TWI538989B - 水研磨組成物及用於化學機械研磨電子,機械及光學裝置基材的方法 - Google Patents
水研磨組成物及用於化學機械研磨電子,機械及光學裝置基材的方法 Download PDFInfo
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- TWI538989B TWI538989B TW100132006A TW100132006A TWI538989B TW I538989 B TWI538989 B TW I538989B TW 100132006 A TW100132006 A TW 100132006A TW 100132006 A TW100132006 A TW 100132006A TW I538989 B TWI538989 B TW I538989B
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Description
本發明係關於一種新穎水研磨組成物,其尤其適用於研磨電子、機械及光學裝置基材。
此外,本發明係關於一種用於研磨基材以用以製造電子、機械及光學裝置的新穎方法。
最後但並非最不重要的是,本發明係關於新穎水研磨組成物用於製造電子、機械及光學裝置的新穎用途。
引用文獻
本申請案中所引用之文獻以全文引用的方式併入本文中。
化學機械平坦化或研磨(CMP)為實現積體電路(IC)裝置局部及全面平坦度之主要方法。該技術典型地應用含有磨料及其他添加劑之CMP組成物或研磨漿作為旋轉之基材表面與所施加負載下之研磨墊之間的活性化學劑。因此,CMP方法聯合諸如磨擦之物理方法及諸如氧化或螯合之化學方法。僅包含物理作用或僅包含化學作用對移除或研磨基材而言並不理想,而為實現快速均勻的移除,兩者之協同組合較理想。
以此種方式移除基材直至獲得所需平坦度,或障壁子層(barrier sublayer)或停止層(stopping layer)暴露。最終,獲得平坦的無瑕疵表面,其使得能夠由後續光刻、圖案化、蝕刻及薄膜加工進行適合的多層IC裝置製造。
淺溝槽隔離(Shallow trench isolation,STI)為特定CMP應用,其一般需要在圖案化晶圓基材上對氮化矽選擇性移除二氧化矽。在此情況下,用介電材料(例如二氧化矽)過量裝填經蝕刻之溝槽,而介電材料使用氮化矽障壁膜作為停止層研磨。在自障壁膜清除二氧化矽同時使暴露之氮化矽及溝槽二氧化矽之移除減至最少的情況下結束CMP方法。
此舉需要CMP研磨漿能夠獲得二氧化矽材料移除率MRR比氮化矽移除率MRR之高相對比,該比率在此項技術中亦稱為氧化物對氮化物之選擇性。
在STI應用中,基於二氧化鈰之CMP研磨漿已因其能夠獲得較高的氧化物對氮化物之選擇性而頗受關注,而該高選擇性係歸因於二氧化鈰對二氧化矽之高化學親和力,此在此項技術中亦稱為二氧化鈰之化學牙齒作用(tooth action)。
儘管如此,基於二氧化鈰之CMP研磨漿的氧化物對氮化物之選擇性必須由「修改」選擇性之添加劑來改良。
已多次嘗試修改基於二氧化鈰之CMP研磨漿的選擇性。
因此,Jae-Don Lee等人在Journal of the Electrochemical Society,149(8),G477-G481,2002中揭示:具有不同親水-親脂平衡(HLB)值之非離子界面活性劑,諸如聚氧化乙烯、氧化乙烯-氧化丙烯共聚物及氧化乙烯-氧化丙烯-氧化乙烯三嵌段共聚物對CMP期間氧化物對多晶矽之選擇性之影響。然而,使用煙霧狀二氧化矽作為磨料。
Jae-Dong Lee等人在Journal of the Electrochemical Society,149(8),G477-G481,2002中揭示:化學機械研磨期間,非離子界面活性劑對氧化物對多晶矽之選擇性的影響,諸如聚氧化乙烯(PEO)及氧化乙烯-氧化丙烯-氧化乙烯三嵌段共聚物之界面活性劑對選擇性的影響。然而,氧化物對氮化物之選擇性並未解決。
美國專利US 5,738,800、US 6,042,741、US 6,132,637及US 6,218,305 B揭示一種基於二氧化鈰之CMP研磨漿,其含有錯合劑,諸如蘋果酸、酒石酸、葡萄糖酸、檸檬酸、鄰二羥基苯甲酸及聚羥基苯甲酸、鄰苯二甲酸、焦兒茶酚、焦五倍子酸、五倍子酸、鞣酸及其鹽。此外,基於二氧化鈰之CMP研磨漿含有陰離子界面活性劑、陽離子界面活性劑、兩性界面活性劑或非離子界面活性劑。聲稱該基於二氧化鈰之CMP研磨漿具有高氧化物對氮化物之選擇性。
美國專利US 5,759,917、US 6,689,692 B1及US 6,984,588 B2揭示一種基於二氧化鈰之CMP研磨漿,其含有羧酸,諸如乙酸、己二酸、丁酸、癸酸、己酸、辛酸、檸檬酸、戊二酸、乙醇酸、甲酸、反丁烯二酸、乳酸、月桂酸、蘋果酸、順丁烯二酸、丙二酸、肉豆蔻酸、乙二酸、棕櫚酸、鄰苯二甲酸、丙酸、丙酮酸、硬脂酸、丁二酸、酒石酸、戊酸、2-(2-甲氧基乙氧基)乙酸、2-[2-(2-甲氧基乙氧基)乙氧基]乙酸、聚(乙二醇)雙(羧甲基)醚及其衍生物及鹽。另外,基於二氧化鈰之CMP研磨漿含有水溶性有機及無機鹽,諸如硝酸鹽、磷酸鹽及硫酸鹽。聲稱該基於二氧化鈰之CMP研磨漿能研磨二氧化矽過量裝填物優先於氮化矽層。
美國專利US 6,299,659 B1揭示一種基於二氧化鈰之CMP研磨漿,其中該等磨料顆粒已用矽烷、鈦酸鹽、鋯酸鹽(circonate)、鋁及磷酸鹽偶合劑處理以便改良氧化物對氮化物之選擇性。
美國專利申請案US 2002/0034875 A1及美國專利US 6,626,968 B2揭示一種基於二氧化鈰之CMP研磨漿,其含有界面活性劑;pH調節劑,諸如氫氧化鉀、硫酸、硝酸、鹽酸或磷酸;及含有親水性官能基及疏水性官能基之聚合物,諸如聚乙烯甲醚(PVME)、聚乙二醇(PEG)、聚氧化乙烯23月桂醚(POLE)、聚丙酸(PPA)、聚丙烯酸(PM)及聚乙二醇二甲醚(PEGBE)。然而,此基於二氧化鈰之CMP研磨漿增加氧化物對多晶矽之選擇性。
美國專利US 6,436,835 B1揭示一種用於淺溝槽隔離方法之基於二氧化鈰之CMP研磨漿,其包含具有羧酸基或羧酸酯基或磺酸基或胺磺酸基之水溶性有機化合物,諸如聚丙烯酸、聚甲基丙烯酸、萘磺酸-福馬林縮合物、蘋果酸、乳酸、酒石酸、葡萄糖酸、檸檬酸、丁二酸、己二酸、反丁烯二酸、天冬胺酸、麩胺酸、甘胺酸、4-胺基丁酸、6-胺基己酸、12-胺基月桂酸、精胺酸、甘胺醯甘胺酸、月桂基苯磺酸及其銨鹽。基於二氧化鈰之CMP研磨漿可具有等於或小於4之pH值,高於4之pH值亦較佳。其聲稱具有高氧化物對氮化物之選擇性。
美國專利US 6,491,843 B1、US 6,544,892 B2及US 6,627,107 B2揭示一種基於二氧化鈰之CMP研磨漿,其含有諸如離胺酸、丙胺酸及脯胺酸之α-胺基酸用於改良氧化物對氮化物之選擇性。
美國專利US 6,616,514 B1揭示一種基於二氧化鈰之CMP研磨漿,其含有具有至少3個在水性介質中不易解離的羥基之有機多元醇;或由至少一種具有至少3個在水性介質中不易解離的羥基之單體形成的聚合物,諸如甘露醇、山梨糖醇、甘露糖、木糖醇、山梨糖、蔗糖及糊精,用於改良氧化物對氮化物之選擇性。
美國專利申請案US 2006/0207188 A1揭示一種基於二氧化鈰之CMP研磨漿,其含有諸如聚丙烯酸或聚(甲基丙烯酸烷基酯)之聚合物與諸如丙烯醯胺、甲基丙烯醯胺、乙基-甲基丙烯醯胺、乙烯基吡啶或乙烯基吡咯啶酮之單體的反應產物。咸信該等反應產物亦增加氧化物對氮化物之選擇性。
美國專利申請案US 2006/0216935 A1揭示一種基於二氧化鈰之CMP研磨漿,其包含蛋白質、離胺酸及/或精胺酸,及吡咯啶酮化合物,諸如聚乙烯基吡咯啶酮(PVP)、N-辛基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-羥乙基-2-吡咯啶酮、N-環己基-2-吡咯啶酮、N-丁基-2-吡咯啶酮、N-己基-2-吡咯啶酮、N-癸基-2-吡咯啶酮、N-十八烷基-2-吡咯啶酮及N-十六烷基-2-吡咯啶酮。基於二氧化鈰之CMP研磨漿可另外含有分散劑,如聚丙烯酸、乙二醇及聚乙二醇。特定實施例使用脯胺酸、聚乙烯基吡咯啶酮或N-辛基-2-吡咯啶酮、PPO/PEO嵌段共聚物及戊二醛。咸信基於二氧化鈰之CMP研磨漿不侵蝕性地移除溝槽二氧化矽,由此允許超出端點之延伸研磨而不實質上增加最小的梯級高度。
美國專利申請案US 2007/0077865 A1揭示一種基於二氧化鈰之CMP研磨漿,其含有較佳來自由BASF銷售之PluronicTM家族的聚氧化乙烯/聚氧化丙烯共聚物。基於二氧化鈰之CMP研磨漿可另外含有胺基醇,諸如2-二甲基胺基-2-甲基-1-丙醇(DMAMP)、2-胺基-2-乙基-1-丙醇(AMP)、2-(2-胺基乙基胺基)乙醇、2-(異丙基胺基)乙醇、2-(甲基胺基)乙醇、2-(二乙基胺基)乙醇、2-(2-二甲基胺基)乙氧基)乙醇、1,1'溴[[3-(二甲基胺基)丙基]亞胺基]-雙-2-丙醇、2-(2-丁基胺基)乙醇、2-(第三丁基胺基)乙醇、2-(二異丙基胺基)乙醇及N-(3-胺基丙基)嗎啉。基於二氧化鈰之CMP研磨漿可另外含有第四銨化合物,如氫氧化四甲基銨;成膜劑,諸如烷基胺、烷醇胺、羥胺、磷酸酯、月桂基硫酸鈉、脂肪酸、聚丙烯酸酯、聚甲基丙烯酸酯、聚乙烯基膦酸酯、聚蘋果酸酯、聚苯乙烯磺酸酯、聚乙烯硫酸酯、苯并三唑、三唑及苯并咪唑;及錯合劑,諸如乙醯丙酮、乙酸鹽、羥乙酸鹽、乳酸鹽、葡糖酸鹽、五倍子酸、乙二酸鹽、鄰苯二甲酸鹽、檸檬酸鹽、丁二酸鹽、酒石酸鹽、蘋果酸鹽、乙二胺四乙酸、乙二醇、焦兒茶酚、焦五倍子酸、鞣酸、鏻鹽及膦酸。咸信基於二氧化鈰之CMP研磨漿提供二氧化矽及/或氮化矽相對於多晶矽之良好選擇性。
美國專利申請案US 2007/0175104 A1揭示一種基於二氧化鈰之CMP研磨漿,其包含多晶矽研磨抑制劑,選自具有經任何選自由以下組成之群之成員取代的N-單取代或N,N-二取代骨架之水溶性聚合物:丙烯醯胺、甲基丙烯醯胺及其α-取代衍生物;聚乙二醇;聚乙烯基吡咯啶酮;烷氧基化之直鏈脂族醇及基於乙炔之二醇的氧化乙烯加合物。基於二氧化鈰之CMP研磨漿可含有額外的水溶性聚合物,諸如多醣,如海藻酸、果膠酸、羧甲基纖維素、瓊脂、卡德蘭(curdlan)及普魯蘭(pullulan);聚羧酸,諸如聚天冬胺酸、聚麩胺酸、聚離胺酸、聚蘋果酸、聚甲基丙烯酸、聚醯亞胺酸、聚順丁烯二酸、聚衣康酸、聚反丁烯二酸、聚(對苯乙烯羧酸)、聚丙烯酸、聚丙烯醯胺、胺基聚丙烯醯胺、聚乙醛酸及其鹽;及乙烯基聚合物,諸如聚乙烯醇及聚丙烯醛。據稱基於二氧化鈰之CMP研磨漿具有高二氧化矽對多晶矽之選擇性。
美國專利申請案US 2007/0191244 A1揭示一種基於二氧化鈰之CMP研磨漿,其含有具有30至500之重量平均分子量且含有羥基及羧基或兩者之化合物,諸如檸檬酸鹽、蘋果酸鹽、葡糖酸鹽、酒石酸鹽、2-羥基異丁酸鹽、己二酸鹽、辛酸鹽、丁二酸鹽、含EDTA之化合物、戊二酸鹽、亞甲基丁二酸鹽、甘露糖、甘油-半乳-庚糖、赤-甘露-辛糖、阿拉伯-半乳-壬糖及麩胺醯胺。基於二氧化鈰之CMP研磨漿可另外含有線性聚合物酸或具有烷氧基聚伸烷二醇側鏈之接枝型聚合物酸。據稱基於二氧化鈰之CMP研磨漿實現研磨晶圓之全面平坦度改良。
美國專利申請案US 2007/0218811 A1揭示一種基於二氧化鈰之CMP研磨漿,其具有4至7.5之pH值且含有分散劑、聚羧酸及100至1000 ppm第一易解離酸基之pKa為3.2或3.2以下之強酸。舉例而言,丙烯酸及甲基丙烯酸之聚合物作為陰離子分散劑而被提及,聚氧化乙烯衍生物作為非離子分散劑而被提及,且聚乙烯基吡咯啶酮作為陽離子分散劑而被提及。特別提及之強酸為硫酸、HCl、硝酸、磷酸、乙二酸、順丁烯二酸、苦味酸(picric acid)、亞硫酸、硫代亞硫酸、胺基磺酸、氯酸、過氯酸、亞氯酸、氫碘酸、過碘酸、碘酸、氫溴酸、過溴酸、鉻酸、亞硝酸、二膦酸、三磷酸、次膦酸、甲基吡啶酸、膦酸、異菸酸、菸鹼酸、三氯乙酸、二氯乙酸、氯乙酸、氰基乙酸、草醯乙酸、硝基乙酸、溴乙酸、氟乙酸、苯氧基乙酸、鄰溴苯甲酸、鄰硝基苯甲酸、鄰氯苯甲酸、對胺基苯甲酸、鄰胺基苯甲酸、鄰苯二甲酸、反丁烯二酸、丙二酸、酒石酸、檸檬酸、鄰氯苯胺、2,2'-聯吡啶、4,4'-聯吡啶、2,6-吡啶二羧酸、丙酮酸、聚苯乙烯磺酸、聚磺酸、麩胺酸、水楊酸、天冬胺酸、2-胺基乙基膦酸、離胺酸、精胺酸、異白胺酸、肌胺酸、鳥胺酸、鳥嘌呤核苷、瓜胺酸、酪胺酸、纈胺酸、次黃嘌呤、甲硫胺酸、離胺酸及白胺酸。基於二氧化鈰之CMP研磨漿引起有效高速運轉、較易方法管理及由於圖案密度差異之膜厚度波動較小。
美國專利申請案US 2008/0085602 A1及US 2008/0124913 A1揭示一種基於二氧化鈰之CMP研磨漿,其含有0.001 wt.%至0.1 wt.%之選自氧化乙烯-氧化丙烯-氧化乙烯三嵌段共聚物及聚丙烯酸之非離子界面活性劑作為分散劑。據稱基於二氧化鈰之研磨漿具有高二氧化矽及氮化矽對多晶矽之選擇性。
電子裝置,尤其半導體積體電路(IC)之製造需要尤其涉及高選擇性CMP之高精度方法。
雖然先前技術之基於二氧化鈰之CMP研磨漿可具有令人滿意的氧化物對氮化物之選擇性且可得到具有如晶圓內非均勻性(WIWNU)及晶圓間非均勻性(WTWNU)所例證之良好的全面及局部平坦度之研磨的晶圓,但IC架構,尤其具有LSI(大規模積體)或VLSI(超大規模積體)之IC之尺寸的不斷減小需要基於二氧化鈰之CMP研磨漿持續改良,以便滿足積體電路裝置製造商日益增長之技術及經濟要求。
然而,此持續改良先前技術之基於二氧化鈰之CMP研磨漿的迫切需要不僅適用於積體電路裝置領域,而且製造以下之領域中之研磨及平坦化功效亦需改良,其他電子裝置,諸如液晶板、有機電致發光板、印刷電路板、微型機器、DNA晶片、微型工廠、光伏打電池及磁頭;以及高精度機械裝置及光學裝置,尤其光學玻璃(諸如光罩、透鏡及稜鏡)、無機導電膜(諸如氧化銦錫(ITO))、光學積體電路、光學交換元件、光學波導、光學單晶(諸如光學纖維端面及閃爍體)、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。該等電子及光學裝置之製造亦需要高精度CMP方法步驟。
本發明之目標
因此,本發明之一目標為提供一種新穎水研磨組成物,詳言之一種新穎化學機械研磨(CMP)組成物,尤其一種新穎的基於二氧化鈰之CMP研磨漿,其不再展現先前技術研磨組成物之缺陷及缺點。
詳言之,新穎水研磨組成物,詳言之新穎化學機械研磨(CMP)組成物,尤其新穎的基於二氧化鈰之CMP研磨漿應展現顯著改良之氧化物對氮化物之選擇性且得到具有如晶圓內非均勻性(WIWNU)及晶圓間非均勻性(WTWNU)所例證之卓越的全面及局部平坦度之研磨的晶圓。因此,其應極適於製造具有尺寸小於50 nm之結構的IC架構,尤其具有LSI(大規模積體)或VLSI(超大規模積體)之IC。
此外,新穎水研磨組成物,詳言之新穎化學機械研磨(CMP)組成物且尤其新穎的基於二氧化鈰之CMP研磨漿將不僅格外適用於積體電路裝置領域,而且將最有效且有利地適用於製造以下之領域:其他電子裝置,諸如液晶板、有機電致發光板、印刷電路板、微型機器、DNA晶片、微型工廠及磁頭;以及高精度機械裝置及光學裝置,尤其光學玻璃(諸如光罩、透鏡及稜鏡)、無機導電膜(諸如氧化銦錫(ITO))、光學積體電路、光學交換元件、光學波導、光學單晶(諸如光學纖維端面及閃爍體)、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。
本發明之另一目標為提供一種用於研磨機械、電子及光學裝置基材的新穎方法,該等基材含有二氧化矽電介質膜及氮化矽膜。
因此,已發現新穎水研磨組成物,其包含(A)至少一種類型之磨料顆粒,當分散於具有範圍介於3至9之pH值的水性介質中時,如電泳遷移率所證明帶正電;(B)至少一種含有羥基之水溶性及水分散性組分,其選自由以下組成之群:(b1)脂族及環脂族羥基羧酸,該分子具有至少兩個碳原子、至少一個羥基及至少一個羧酸基,其中羥基比羧酸基之莫耳比為至少1;(b2)具有至少一個選自由內酯基、酯化羥基、酯化羧酸基及其混合物組成之群之基團的羥基羧酸(b1)之酯,其限制條件為(b2)中存在至少一個羥基;及(b3)其混合物;及(C)至少一種水溶性及水分散性聚合物組分,其選自由以下組成之群:(c1)線性及分枝氧化烯均聚物及共聚物;(c2)線性及分枝脂族及環脂族聚(N-乙烯基醯胺)均聚
物及共聚物;及(c3)具有小於100,000道爾頓之重量平均分子量的陽離子聚合物絮凝劑。
在下文中,該新穎水研磨組成物稱為「本發明之組成物」。
此外,已發現用於研磨機械、電子及光學裝置基材的新穎方法,該方法係藉由使基材與本發明之組成物接觸至少一次且研磨基材直至達成所需平坦度。
在下文中,用於研磨機械、電子及光學裝置基材的新穎方法稱為「本發明之方法」。
另外,已發現本發明之組成物用於製造電子、機械及光學裝置之新穎用途及經陽離子修飾之絮凝劑用於穩定顆粒之水性分散液之新穎用途,該等用途在下文稱為「本發明之用途」。
本發明之優勢
鑒於先前技術,令熟習此項技術者驚訝且未能預期的是,本發明之目標可藉由本發明之組成物、本發明之方法及用途來解決。
尤其令人驚訝的是,本發明之組成物展現顯著改良之氧化物對氮化物之選擇性且得到具有如晶圓內非均勻性(WIWNU)及晶圓間非均勻性(WTWNU)所例證之卓越的全面及局部平坦度之研磨的晶圓。因此,其極適於製造具有尺寸小於50nm之結構的IC架構,尤其具有LSI(大規模積體)或VLSI(超大規模積體)之IC。
另外,本發明之組成物在長期運輸及儲存期間為穩定的,該穩定性顯著改良後勤及方法管理。
此外,本發明之組成物不僅格外適用於積體電路裝置領域,而且最有效且有利地適用於製造以下之領域:其他電子裝置,諸如液晶板、有機電致發光板、印刷電路板、微型機器、DNA晶片、微型工廠及磁頭;以及高精度機械裝置及光學裝置,尤其光學玻璃(諸如光罩、透鏡及稜鏡)、無機導電膜(諸如氧化銦錫(ITO))、光學積體電路、光學交換元件、光學波導、光學單晶(諸如光學纖維端面及閃爍體)、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。
最特定言之,本發明之組成物格外適於本發明之用途。
因此,本發明之組成物最特定言之適用於本發明之方法。本發明之方法可最適宜用於研磨,詳言之化學機械研磨電子裝置基材,該等電子裝置諸如液晶板、有機電致發光板、印刷電路板、微型機器、DNA晶片、微型工廠及磁頭;以及高精度機械裝置及光學裝置基材,該等裝置尤其為光學玻璃(諸如光罩、透鏡及稜鏡)、無機導電膜(諸如氧化銦錫(ITO))、光學積體電路、光學交換元件、光學波導、光學單晶(諸如光學纖維端面及閃爍體)、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。
然而,最特定言之,本發明之方法極適於研磨含有二氧化矽電介質膜及氮化矽膜之半導體晶圓。本發明之方法
得到具有如晶圓內非均勻性(WIWNU)及晶圓間非均勻性(WTWNU)所例證之卓越的全面及局部平坦度及均衡性且無盤狀凹陷、杯狀凹陷或熱斑(hotspot)之研磨的晶圓。因此,其極適於製造具有尺寸小於50nm之結構的IC架構,尤其具有LSI(大規模積體)或VLSI(超大規模積體)之IC。
本發明之組成物為一種水性組成物。其意指該組成物含有水(尤其超純水)作為主溶劑,及分散劑。儘管如此,本發明之組成物可含有至少一種可與水混溶的有機溶劑,然而僅含有少量以使其不改變本發明之組成物的水性性質。
本發明之組成物較佳含有60wt.%至99.95wt.%、更佳70wt.%至99.9wt.%、甚至更佳80wt.%至99.9wt.%且最佳90wt.%至99.9wt.%之量的水,該等重量百分比以本發明之組成物的總重量計。
「水溶性」意指本發明之組成物的相關組分或成分可在分子水平上溶解於水相中。
「水分散性」意指本發明之組成物的相關組分或成分可分散於水相中且形成穩定的乳液或懸浮液。
「聚合物」或「聚合」意指本發明之組成物的相關組分或成分由12個以上連接之單體結構單元組成,所有該等結構單元可具有相同結構。然而,該等結構單元亦可選自至少兩種不同結構。
本發明之組成物的第一必需成分為至少一種(較佳一種)類型之磨料顆粒(A)。
當分散於具有範圍介於3至9之pH值的水性介質中時,磨料顆粒(A)帶正電。帶正電由磨料顆粒(A)之電泳遷移率μ(μm/s)(V/cm)來證明。電泳遷移率μ可使用諸如Malvern,Ltd之Zetasizer Nano之儀器直接量測。
磨料顆粒(A)之平均粒徑可大範圍變化,且因此可最有利地調節至本發明之既定組成物及方法的特定要求。如動態雷射光散射所測定之平均粒徑較佳在1 nm至2000 nm、較佳1 nm至1000 nm、更佳1 nm至750 nm且最佳1 nm至500 nm之範圍內。
磨料顆粒(A)之粒徑分佈可為單峰、雙峰或多峰。粒徑分佈較佳為單峰以便在本發明之方法期間具有易重現的磨料顆粒(A)之性質特徵及易重現的條件。
此外,磨料顆粒(A)之粒徑分佈可為窄的或寬的。粒徑分佈較佳為窄的,僅具有少量小顆粒及大顆粒,以便在本發明之方法期間具有易重現的磨料顆粒(A)之性質特徵及易重現的條件。
磨料顆粒(A)可具有多種形狀。因此,其可具有一種或基本上一種類型之形狀。然而,磨料顆粒(A)亦可能具有不同形狀。詳言之,兩種類型形狀不同的磨料顆粒(A)可存在於本發明之既定組成物中。關於形狀本身,其可為立方體、具有斜切邊之立方體、八面體、二十面體、不規則球狀(nodule)及具有或不具有突起或凹穴之球體。形狀最佳為無或僅具有極少突起或凹穴之球體。照例此形狀較佳,因為其一般增加CMP方法期間磨料顆粒(A)對其所暴露之機械力的抗性。
原則上,任何類型之磨料顆粒(A)均可用於本發明之組成物,只要其具有上述性質特徵。因此,磨料顆粒(A)可為有機或無機顆粒或有機-無機混雜顆粒。磨料顆粒(A)較佳為無機顆粒。
原則上,任何類型之無機磨料顆粒(A)均可用於本發明之組成物,只要其具有上述性質特徵。然而,最佳使用含有二氧化鈰或由二氧化鈰組成之無機磨料顆粒(A)。
含有二氧化鈰之磨料顆粒(A)可含有少量其他稀土金屬氧化物。
含有二氧化鈰之磨料顆粒(A)較佳為包含含有至少一種其他磨料顆粒材料或由至少一種其他磨料顆粒材料組成之核心的複合顆粒,其他磨料顆粒材料不同於二氧化鈰,詳言之為氧化鋁、二氧化矽、二氧化鈦、氧化鋯、氧化鋅及其混合物。
該等複合顆粒(A)可自例如以下中知曉:WO 2005/035688 A1;US 6,110,396;US 6,238,469 B1;US 6,645,265 B1;K. S. Choi等人,Mat. Res. Soc. Symp. Proc. 第671卷,2001 Materials Research Society,M5.8.1至M5.8.10;S.-H. Lee等人,J. Mater. Res.,第17卷,第10期,(2002),第2744至2749頁;A. Jindal等人,Journal of the Electrochemical Society, 150(5) G314-G318(2003);Z. Lu,Journal of Materials Research,第18卷,第10期,2003年10月,Materials Research Society或S. Hedge等人,Electrochemical and Solid-State Letters,7(12) G316-G318(2004)。
複合顆粒(A)最佳為包含選自由氧化鋁、二氧化矽、二氧化鈦、氧化鋯、氧化鋅及其混合物組成之群且具有20 nm至100 nm核心尺寸之核心的樹莓型塗佈顆粒,其中該核心經具有小於10 nm之粒徑的二氧化鈰顆粒塗佈。
本發明之組成物中所用的磨料顆粒(A)之量可大範圍變化,且因此可最有利地調節至本發明之既定組成物及方法的特定要求。本發明之組成物較佳含有0.005 wt.%至10 wt.%、更佳0.01 wt.%至8 wt.%且最佳0.01 wt.%至6 wt.%之磨料顆粒(A),該等重量百分比以本發明之組成物的總重量計。
本發明之組成物含有至少一種(較佳一種)含有羥基的水溶性或水分散性(較佳水溶性)組分(B)作為第二必需成分。
組分(B)係選自由以下組成之群:
(b1)脂族及環脂族羥基羧酸,該分子具有
-至少兩個、較佳至少三個、更佳至少四個、甚至更佳至少五個且最佳至少六個碳原子,
-至少一個、較佳至少兩個、更佳至少三個且最佳至少四個羥基,及
-至少一個羧酸基,
其中羥基比羧酸基之莫耳比為至少1、較佳至少2、更佳至少3且最佳至少4;
(b2)具有至少一個選自由內酯基、酯化羥基、酯化羧酸基及其混合物組成之群之基團的羥基羧酸(b1)之酯,其限制條件為(b2)中存在至少一個羥基、較佳至少兩個且最佳至少三個羥基;及
(b3)其混合物。
羥基羧酸(b1)較佳選自由乙醇酸、乳酸、奎尼酸(quinic acid)、糖酸及其混合物組成之群。
酯(b2)較佳選自由乙醇酸酯、乳酸酯、奎尼酸酯及糖酸酯及內酯及其混合物組成之群。
糖酸(b1)更佳選自由醛醣酸、糖醛酸、葡醛酸、醛醣二酸、酮糖酸、神經胺糖酸、唾液酸及其混合物組成之群。
糖酸酯(b2)更佳選自由醛醣酸酯、糖醛酸酯、葡醛酸酯、醛醣二酸酯、酮糖酸酯、神經胺糖酸酯、唾液酸酯及內酯及其混合物組成之群。
糖酸(b1)甚至更佳選自由甘油酸、酒石酸、蘇糖酸、赤酮酸、木糖酸、葡糖醛酸、抗壞血酸、葡萄糖酸、半乳糖醛酸、艾杜糖醛酸(iduronic acid)、甘露糖醛酸、葡糖醛酸、古洛糖酸(guluronic acid)、葡醛酸、葡糖二酸、酮糖酸、神經胺糖酸、唾液酸、胞壁酸、乳糖酸及其混合物組成之群。
糖酸酯(b2)甚至更佳選自由甘油酸酯、酒石酸酯、蘇糖酸酯、赤酮酸酯、木糖酸酯、葡糖醛酸酯、抗壞血酸酯、葡萄糖酸酯、半乳糖醛酸酯、艾杜糖醛酸酯、甘露糖醛酸酯、葡糖醛酸酯、古洛糖酸酯、葡醛酸酯、葡糖二酸酯、酮糖酸酯、神經胺糖酸酯、唾液酸酯、胞壁酸酯、乳糖酸酯及內酯、葡萄糖酸-δ-內酯、平葡酸(pangamic acid)及其混合物組成之群。
組分(B)最佳選自由奎尼酸、葡糖醛酸、乳糖酸、葡萄糖酸-δ-內酯及其混合物組成之群。
本發明之組成物中組分(B)之濃度可大範圍變化,且因此可最有利地調節至本發明之既定組成物及方法的特定要求。本發明之組成物較佳含有0.005 wt.%至5 wt.%、更佳0.01 wt.%至4 wt.%且最佳0.01 wt.%至3 wt.%之量的組分(B),該等重量百分比以本發明之組成物的總重量計。
作為第三必需成分,本發明之組成物含有至少一種(較佳兩種)水溶性或水分散性(較佳水溶性)之選自由以下組成之群的聚合物組分(C)。
組分(C)選自由以下組成之群:
(c1)線性及分枝氧化烯均聚物及共聚物;
(c2)線性及分枝脂族及環脂族聚(N-乙烯基醯胺)均聚物及共聚物;及
(c3)陽離子聚合物絮凝劑,其具有小於100,000、較佳小於75,000、甚至更佳小於50,000且最佳小於30,000道爾頓之重量平均分子量。
氧化烯均聚物或共聚物(b1)較佳選自由線性及分枝氧化乙烯及氧化丙烯均聚物及共聚物組成之群。
氧化乙烯-氧化丙烯共聚物(b1)可為含有聚氧化乙烯嵌段及聚氧化丙烯嵌段之無規共聚物、交替共聚物或嵌段共聚物。在氧化乙烯-氧化丙烯嵌段共聚物(b1)中,聚氧化乙烯嵌段較佳具有10至15之親水-親脂平衡(HLB)值。聚氧化丙烯嵌段可較佳具有28至約32之HLB值。
氧化烯均聚物(b1)較佳為氧化乙烯聚合物,諸如聚乙二醇(PEG)。
水溶性聚合物(b1)較佳具有2000道爾頓至1,000,000道爾頓、更佳5000道爾頓至500,000道爾頓且最佳10,000道爾頓至250,000道爾頓之重量平均分子量。
水溶性聚合物(b1)為慣用且已知的市售材料。適合的水溶性聚合物(b1)描述於以下中:日本專利申請案JP 2001-240850 A申請專利範圍第2項以及段落[0007]至[0014]、美國專利申請案US 2007/0077865 A1欄頁第1頁段落[0008]至第2頁段落[0010]、美國專利申請案US 2006/0124594 A1第3頁段落[0036]及[0037]及美國專利申請案US 2008/0124913 A1第3頁段落[0031]至[0033]以及申請專利範圍第14項,或其如BASF公司之公司手冊「PluronicTM & TetronicTM Block Copolymer Surfactants,1996」或美國專利US 2006/0213780 A1所示,由BASF公司及BASF SE以商標PluronicTM、TetronicTM及BasensolTM銷售。
最佳使用聚乙二醇(PEG)作為聚合物(b1)。
作為線性及分枝脂族及環脂族聚(N-乙烯基醯胺)均聚物及共聚物(c2)之構築嵌段的脂族及環脂族N-乙烯基醯胺單體較佳選自由N-乙烯基乙醯胺、N-乙烯基吡咯啶酮、N-乙烯基戊內醯胺、N-乙烯基己內醯胺、N-乙烯基丁二醯亞胺及其混合物組成之群。
聚(N-乙烯基醯胺)共聚物(c2)可含有除N-乙烯基醯胺以外的自慣用及已知烯系不飽和單體衍生之單體單元,例如乙烯基酯及乙烯基醚、丙烯酸酯及甲基丙烯酸酯、烯丙基酯及烯丙基醚、可經鹵素原子或腈基取代之烯烴、及苯乙烯單體,其限制條件為該等單體單元僅以不危及水溶性之量含有。
水溶性聚合物(c2)較佳具有2000道爾頓至1,000,000道爾頓、更佳5000道爾頓至500,000道爾頓且最佳10,000道爾頓至250,000道爾頓之重量平均分子量。
陽離子聚合物絮凝劑(c3)較佳選自由陽離子改質之聚丙烯醯胺、多元胺、聚乙烯亞胺、聚(二烯丙基-N,N-二烷基鹵化銨)及其混合物組成之群。
陽離子基團更佳選自由第四銨基、鋶基、鏻基及其混合物組成之群。最佳使用第四銨基。
聚(二烯丙基-N,N-二烷基鹵化銨)(c3)之烷基更佳選自由甲基、乙基、丙基及異丙基及其混合物組成之群。最佳使用甲基。鹵化物更佳選自由氟化物、氯化物及溴化物組成之群。最佳使用氯化物。最佳使用聚(二烯丙基-N,N-二甲基氯化銨)(poly-DADMAC)。
本發明之組成物中陽離子改質之絮凝劑(c3)之濃度可大範圍變化,且因此可最有利地調節至本發明之既定組成物及方法的特定要求。絮凝劑(c3)之使用量較佳為0.0001 wt.%至1 wt.%,較佳0.0002 wt.%至1 wt.%且最佳0.0003 wt.%至1 wt.%,該等重量百分比以本發明之組成物的總重量計。
陽離子改質之絮凝劑(c3)為慣用且已知的材料,其以例如商標SedipurTM C由BASF SE市售。
最令人驚訝的是,根據一種本發明之用途,陽離子改質之絮凝劑(c3)可用於穩定磨料顆粒(A)之水性分散液。
本發明之組成物可含有至少一種功能組分(D),其本質上不同於成分(A)、(B)及(C)。
功能組分(D)較佳選自慣用於基於二氧化鈰之CMP研磨漿中之化合物之群。
該等化合物(D)之實例揭示於例如Y. N. Prasad等人,Electrochemical and Solid-State Letters,9(12) G337-G339(2006);Hyun-Goo Kang等人,Journal of Material Research,第22卷,第3期,2007,第777至787頁;S. Kim等人,Journal of Colloid and Interface Science,319(2008),第48至52頁;S. V. Babu等人,Electrochemical and Solid-State Letters,7(12) G327-G330(2004);Jae-Dong Lee等人,Journal of the Electrochemical Society,149(8) G477-G481,2002;美國專利US 5,738,800、US 6,042,741、US 6,132,637、US 6,218,305 B、US 5,759,917、US 6,689,692 B1、US 6,984,588 B2、US 6,299,659 B1、US 6,626,968 B2、US 6,436,835 B1、US 6,491,843 B1、US 6,544,892 B2、US 6,627,107 B2、US 6,616,514 B1及US 7,071,105 B2;美國專利申請案US 2002/0034875 A1、US 2006/0144824 A1、US 2006/0207188 A1、US 2006/0216935 A1、US 2007/0077865 A1、US 2007/0175104 A1、US 2007/0191244 A1及US 2007/0218811 A1;及日本專利申請案JP 2005-336400 A。
此外,功能組分(D)選自由以下組成之群:不同於顆粒(D)之有機、無機及有機-無機混雜磨料顆粒;具有至少兩個羥基之多元醇;具有下限臨界溶解溫度LCST或上限臨界溶解溫度UCST之材料;氧化劑;鈍化劑;電荷反轉劑;錯合劑或螯合劑;摩擦劑;穩定劑;流變劑;界面活性劑;金屬陽離子及有機溶劑。
適合之有機磨料顆粒(D)及其有效量可自例如美國專利申請案US 2008/0254628 A1第4頁段落[0054]或國際申請案WO 2005/014753 A1中知曉,其中揭示由三聚氰胺及三聚氰胺衍生物(諸如乙醯胍胺、苯并胍胺及二氰二胺)組成之固體顆粒。
適合之無機磨料顆粒(D)及其有效量可自例如國際專利申請案WO 2005/014753 A1第12頁第1至8行或美國專利US 6,068,787第6欄第41行至第7欄第65行中知曉。
適合之有機-無機混雜磨料顆粒(D)及其有效量可自例如美國專利申請案US 2008/0254628 A1第4頁段落[0054]或US 2009/0013609 A1第3頁段落[0047]至第6頁段落[0087]中知曉。
適合之多元醇(D)為二醇,諸如乙二醇及丙二醇;三醇,諸如甘油;季戊四醇;醛醣醇;環醣醇及甘油、三羥甲基丙烷、季戊四醇、醛醣醇及環醣醇之二聚物及寡聚物。
適合之氧化劑(D)及其有效量可自例如歐洲專利申請案EP 1 036 836 A1第8頁段落[0074]及[0075]或美國專利US 6,068,787第4欄第40行至第7欄第45行或US 7,300,601 B2第4欄第18至34行中知曉。較佳使用有機及無機過氧化物,更佳使用無機過氧化物。尤其使用過氧化氫。
適合之鈍化劑(D)及其有效量可自例如美國專利US 7,300,601 B2第3欄第59行至第4欄第9行或美國專利申請案US 2008/0254628 A1跨接第4頁及第5頁之段落[0058]中知曉。
適合之錯合劑或螯合劑(D),有時亦稱為摩擦劑(參照美國專利申請案US 2008/0254628 A1第5頁段落[0061])或蝕刻劑(etching agent/etchant)(參照美國專利申請案US 2008/0254628 A1第4頁段落[0054])及其有效量可自例如美國專利US 7,300,601 B2第4欄第35至48行中知曉。尤其最佳使用胺基酸(尤其甘胺酸)及此外含有至少一個、較佳兩個且更佳三個一級胺基之二氰二胺及三,諸如三聚氰胺及水溶性胍胺,尤其三聚氰胺、甲醯胍胺、乙醯胍胺及2,4-二胺基-6-乙基-1,3,5-三。
適合之穩定劑(D)及其有效量可自例如美國專利US 6,068,787第8欄第4至56行中知曉。
適合之流變劑(D)及其有效量可自例如美國專利申請案US 2008/0254628 A1第5頁段落[0065]至第6頁段落[0069]中知曉。
適合之界面活性劑(D)及其有效量可自例如國際專利申請案WO 2005/014753 A1第8頁第23行至第10頁第17行或美國專利US 7,300,601 B2第5欄第4行至第6欄第8行中知曉。
適合之多價金屬離子(D)及其有效量可自例如歐洲專利申請案EP 1 036 836 A1第8頁段落[0076]至第9頁段落[0078]中知曉。
適合之有機溶劑(D)及其有效量可自例如美國專利US 7,361,603 B2第7欄第32至48行或美國專利申請案US 2008/0254628 A1第5頁段落[0059]中知曉。
展現下限臨界溶解溫度LCST或上限臨界溶解溫度UCST之適合之材料(D)描述於以下文獻中:例如H. Mori,H. Iwaya,A. Nagai及T. Endo之文章,Controlled synthesis of thermoresponsive polymers derived from L-proline via RAFT polymerization,Chemical Communication,2005,4872-4874;或D. Schmaljohann之文章,Thermo- and pH-responsive polymers and drug delivery,Advanced Drug Delivery Reviews,第58卷(2006),1655-1670或美國專利申請案US 2002/0198328 A1、US 2004/0209095 A1、US 2004/0217009 A1、US 2006/0141254 A1、US 2007/0029198 A1、US 2007/0289875 A1、US 2008/0249210 A1、US 2008/0050435 A1或US 2009/0013609 A1;美國專利US 5,057,560、US 5,788,82及US 6,682,642 B2;國際專利申請案WO 01/60926 A1、WO 2004/029160 A1、WO 2004/0521946 A1、WO 2006/093242 A2或WO 2007/012763 A1;歐洲專利申請案EP 0 583 814 A1、EP 1 197 587 B1及EP 1 942 179 A1;或德國專利申請案DE 26 10 705。
原則上,可使用慣用於CMP領域中之任何已知電荷反轉劑(D)。電荷反轉劑(D)較佳選自由含有至少一個選自由羧酸酯基、磺酸酯基、硫酸酯基及膦酸酯基組成之群的陰離子基團之單體化合物、寡聚化合物及聚合化合物組成之群。
若功能組分(D)存在,則其含量可變化。以相應CMP組成物之總重量計,(D)之總量較佳不超過10 wt.%(「wt.%」意指「重量百分比」)、更佳不超過2 wt.%、最佳不超過0.5 wt.%、尤其不超過0.1 wt.%,例如不超過0.01 wt.%。以相應組成物之總重量計,(D)之總量較佳為至少0.0001 wt.%、更佳至少0.001 wt.%、最佳至少0.008 wt.%、尤其至少0.05 wt.%,例如至少0.3 wt.%。
本發明之組成物可視情況含有至少一種pH調節劑或緩衝劑(E),其本質上不同於成分(A)、(B)及(C)。
適合之pH調節劑或緩衝劑(E)及其有效量可自例如歐洲專利申請案EP 1 036 836 A1第8頁段落[0080]、[0085]及[0086];國際專利申請案WO 2005/014753 A1第12頁第19至24行;美國專利申請案US 2008/0254628 A1第6頁段落[0073]或美國專利US 7,300,601 B2第5欄第33至63行中知曉。pH調節劑或緩衝劑(E)之實例為氫氧化鉀、氫氧化銨、氫氧化四甲基銨(TMAH)、硝酸及硫酸。
若pH調節劑或緩衝劑(E)存在,則含量可變化。以相應CMP組成物之總重量計,(E)之總量較佳不超過20 wt.%、更佳不超過7 wt.%、最佳不超過2 wt.%、尤其不超過0.5 wt.%,例如不超過0.1 wt.%。以相應組成物之總重量計,(E)之總量較佳為至少0.001 wt.%、更佳至少0.01 wt.%、最佳至少0.05 wt.%、尤其至少0.1 wt.%,例如至少0.5 wt.%。
本發明之組成物的pH值較佳使用上述pH調節劑(E)設定在較佳2.5與4之間。
本發明之組成物的製備不展現任何特殊性,而是可藉由將上述成分(A)、(B)及(C)及視情況選用之(D)及/或(E)溶解或分散於水性介質(詳言之,去離子水)中來進行。出於此目的,可使用慣用及標準混合方法及混合設備,諸如攪拌容器、在線溶解器、高剪切葉輪、超音波混合器、均化器噴嘴或對流混合器。由此獲得之本發明之組成物較佳可經由具有適當篩孔之過濾器過濾以便移除粗粒狀顆粒,諸如精細分散之固體磨料顆粒(A)的聚結物或聚集物。
本發明之組成物極適於本發明之方法。
在本發明之方法中,使電子、機械及光學裝置(尤其電子裝置,最佳積體電路裝置)基材與本發明之組成物接觸至少一次且研磨(尤其化學及機械研磨)直至獲得所需平坦度。
本發明之方法在具有由低k或超低k二氧化矽材料組成之隔離層且具有氮化矽層作為停止層或障壁層的矽半導體晶圓之CMP中展現出其特殊優勢。
適合之低k或超低k材料及製備絕緣介電層之適合方法描述於例如美國專利申請案US 2005/0176259 A1第2頁段落[0025]至[0027]、US 2005/0014667 A1第1頁段落[0003]、US 2005/0266683 A1第1頁段落[0003]及第2頁段落[0024]或US 2008/0280452 A1段落[0024]至[0026]或美國專利US 7,250,391 B2第1欄第49至54行或歐洲專利申請案EP 1 306 415 A2第4頁段落[0031]中。
本發明之方法尤其適於淺溝槽隔離(STI),其需要在圖案化晶圓基材上優先於氮化矽選擇性地移除二氧化矽。在此方法中,用介電材料(例如二氧化矽)過量裝填經蝕刻之溝槽,過量裝填之介電材料使用氮化矽障壁膜作為停止層研磨。在此較佳具體實例中,在自障壁膜清除二氧化矽同時使暴露之氮化矽及溝槽二氧化矽移除減至最少的情況下結束本發明之方法。
因此,本發明之方法展現氧化物對氮化物之選擇性大於50、較佳大於75且最佳大於100。
本發明之方法不展現特殊性,而是可用慣用於具有IC之半導體晶圓製造中之CMP的方法及設備來進行。
如此項技術中已知,用於CMP之典型設備由用研磨墊覆蓋的旋轉平台組成。晶圓安裝在載體或夾頭上,使其上端向下面向研磨墊。載體將晶圓緊固在水平位置。此研磨及夾持裝置之特殊佈置亦稱為硬平台設計。載體可保留載體墊,其位於載體保留表面與未研磨之晶圓表面之間。此墊可充當晶圓之緩衝墊。
在載體下方,一般亦水平安置較大直徑平台且呈現與待研磨晶圓之表面平行的表面。其研磨墊在平坦化過程期間接觸晶圓表面。在本發明之CMP方法期間,本發明之組成物以連續流形式或以逐滴方式施用於研磨墊上。
使載體與平台均圍繞自載體及平台垂直延伸之相應軸旋轉。旋轉之載體軸可相對於旋轉之平台仍固定在原位或可相對於平台水平擺動。載體之旋轉方向典型地(但不一定)與平台之旋轉方向相同。載體及平台之旋轉速度一般(但不一定)設定為不同值。
平台之溫度慣常設定為10℃與70℃之間的溫度。
關於其他詳情,參考國際專利申請案WO 2004/063301 A1,詳言之第16頁段落[0036]至第18頁段落[0040]以及圖1。
藉由本發明之方法可獲得具有包含圖案化之低k及超低k材料層(詳言之二氧化矽層)之IC的半導體晶圓,其具有極佳平坦度。因此,可獲得銅鑲嵌圖案,其亦具有極佳平坦度,且在成品中,IC具有極佳電子功能。
實施例及比較實驗
比較實驗C1至C5
用比較水研磨組成物C1至C5對二氧化矽塗佈及氮化矽塗佈之毯覆式晶圓進行之CMP及氧化物對氮化物之選擇性
比較水研磨組成物C1至C5之組成彙編於表1中。
關於CMP,使用以下方法參數:
-研磨設備:AMAT Mirra(旋轉型);
-平台速度:90 rpm;
-載體速度:70 rpm;
-由Rohm & Haas製造之IC 1000/Suba 400 K凹槽研磨墊;
-原位修整使用S60 3M金剛石修整器(diamond conditioner);
-研磨漿流速:200 ml/min;
-基材:來自SKW之2000 nm熱二氧化矽塗佈之毯覆式晶圓及來自Montco Silicon之500 nm氮化矽塗佈之毯覆式晶圓;實施例20至22:TEOS二氧化矽塗佈之毯覆式晶圓;
-下壓力:3.5 psi(240毫巴);
-研磨時間:1分鐘。
使用反射計量測材料移除率MRR。所得結果彙編於表2中。
由彙編於表2中之結果顯而易知:僅使用羥基羧酸及含有羥基之內酯可獲得高氧化物對氮化物之選擇性。然而,僅含有此等添加劑之比較水研磨組成物在STI方法中之溝槽氧化物之盤狀凹陷及過度研磨及分散穩定性(適用期)方面需要相當大的改良。
實施例1至4及比較實驗C6及C7
二氧化矽及氮化矽毯覆式晶圓及圖案化之晶圓的CMP
實施例1至4之水研磨組成物及比較水研磨組成物C6及C7之組成彙編於表3中。
關於CMP,使用以下方法參數:
-實施例1及2及比較試驗C6中之研磨設備:AMAT Mirra(旋轉型);
-實施例3及4及比較試驗C7中之研磨設備:Strasbaugh 6EG nHance;
-平台速度:90 rpm;
-載體速度:70 rpm;
-由Rohm & Haas製造之IC 1000/Suba 400 K凹槽研磨墊;
-原位修整使用Rohm & Haas或3M之A160金剛石修整器;
-研磨漿流速:200 ml/min;
-基材:來自SKW之2000 nm熱二氧化矽塗佈之毯覆式晶圓及來自Montco Silicon之500 nm氮化矽塗佈之毯覆式晶圓;
-下壓力:3 psi(205毫巴)。
在CMP之前及之後,由Therma Wave Optiprobe 2600量測材料移除率(MRR)。
使用市售CMP研磨漿(Cabot SS25,1:1稀釋)研磨SKW之二氧化矽-氮化矽-場氧化物(field oxide)圖案化之晶圓STI 3-2之初始構形或梯級高度,以便「敲出」構形。所施加之下壓力為5 psi(341.66毫巴)。此P1方法之目的在於達成近乎平坦化,將少量氧化物厚度留在氮化矽停止層頂部。在兩個部位對圖案化之晶圓進行量測,亦即(i)在活性氧化物部位量測留下的剩餘氧化物及(ii)在場氧化物部位量測溝槽氧化物。
在上述條件下,研磨毯覆式晶圓。使用所得材料移除率MRR計算移除在P1方法後留在氮化矽停止層頂部之活性氧化物的時間。此時間稱為「端點(EP)」且在端點之後的任何額外的研磨時間稱為「過度研磨(OP)」。
所得結果彙編於表4中。
由表4顯而易知:與比較實驗C6及C7相比,添加抗盤狀凹陷劑PEG10K及PVP17K未在毯覆式或活性氧化物MRR方面引起顯著差異,但顯著減少溝槽氧化物消耗及盤狀凹陷。
實施例5
陽離子改質之絮凝劑對基於二氧化鈰之水研磨組成物的穩定作用
向pH為3且含有0.5 wt.%二氧化鈰及0.025 wt.%葡糖醛酸之水研磨組成物中添加各種量之陽離子改質之絮凝劑(BASF SE之SedipurTM CL 520)。用Horiba Instrument粒徑分析器量測平均粒徑。所得結果彙編於表5中。
由表5顯而易知:即使添加諸如10 ppm之較低量亦已足夠控制二氧化鈰顆粒之聚集,由此增加水研磨組成物之穩定性及其適用期。
實施例6及比較試驗C8
使用具有(實施例6)及不具有(比較試驗C8)陽離子改質之絮凝劑的水研磨組成物之CMP及氧化物對氮化物之選擇性
比較試驗C8使用pH為3且含有0.5 wt.%二氧化鈰及0.025 wt.%葡糖醛酸之水研磨組成物。
實施例6使用pH為3且含有0.5 wt.%二氧化鈰、0.025 wt.%葡糖醛酸及70 ppm SedipurTM CL 520之水研磨組成物。
如上文在比較實驗C1至C5中所述,研磨二氧化矽塗佈之毯覆式晶圓及氮化矽塗佈之毯覆式晶圓。
所得結果彙編於表6中。
由表6顯而易知:添加SedipurTM CL 520不影響研磨結果。然而,實施例6之水研磨組成物展現比比較試驗C8之水研磨組成物長很多的適用期。
Claims (19)
- 一種水研磨組成物,其包含(A)至少一種類型之無機磨料顆粒(A),其含有二氧化鈰或由二氧化鈰組成,當分散於具有範圍介於3至9之pH值的水性介質中時,以電泳遷移率所證明帶正電;(B)至少一種含有羥基之水溶性及水分散性組分,選自由以下組成之群:(b1)脂族及環脂族羥基羧酸,該分子具有至少三個碳原子、至少兩個羥基及至少一個羧酸基,其中羥基比羧酸基之莫耳比為至少2;(b2)具有至少一個選自由內酯基、酯化羥基、酯化羧酸基及其混合物組成之群之基團的羥基羧酸(b1)之酯,其限制條件為(b2)中存在至少兩個羥基;及(b3)其混合物;及(C)至少一種水溶性及水分散性聚合物組分,選自由以下組成之群:(c1)線性及分枝氧化烯均聚物及共聚物;(c2)線性及分枝脂族及環脂族聚(N-乙烯基醯胺)均聚物及共聚物;及(c3)具有小於100,000道爾頓之重量平均分子量的陽離子聚合物絮凝劑。
- 如申請專利範圍第1項之水研磨組成物,其中該等羥基羧酸(b1)係選自由乙醇酸、乳酸、奎尼酸(quinic acid)、糖酸及其混合物組成之群;且該等酯(b2)係選自由乙醇 酸酯、乳酸酯、奎尼酸酯及糖酸酯及內酯及其混合物組成之群。
- 如申請專利範圍第2項之水研磨組成物,其中該等糖酸(b1)係選自由醛醣酸、糖醛酸、葡醛酸、醛醣二酸、酮糖酸、神經胺糖酸、唾液酸及其混合物組成之群;且該等糖酸酯(b2)係選自由醛醣酸酯、糖醛酸酯、葡醛酸酯、醛醣二酸酯、酮糖酸酯、神經胺糖酸酯、唾液酸酯及內酯及其混合物組成之群。
- 如申請專利範圍第3項之水研磨組成物,其中該等糖酸(b1)係選自由甘油酸、酒石酸、蘇糖酸、赤酮酸、木糖酸、葡糖醛酸、抗壞血酸、葡萄糖酸、半乳糖醛酸、艾杜糖醛酸(iduronic acid)、甘露糖醛酸、葡糖醛酸、古洛糖酸(guluronic acid)、葡醛酸、葡糖二酸、酮糖酸、神經胺糖酸、唾液酸、胞壁酸、乳糖酸及其混合物組成之群;且該等糖酸酯(b2)係選自由甘油酸酯、酒石酸酯、蘇糖酸酯、赤酮酸酯、木糖酸酯、葡糖醛酸酯、抗壞血酸酯、葡萄糖酸酯、半乳糖醛酸酯、艾杜糖醛酸酯、甘露糖醛酸酯、葡糖醛酸酯、古洛糖酸酯、葡醛酸酯、葡糖二酸酯、酮糖酸酯、神經胺糖酸酯、唾液酸酯、胞壁酸酯及乳糖酸酯及內酯、葡萄糖酸-δ-內酯、平葡酸及其混合物組成之群。
- 如申請專利範圍第1項之水研磨組成物,其中該等水溶性或水分散性線性或分枝氧化烯均聚物或共聚物(c1)係選自由氧化乙烯及氧化丙烯均聚物及共聚物及其混合物組成之群;該等線性或分枝脂族或環脂族聚(N-乙烯基醯胺) 均聚物或共聚物(c2)係選自由脂族及環脂族N-乙烯基醯胺單體之均聚物及共聚物組成之群,該等脂族及環脂族N-乙烯基醯胺單體選自由N-乙烯基乙醯胺、N-乙烯基吡咯啶酮、N-乙烯基戊內醯胺、N-乙烯基己內醯胺、N-乙烯基丁二醯亞胺及其混合物組成之群;且該等陽離子聚合物絮凝劑(c3)係選自由陽離子改質之聚丙烯醯胺、多元胺、聚乙烯亞胺、聚(二烯丙基-N,N-二烷基鹵化銨)及其混合物組成之群。
- 如申請專利範圍第1項之水研磨組成物,其中其含有至少一種不同於該等組分(A)、(B)及(C)之功能組分(D)。
- 如申請專利範圍第6項之水研磨組成物,其中該功能組分(D)係選自由不同於該等顆粒(A)之有機、無機及有機-無機混雜磨料顆粒;具有至少兩個羥基之多元醇;具有下限臨界溶解溫度LCST或上限臨界溶解溫度UCST之材料;氧化劑;鈍化劑;電荷反轉劑;錯合劑或螯合劑;摩擦劑;穩定劑;流變劑;界面活性劑;金屬陽離子及有機溶劑組成之群。
- 如申請專利範圍第1項之水研磨組成物,其中其含有至少一種不同於該等組分(A)、(B)及(C)之pH調節劑或緩衝劑(E)。
- 如申請專利範圍第1項之水研磨組成物,其中其具有範圍介於2.5至4之pH值。
- 一種用於研磨電子、機械及光學裝置基材之方法,其係藉由使該基材與水研磨組成物接觸至少一次且研磨該 基材直至達成所需平坦度,該方法之特徵在於使用如申請專利範圍第1項至第9項中任一項之水研磨組成物。
- 如申請專利範圍第10項之方法,其中該基材包含至少一個含有至少一種介電質二氧化矽材料或由至少一種介電質二氧化矽材料組成之層及至少一個含有氮化矽或由氮化矽組成之層。
- 如申請專利範圍第11項之方法,其中其氧化物對氮化物之選擇性大於50。
- 如申請專利範圍第10項至第12項中任一項之方法,其中該等電子裝置為積體電路裝置、液晶板、有機電致發光板、印刷電路板、微型機器、DNA晶片、微型工廠及磁頭;該等機械裝置為高精度機械裝置;且該等光學裝置為光學玻璃、無機導電膜、光學積體電路、光學交換元件、光學波導、光學單晶、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。
- 如申請專利範圍第13項之方法,其中該光學玻璃選自光罩、透鏡及稜鏡。
- 如申請專利範圍第13項之方法,其中該無機導電膜選自氧化銦錫(ITO)。
- 如申請專利範圍第13項之方法,其中該光學單晶選自光學纖維端面及閃爍體。
- 如申請專利範圍第13項之方法,其中該等積體電路裝置含有具有尺寸小於50nm之結構的大規模積體或超大規模積體之積體電路。
- 一種如申請專利範圍第1項至第9項中任一項之水研磨組成物的用途,其係用於製造電子、機械及光學裝置。
- 一種具有小於100,000道爾頓之重量平均分子量的陽離子改質之絮凝劑(c3)的用途,其係用於穩定含有至少一種類型之磨料顆粒(A)的分散液,當該等磨料顆粒(A)分散於具有範圍介於3至9之pH值的水性介質中時,以電泳遷移率所證明帶正電。
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TWI765140B (zh) * | 2018-03-14 | 2022-05-21 | 美商Cmc材料股份有限公司 | 用於sti應用之cmp組合物 |
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EP2614123B1 (en) | 2017-06-28 |
JP6196155B2 (ja) | 2017-09-13 |
EP2614123A4 (en) | 2014-07-30 |
KR20130133177A (ko) | 2013-12-06 |
SG10201506220PA (en) | 2015-09-29 |
SG188460A1 (en) | 2013-04-30 |
WO2012032469A1 (en) | 2012-03-15 |
US20130161285A1 (en) | 2013-06-27 |
RU2013115235A (ru) | 2014-10-20 |
KR101907863B1 (ko) | 2018-10-15 |
TW201211223A (en) | 2012-03-16 |
IL225085A (en) | 2017-09-28 |
EP2614123A1 (en) | 2013-07-17 |
CN103189457A (zh) | 2013-07-03 |
MY164859A (en) | 2018-01-30 |
RU2577281C2 (ru) | 2016-03-10 |
JP2013540851A (ja) | 2013-11-07 |
CN103189457B (zh) | 2015-12-09 |
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