提供的化學機械拋光墊包括含有聚合物中空芯微粒的聚胺酯拋光層以及聚胺酯浸漬的非織造子墊。較佳的是,所提供的化學機械拋光墊在拋光表面上具有至少一個凹槽。
較佳的是,在本發明的拋光襯底的方法中,在化學機械拋光墊與襯底之間的介面處或介面附近將所提供的化學機械拋光組成物分配到所提供的化學機械拋光墊的拋光表面上。
較佳的是,在本發明的拋光襯底的方法中,使用0.69至34.5 kPa的垂直於被拋光襯底的表面的下壓力,在所提供的化學機械拋光墊與襯底之間的介面處產生動態接觸。
在拋光包括二氧化矽、氮化矽或其組合的襯底的方法中,在200 mm的拋光機上在93-113轉/分鐘的壓板速度、87-111轉/分鐘的托架速度、125-300 mL/min的酸性化學機械拋光組成物流速、21.4 kPa的標稱下壓力下進行拋光;並且其中,該化學機械拋光墊包含含有聚合物中空芯微粒的聚胺酯拋光層以及聚胺酯浸漬的非織造子墊。
以下實例旨在說明本發明,但是並不旨在限制其範圍。
在以下實例中,除非另外指示,否則溫度和壓力條件係環境溫度和標準壓力。
在八英吋的毯覆式晶圓上進行拋光移除速率實驗。Applied Materials Mirra®拋光機用於所有實例。所有拋光實驗均使用AMAT Reflexion IC1000聚胺酯拋光墊或VisionPad 6000TM
聚胺酯拋光墊(從羅門哈斯電子材料CMP公司(Rohm and Haas Electronic Materials CMP Inc.)可商購),用34.5 kPa(5 psi)的下壓力、125 mL/min的酸性化學機械拋光組成物流速、93 rpm的台旋轉速度以及87 rpm的托架旋轉速度進行。藉由使用KLA-Tencor FX200度量工具測量拋光之前和之後的膜厚度來確定移除速率。實例中報告的缺陷率性能係在氟化氫後拋光洗滌(「Pst HF」)之後使用掃描電子顯微鏡確定的。使用從科磊公司(KLA-Tencor)可獲得的Surfscan® SP2缺陷檢查系統檢查在Pst-HF洗滌後的所有TEOS晶圓。缺陷資訊(包括其在晶圓上的座標)記錄在KLARF(KLA結果文件)中,然後將其轉移到從科磊公司可獲得的eDR-5200缺陷評審系統中。選擇了100個缺陷圖像的隨機樣本,並藉由DR-5200系統對其進行了評審。這100個圖像被分類為各種缺陷類型,例如,顫痕(劃痕)、顆粒和墊碎片。基於來自這100個圖像的分類結果,確定了晶圓上劃痕的總數。
實例1化學機械拋光組成物
以下化學機械拋光組成物為拋光漿料,並且製備成包含下表1中揭露的組分和量。將組分與餘量去離子水組合,而沒有進一步調節pH。用水性琥珀酸維持pH。
[表1]
Ƌ
磨料:由AZ電子材料公司製造從陶氏化學公司可獲得的(80 ppm DEAMS至1 wt%的二氧化矽)表面改性的FUSO BS-3™淨(+)ζ電勢的磨料漿料與具有淨(+)ζ電勢的KLEBOSOL™ 1598-B25磨料漿料的3 : 1重量比的混合磨料。
實例2TEOS 移除速率和缺陷性能
漿料 # | 磨料Ƌ (wt% ) | 三乙氧基矽基丙基- 琥珀酸酐 (wt% ) | pH |
PS-1 | 2 | 0.00075 | 4.5 |
PS-2 | 2 | 0.00375 | 4.5 |
PS-3 | 2 | 0.003 | 4.5 |
PS-4 | 2 | 0.006 | 4.5 |
PS-5 | 2 | 0.006 | 4.5 |
CS-1 | 2 | 0 | 4.5 |
CS-2 | 2 | 0 | 4.5 |
CS-3 | 2 | 0 | 4.5 |
將實例1中的以上表1的本發明的化學機械拋光漿料組成物(PS-3
和PS-4
)的TEOS移除速率和缺陷性能與同樣在實例1中的以上表1中揭露的對比漿料(CS-2
)的TEOS移除速率和缺陷性能進行比較。AMAT Reflexion IC1000聚胺酯拋光墊用於拋光襯底。性能結果在下表2中。
[表2]
漿料 # | TEOS RR (Å/min ) | Pst-HF 總缺陷 | Pst-HF 劃痕 |
CS-2 | 3507 | 259 | 40 |
PS-3 | 3497 | 158 | 30 |
PS-4 | 3371 | 116 | 18 |
與對照配製物相對比,本發明的酸性化學機械拋光組成物示出顯著減少的二氧化矽介電材料的缺陷和劃痕。此外,本發明的酸性化學機械拋光組成物即使具有減少的二氧化矽介電材料的缺陷和劃痕,也仍然具有良好的TEOS RR。
實例3TEOS 移除速率和缺陷性能
用來自以上實例1的表1的CS-3
和PS-5
重複化學機械拋光漿料組成物的TEOS移除速率和缺陷性能。VisionPad 6000TM
聚胺酯拋光墊用於拋光襯底。所有其他拋光條件和參數與以上實例2中的相同。性能結果在下表3中。
[表3]
漿料 # | TEOS RR (Å/min ) | Pst-HF 總缺陷 | Pst-HF 劃痕 |
CS-3 | 3252 | 200 | 20 |
PS-5 | 3004 | 138 | 7 |
如以上實例2中的,與對照配製物相對比,本發明的酸性化學機械拋光組成物示出顯著減少的二氧化矽介電材料的缺陷和劃痕。此外,本發明的酸性化學機械拋光組成物仍然具有良好的TEOS RR。
實例4TEOS 和 SiN 移除速率
在八英吋的毯覆式晶圓上進行拋光移除速率實驗。Applied Materials Mirra®拋光機用於所有實例。所有拋光實驗均使用VisionPad 6000TM
聚胺酯拋光墊(從羅門哈斯電子材料CMP公司可商購),用34.5 kPa(5 psi)的下壓力、125 mL/min的化學機械拋光漿料組成物流速、93 rpm的台旋轉速度以及87 rpm的托架旋轉速度進行。藉由使用KLA-Tencor FX200度量工具測量拋光之前和之後的膜厚度來確定移除速率。拋光結果在下表4中示出。
[表4]
儘管引入三乙氧基矽基丙基-琥珀酸酐使良好的TEOS和Si3
N4
移除速率成為可能,但是三乙氧基矽基丙基-琥珀酸酐似乎對目標TEOS移除速率產生了較小的影響,而Si3
N4
移除速率具有輕微的增加。
漿料 # | TEOS RR (Å/min ) | Si3 N4 RR (Å/min ) |
CS-1 | 2296 | 234 |
PS-1 | 2314 | 246 |
PS-2 | 2237 | 312 |
無
無
無
Claims (10)
- 如申請專利範圍第1項所述之酸性化學機械拋光組成物,其中,該化學機械拋光組成物包含以下項作為初始組分: 該水; 0.1至40 wt%的量的該具有正ζ電勢的膠體二氧化矽磨料; 0.0001至0.1 wt%的量的該具有式 (I) 之烷氧基矽烷琥珀酸酐; 該pH為2至6.5; 視需要該pH調節劑; 視需要該季銨化合物;以及 視需要該殺生物劑。
- 如申請專利範圍第1項所述之酸性化學機械拋光組成物,其中,該具有式 (I) 之烷氧基矽烷琥珀酸酐選自由以下項組成之群組:3-三甲氧基矽基丙基琥珀酸酐;3-甲基二甲氧基矽基丙基琥珀酸酐;3-二甲基甲氧基矽基丙基琥珀酸酐;3-三乙氧基矽基丙基琥珀酸酐;3-甲基二乙氧基矽基丙基琥珀酸酐;3-二甲基乙氧基矽基丙基琥珀酸酐;3-三-(甲氧基伸乙氧基)-矽基丙基琥珀酸酐;3-甲基雙-(甲氧基伸乙氧基)-矽基丙基琥珀酸酐;以及3-二甲基甲氧基伸乙氧基矽基丙基琥珀酸酐。
- 如申請專利範圍第1項所述之酸性化學機械拋光組成物,其中,該具有正ζ電勢的膠體二氧化矽磨料顆粒包括含氮化合物。
- 如申請專利範圍第4項所述之酸性化學機械拋光組成物,其中,該含氮化合物係胺基矽烷化合物。
- 一種用於對襯底進行化學機械拋光之方法,該方法包括: 提供襯底,其中該襯底包括氧化矽、氮化矽或其組合的介電材料; 提供如申請專利範圍第1項所述之酸性化學機械拋光組成物; 提供具有拋光表面的化學機械拋光墊; 用0.69至34.5 kPa的下壓力在該酸性化學機械拋光墊的拋光表面與該襯底之間的介面處產生動態接觸;以及 在該化學機械拋光墊與該襯底之間的介面處或介面附近將該酸性化學機械拋光組成物分配到該化學機械拋光墊上; 其中該襯底被拋光;並且其中,將該氧化矽、氮化矽或其組合中的至少一些從該襯底上移除。
- 如申請專利範圍第6項所述之方法,其中,在200 mm的拋光機上在93-113轉/分鐘的壓板速度、87-111轉/分鐘的托架速度、125-300 mL/min的酸性化學機械拋光組成物流速、21.4 kPa的標稱下壓力下進行拋光;並且其中,該化學機械拋光墊包含含有聚合物中空芯微粒的聚胺酯拋光層以及聚胺酯浸漬的非織造子墊。
- 如申請專利範圍第6項所述之方法,其中,所提供的該酸性化學機械拋光組成物包含以下項作為初始組分: 水; 0.1至40 wt%的量的具有正ζ電勢的膠體二氧化矽磨料顆粒; 0.0001至0.1 wt%的量的具有式 (I) 之烷氧基矽烷琥珀酸酐; 2至6.5的pH; 視需要該pH調節劑; 視需要該季銨化合物;以及 視需要該殺生物劑。
- 如申請專利範圍第6項所述之方法,其中,該具有式 (I) 之烷氧基矽烷琥珀酸酐選自由以下項組成之群組:3-三甲氧基矽基丙基琥珀酸酐;3-甲基二甲氧基矽基丙基琥珀酸酐;3-二甲基甲氧基矽基丙基琥珀酸酐;3-三乙氧基矽基丙基琥珀酸酐;3-甲基二乙氧基矽基丙基琥珀酸酐;3-二甲基乙氧基矽基丙基琥珀酸酐;3-三-(甲氧基伸乙氧基)-矽基丙基琥珀酸酐;3-甲基雙-(甲氧基伸乙氧基)-矽基丙基琥珀酸酐;以及3-二甲基甲氧基伸乙氧基矽基丙基琥珀酸酐。
- 如申請專利範圍第6項所述之方法,其中,該具有正ζ電勢的膠體二氧化矽磨料顆粒包括含氮化合物。
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