TW201425558A - 硏磨用組成物 - Google Patents
硏磨用組成物 Download PDFInfo
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- TW201425558A TW201425558A TW102140485A TW102140485A TW201425558A TW 201425558 A TW201425558 A TW 201425558A TW 102140485 A TW102140485 A TW 102140485A TW 102140485 A TW102140485 A TW 102140485A TW 201425558 A TW201425558 A TW 201425558A
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- TW
- Taiwan
- Prior art keywords
- polishing
- acid
- polished
- polishing composition
- cerium oxide
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 165
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 150000007524 organic acids Chemical class 0.000 claims abstract description 54
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- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 60
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 56
- 239000000463 material Substances 0.000 claims description 48
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture 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
- H01L21/18—Manufacture 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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment 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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Mechanical Engineering (AREA)
Abstract
本發明提供一種保存安定性良好,可高速研磨缺乏化學反應性之研磨對象物之研磨用組成物。本發明係一種研磨用組成物,其係含有於表面固定有有機酸之二氧化矽、分子量未達2萬之2元醇與pH調整劑,且pH為6以下。
Description
本發明係關於半導體裝置製造製程中使用之研磨用組成物及使用其之研磨方法。
半導體裝置製造製程中存在有能以高速對缺乏化學反應性之金屬碳化物、金屬氮化物或該等之複合材料等的研磨對象物進行研磨之要求。
用以研磨上述研磨對象物之過去使用之研磨用組成物大多含有研磨粒及酸。
例如,特開2010-41037號公報(美國專利第8419970號說明書)中揭示含有二氧化矽與具有磺酸基或膦酸基之有機酸之pH為2.5~5之研磨用組成物。
然而,過去之研磨用組成物有對於如上述之缺乏化學反應性之研磨對象物之研磨速度仍低之問題。且,作為研磨粒使用之二氧化矽在酸性狀態下之保存安定性差,亦有容易凝聚之問題。
因此本發明之目的係提供一種保存安定性良好、可以高速研磨缺乏化學反應性之研磨對象物的研磨用組成物。
本發明人欲解決上述問題而積極重複研究。結果,發現藉由於酸性之研磨用組成物中含有於表面固定有有機酸之二氧化矽、以及分子量未達2萬之2元醇可解決上述課題,因而完成本發明。
亦即,本發明係一種研磨用組成物,其含有於表面固定有有機酸之二氧化矽、分子量未達2萬之2元醇與pH調整劑,且pH為6以下。
以下,說明本發明。
本發明之第一目的係一種研磨用組成物,其係含有於表面固定有有機酸之二氧化矽、分子量未達2萬之2元醇與pH調整劑,且pH為6以下。藉由成為該構成,可使保存安定性良好,且可以高速研磨缺乏化學反應性之研磨對象物。
藉由使用本發明之研磨用組成物,可以高速研磨缺乏化學反應性之研磨對象物之詳細理由並不清楚,但推測為以下之機制。
以研磨對象物為氮化矽之情況為例進行說明。於表面固定有有機酸之二氧化矽的Zeta電位為負值,且絕對值
亦變大。且,同樣在pH6以下時之氮化矽之Zeta電位為正值。因此,研磨用組成物之pH若為6以下,則研磨用組成物中之於表面固定有有機酸之二氧化矽對於氮化矽不會有電性排斥,反而會相吸。因此,藉由使用本發明之研磨用組成物,可以高速研磨氮化矽。
且,表面未固定有機酸之二氧化矽在酸性條件下之Zeta電位成為0附近,不易引起二氧化矽彼此之排斥。而且,藉由添加2元醇,由於藉由與表面未固定有機酸之二氧化矽中之羥基相互作用而成為接近疏水性之狀態,故表面未固定有機酸之二氧化矽易於凝聚、沉降。
相對於此,本發明所用之表面固定有有機酸之二氧化矽具有羥基以外之源自有機酸之官能基。該源自有機酸之官能基與2元醇不會相互作用,且具有二氧化矽原有之親水性。再者於酸性條件下,表面固定有有機酸之二氧化矽之Zeta電位較大,故表面固定有有機酸之二氧化矽彼此會引起電性排斥,使表面固定有有機酸之二氧化矽之分散安定性變好。因此,認為使本發明之研磨用組成物之保存安定性變良好。
又,上述機制係推測者,本發明不受上述機制之任何限制。
本發明之研磨用組成物中含有之表面固定有有機酸之二氧化矽為作為研磨粒使用之於表面上化學鍵結有有機酸
之二氧化矽。前述二氧化矽包含發煙二氧化矽或膠體二氧化矽等,但以膠體二氧化矽特別佳。前述有機酸並無特別限制,但列舉為磺酸、羧酸、磷酸等,較好為磺酸或羧酸。又,本發明之研磨用組成物中所含之「表面固定有有機酸之二氧化矽」之表面上,上述源自有機酸之酸性基(例如磺基、羧基、磷酸基等)係藉由(視情況透過鍵聯基構造)共價鍵而固定。
表面固定有有機酸之二氧化矽可使用合成品,亦可使用市售品。且,固定有有機酸之二氧化矽可單獨使用,亦可混合2種以上使用。
將該等有機酸導入二氧化矽表面之方法並無特別限制,可有以下方法:以巰基或烷基等之狀態導入二氧化矽表面,隨後,氧化成磺酸或羧酸之方法,以及於上述有機酸基上鍵結保護基之狀態下導入二氧化矽表面,隨後,使保護基脫離之方法。且,將有機酸導入二氧化矽表面時使用之化合物具有至少1個能成為有機酸之官能基,進而較好含有與二氧化矽表面之羥基鍵結所用之官能基、用於控制疏水性‧親水性而導入之官能基、用於控制立體體積而導入之官能基等。
表面固定有有機酸之二氧化矽之具體合成方法若為使有機酸之一種的磺酸固定於二氧化矽之表面上,則可藉例如“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”,Chem.Commun.246-247(2003)中所記載之方法進行。具體而言,使3-巰丙基三甲氧基矽
烷等之具有硫醇基之矽烷偶合劑偶合於二氧化矽上之後,以過氧化氫使硫醇基氧化,藉此可獲得表面固定有磺酸之二氧化矽。或者,若將羧酸固定於二氧化矽之表面上,則可藉例如“Novel Silane Coupling Agents Containing a Photo labile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”,Chemistry Letters,3,228-229(2000)中所記載之方法進行。具體而言,將含有光反應性2-硝基苄酯之矽烷偶合劑偶合於二氧化矽上之後,藉由光照射,可獲得於表面固定有羧酸之二氧化矽。
研磨用組成物中之於表面固定有有機酸之二氧化矽之平均一次粒徑較好為5nm以上,更好為7nm以上,又更好為10nm以上。隨著表面固定有有機酸之二氧化矽之平均一次粒徑變大,而有提高研磨用組成物對研磨對性象物之研磨速度之優點。
研磨用組成物中之表面固定有有機酸之二氧化矽之平均一次粒徑較好為150nm以下,更好為120nm以下,又更好為100nm以下。隨著表面固定有有機酸之二氧化矽之平均一次粒徑變小,而有可抑制使用研磨用組成物研磨後之研磨對象物之表面上產生刮痕之優點。又,表面固定有有機酸之二氧化矽之平均一次粒徑之值係基於例如以BET法測定之表面固定有有機酸之二氧化矽之比表面積而算出。
研磨用組成物中之表面固定有有機酸之二氧化矽之平
均二次粒徑較好為10nm以上,更好為15nm以上,又更好為20nm以上。隨著表面固定有有機酸之二氧化矽之平均二次粒徑變大,而有提高研磨用組成物對研磨對象物之研磨速度之優點。
研磨用組成物中之表面固定有有機酸之二氧化矽之平均二次粒徑較好為200nm以下,更好為180nm以下,又更好為150nm以下。隨著表面固定有有機酸之二氧化矽之平均二次粒徑變小,而有可抑制使用研磨用組成物研磨後之研磨對象物之表面產生刮痕之優點。又,二氧化矽之平均二次粒徑之值係基於例如以使用BET雷射光之光散射法測定之二氧化矽之比表面積而算出。
研磨用組成物中之表面固定有有機酸之二氧化矽之含量較好為0.0005重量%以上,更好為0.001重量%以上,又更好為0.005重量%以上。隨著表面固定有有機酸之二氧化矽之含量變多,而有提高研磨用組成物對研磨對象物之研磨速度之優點。
且研磨用組成物中之表面固定有有機酸之二氧化矽之含量較好為10重量%以下,更好為5重量%以下,又更好為1重量%以下。隨著表面固定有有機酸之二氧化矽之含量變少,而有與被研磨材料之摩擦減少、進一步抑制包含多晶矽或TEOS等之與研磨對象物不同材料之層的研磨速度之優點。
又,上述固定化有有機酸之二氧化矽可單獨使用亦可混合2種以上使用。
本發明中使用之分子量未達2萬之2元醇並無特別限制,較好為以下述化學式(1)表示之化合物。
上述化學式(1)中,R為經取代或無取代之鏈狀或環狀之伸烷基,n為1以上之整數。
該2元醇可使用市售品亦可使用合成品。且,該2元醇可單獨使用亦可混合2種以上使用。
2元醇之進一步具體例列舉為例如甲烷二醇、乙二醇(1,2-乙烷二醇)、1,2-丙烷二醇、丙二醇(1,3-丙烷二醇)、1,2-丁烷二醇、1,4-丁烷二醇、1,2-戊烷二醇、1,5-戊烷二醇、1,6-己烷二醇、1,2-己烷二醇、1,5-己烷二醇、2,5-己烷二醇、1,7-庚烷二醇、1,8-辛烷二醇、1,2-辛烷二醇、1,9-壬烷二醇、1,2-癸烷二醇、1,10-癸烷二醇、1,12-十二烷二醇、1,2-十二烷二醇、1,14-十四烷二醇、1,2-十四烷二醇、1,16-十六烷二醇、1,2-十六烷二醇、2-甲基-2,4-戊烷二醇、3-甲基-1,5-戊烷二醇、2-甲基-2-丙基-1,3-丙烷二醇、2,4-二甲基-2,4-二甲基庚烷二醇、2,2-二乙基-1,3-丙烷二醇、2,2,4-三甲基-1,3-戊烷二醇、二羥甲基辛烷、2-乙基-1,3-己烷二醇、2,5-二甲基-2,5-己烷二醇、2-
甲基-1,8-辛烷二醇、2-丁基-2-乙基-1,3-丙烷二醇、2,4-二乙基-1,5-戊烷二醇、1,2-環己烷二醇、1,4-環己烷二醇、1,4-環己烷二甲醇、1,2-環庚烷二醇、三環癸烷二甲醇、氫化兒茶酚、氫化間苯二酚、氫化氫醌、二乙二醇、聚乙二醇、聚丙二醇等聚烷二醇、聚酯多元醇等。
該等中以乙二醇、丙二醇、二乙二醇、聚乙二醇、聚烷二醇較佳。
2元醇之分子量必須未達2萬,分子量為2萬以上時,變得難以均勻分散於分散介質中,因作為固體析出等之影響而難以作為漿料處理。且,例如使用聚乙二醇等聚合物作為2元醇時,分子量係使用重量平均分子量,其重量平均分子量必須未達2萬,較好為1萬以下,更好為5000以下。若在該重量平均分子量之範圍,則可充分發揮於分散介質中之均一分散、抑制含有多晶矽或TEOS等之與研磨對象物不同材料之層的研磨速度之優點。又,上述聚合物之重量平均分子量可藉由凝膠透過層析法(GPC法)進行測定。
研磨用組成物中之前述2元醇之含量較好為0.0001重量%以上,更好為0.0005重量%以上,又更好為0.001重量%以上。隨著前述2元醇之含量變多,而有進一步抑制含有多晶矽或TEOS等之與研磨對象物不同材料之層的研磨速度之優點。
且,研磨用組成物中之前述2元醇之含量較好為10重量%以下,更好為5重量%以下,又更好為1重量%以
下。隨著前述2元醇之含量變少,而有可避免研磨粒凝聚之優點。
本發明之研磨用組成物之pH為6以下。由於pH為鹼性時,多晶矽或TEOS會開始溶解,故抑制使用研磨用組成物之多晶矽或TEOS等之研磨速度變得困難。此外,超過pH6時,氮化矽之Zeta電位轉成負值側,使用Zeta電位為負值的研磨粒以高速度研磨氮化矽亦變得困難。基於進一步提高研磨用組成物對氮化矽之研磨速度方面而言,研磨用組成物之pH值較好為5以下,更好為4.5以下,又更好為4以下。
研磨用組成物之pH值又較好為1.5以上,更好為1.75以上,又更好為2以上。隨著研磨用組成物之pH變高,可進一步抑制圖型晶圓上之多晶矽或TEOS等之研磨速度。
為了將研磨用組成物之pH調整為期望之值,本發明之研磨用組成物包含pH調整劑。pH調整劑可使用如下述之酸或螯合劑。
酸列舉為例如甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸、肉荳蔻酸、棕櫚酸、十七烷酸(margaric acid)、硬脂酸、油酸、亞油酸、亞麻酸、花生酸、二十二碳六烯酸(docosahexaenoic acid)、二十碳五烯酸(eicosapentaenoic acid)、乳酸、
蘋果酸、檸檬酸、苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、水楊酸、沒食子酸、苯六甲酸(mellitic acid)、桂皮酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、富馬酸、馬來酸、烏頭酸(aconitic acid)、胺基酸、硝基羧酸之羧酸或甲烷磺酸、乙烷磺酸、苯磺酸、對-甲苯磺酸、10-樟腦磺酸、羥乙基磺酸、牛磺酸(taurine)等磺酸。另列舉碳酸、鹽酸、硝酸、磷酸、次磷酸、亞磷酸、膦酸、硫酸、硼酸、氫氟酸、原磷酸、焦磷酸、聚磷酸、偏磷酸、六偏磷酸等無機酸。
螯合劑舉例有聚胺、聚膦酸、聚胺基羧酸、聚胺基膦酸等。
該等pH調整劑可單獨使用亦可混合2種以上使用。該等pH調整劑中以硝酸、磷酸、檸檬酸、馬來酸較佳。
pH調整劑之添加量並無特別限制,只要適宜選擇可成為上述pH範圍之添加量即可。
本發明之研磨用組成物使用有用以使通常各成分分散或溶解之分散介質或溶劑。分散介質或溶劑可考慮有機溶劑、水,但其中以包含水較佳。就阻礙其他成分作用之觀點而言,較好為儘可能不含雜質之水。具體而言,較好為利用離子交換樹脂去除雜質離子後通過過濾器去除異物之純水或超純水、或蒸餾水。
本發明之研磨用組成物亦可視需要進一步含有表面固定有有機酸之二氧化矽以外之研磨粒、錯化劑、金屬防腐蝕劑、防腐劑、防黴劑、氧化劑、還原劑、界面活性劑等其他成分。以下針對研磨粒、氧化劑、防腐劑、防黴劑加以說明。
本發明中使用之表面固定有有機酸之二氧化矽以外之研磨粒可為無機粒子、有機粒子及有機無機複合粒子之任一種。無機粒子之具體例列舉為例如由氧化鋁、氧化鈰、氧化鈦等之金屬氧化物所成之粒子,以及氮化矽粒子、碳化矽粒子、氮化硼粒子。有機粒子之具體例列舉為例如聚甲基丙烯酸甲酯(PMMA)粒子。該研磨粒可單獨使用或混合2種以上使用。另外,該研磨粒可使用市售品亦可使用合成品。
研磨用組成物中所含氧化劑具有使研磨對象物的表面氧化之作用,並提高研磨用組成物對研磨對象物之研磨速度。
可使用之氧化劑為例如過氧化物。過氧化物之具體例列舉為過氧化氫、過乙酸、過碳酸鹽、過氧化尿素及過氯酸、以及過硫酸鈉、過硫酸鉀、過硫酸銨等過硫酸鹽。該
等氧化劑可單獨使用亦可混合2種以上使用。其中以過硫酸鹽及過氧化氫較佳,最好為過氧化氫。
研磨用組成物中之氧化劑含量較好為0.1g/L以上,更好為1g/L以上,又更好為3g/L以上。隨著氧化劑之含量變多,更提高研磨用組成物對研磨對象物之研磨速度。
研磨用組成物中之氧化劑含量較好為200g/L以下,更好為100g/L以下,又更好為40g/L以下。隨著氧化劑之含量變少,除了可抑制研磨用組成物之材料成本以外,亦可減輕研磨使用後之研磨用組成物之處理、亦即廢液處理之負荷。此外,亦可減少因氧化劑引起研磨對象物表面之過度氧化之虞。
本發明中使用之防腐劑及防黴劑列舉為例如2-甲基-4-異噻唑啉-3-酮或5-氯-2-甲基-4-異噻唑啉-3-酮等之異噻唑啉系防腐劑、對-羥基苯甲酸酯類、及苯氧基乙醇等。該等防腐劑及防黴劑可單獨使用亦可混合2種以上使用。
本發明之研磨用組成物之製造方法並無特別限制,例如可使表面固定有有機酸之二氧化矽、分子量未達2萬之2元醇、pH調整劑、及視需要之其他成分予以攪拌混合。
混合各成分時之溫度並無特別限制,較好為10~40℃,為了提高溶解速度亦可進行加熱。
本發明之被研磨材料並無特別限制,列舉為例如含有碳化矽、碳化硼等之金屬碳化物、氮化矽、氮化硼、氮化鎵、氮化鈦、氮化鋰等之金屬氮化物、或者該等之複合材料等之研磨對象物之被研磨材料。該等研磨對象物可單獨使用或組合2種以上使用。又,研磨對象物可為單層構造亦可為2種以上之多層構造。多層構造之情況,各層可含相同材料,亦可含不同材料。
再者,本發明中之被研磨材料較好具有上述研磨對象物、及含有與前述研磨對象物不同材料之層。藉由使用本發明之研磨用組成物,研磨對象物與表面固定有有機酸之二氧化矽之親和性變高,含有多晶矽或TEOS等之與研磨對象物不同材料之層與表面固定有有機酸之二氧化矽之親和性變低。結果,藉由使用本發明之研磨用組成物,可一面抑制含有與研磨對象物不同材料之層的研磨速度,一面選擇性的、亦即以比含有與前述研磨對象物不同材料之層更高的研磨速度研磨研磨對象物。
為何以本發明之研磨用組成物可選擇性研磨研磨對象物之詳細理由並不清楚,但推測為以下之機制。
本發明之研磨用組成物中,藉由含有表面固定有有機酸之二氧化矽與分子量2萬以下之2元醇,仍維持表面固定有有機酸之二氧化矽表面之Zeta電位或親水性,使表面固定有有機酸之二氧化矽表面之羥基與2元醇相互作
用,且表面固定有有機酸之二氧化矽之羥基被部分地被覆。藉此,認為能藉由二氧化矽之羥基之相互作用被研磨之含有多晶矽或TEOS等之與研磨對象物不同材料之層與表面固定有有機酸之二氧化矽的親和性變低。結果,一面維持了研磨對象物與表面固定有有機酸之二氧化矽之親和性,一面降低與研磨對象物不同之材料與表面固定有有機酸之二氧化矽之親和性,故認為可抑制多晶矽、TEOS等之研磨速度,且選擇性地以高速研磨氮化矽等之研磨對象物。使用超過2元之多元醇時,源自多元醇之羥基過多,反而提高對多結晶矽等之親和性,使多結晶矽等之研磨速度之抑制變得不充分。又,上述機制係推測所得者,本發明並不受上述機制之任何限制。
與前述研磨對象物不同之材料的例列舉為多晶矽、單晶矽、原矽酸四乙酯(TEOS)、矽氧化物等。該等材料可單獨使用或以2種以上之組合使用。又,含有與研磨對象物不同材料之層可為單層構造亦可為2種以上之多層構造。多層構造時,各層可含相同材料,亦可含不同材料。
該等中,就更有效地獲得本發明效果之觀點而言,研磨對象物較好包含氮化矽,含有與前述研磨對象物不同材料之層較好包含多晶矽及原矽酸四乙酯之至少一種材料。
如上述,本發明之研磨用組成物係較好地用於具有研磨對象物與含有與前述研磨對象物不同材料之層的被研磨
材料之研磨。據此,本發明之第二目的係研磨方法,其係使用本發明之研磨用組成物研磨具有研磨對象物、與含有與前述研磨對象物不同之材料的層之被研磨材料。此外,本發明之第三目的係基板製造方法,係包含以前述研磨方法研磨具有研磨對象物、及與前述研磨對象物不同之材料的被研磨材料之研磨步驟。
使用本發明之研磨用組成物研磨具有研磨對象物、與含有與前述研磨對象物不同之材料的層之被研磨材料時,可使用一般金屬研磨所用之裝置或條件進行。一般之研磨裝置有單面研磨裝置或雙面研磨裝置。單面研磨裝置係使用稱為載具之保持具保持基板,邊自上方供給研磨用組成物,邊將貼附有研磨墊之壓盤壓抵於基板之對向面並使壓盤旋轉,藉此研磨被研磨材料之單面。此時,係藉由利用研磨墊及研磨用組成物與被研磨材料之摩擦的物理作用,以及研磨用組成物對被研磨材料所致之化學作用進行研磨。前述研磨墊可無特別限制地使用不織布、聚胺基甲酸酯、麂皮等之多孔質體。研磨墊較好施以加工以使研磨液能積存。
本發明之研磨方法中之研磨條件列舉為研磨荷重、壓盤轉數、載體轉數、研磨用組成物之流量、研磨時間。該等研磨條件並無特別限制,例如研磨荷重較好為基板之每單位面積為0.1psi以上且10psi以下,更好為0.5psi以上且8.0psi以下,又更好為1.0psi以上且6.0psi以下。一般荷重愈高則因研磨粒造成之摩擦力愈高,為了提高機械之
加工力故提高研磨速度。若為該範圍,則可發揮充分之研磨速度,可抑制因荷重造成之基板破損、或表面發生損傷之缺陷。壓盤轉數及載體轉數較好為10~500rpm。研磨用組成物之供給量只要為可被覆被研磨材料之基盤整體之供給量即可,且只要依據基板大小等之條件調整即可。
本發明之研磨用組成物可為一液型,亦可為以二液型為代表之多液型。且,本發明之研磨用組成物亦可使用水等稀釋液,將研磨用組成物之原液稀釋成例如10倍以上而調整。
本發明之研磨用組成物亦可使用於上述被研磨材料以外之研磨。該等被研磨材料之例列舉為形成於基板上之玻璃等之無機絕緣層、含有Al、Cu、Ti、W、Ta等作為主成分之層、光罩‧透鏡‧稜鏡等之光學玻璃、ITO等之無機導電層、以玻璃及結晶質材料構成之光積體電路‧光開關元件‧光波導、光纖之端面、閃爍計(scintillator)等之光學用單晶、固體雷射單晶、藍光雷射LED用藍寶石基板、GaP、GaAs等之光半導體單晶、磁碟用玻璃基板、磁頭等。
使用以下實施例及比較例更詳細說明本發明。但,本發明之技術範圍並非僅限制於以下實施例。
研磨用組成物係以表2所示之組成,在水中混合研磨粒、2元醇及pH調整劑而獲得(混合溫度約25℃,混合時間:約10分鐘)。研磨用組成物之pH係以pH計確認。
又,表2所示之研磨粒、2元醇、多元醇及被研磨材料之種類係如下表1。
又,表2之研磨速度(圖型晶圓)欄係顯示測定研磨上述圖型晶圓時之下層的多晶矽或TEOS之研磨速度之結果。
保存安定性係以使研磨用組成物在60℃保存一週者,與在25℃保存一週者研磨Poly、SiN、TEOS,藉由確認研磨率之變化加以評價。而且研磨率之變化收斂在10%以內時為保存安定性良好,故記載為○。且研磨率之變化未收斂在10%以內時為保存安定性差,故記載為×。再者因研磨粒之沉降、或2元醇作為固體析出等之影響而對研磨評價帶來阻礙者記為××。
使用所得研磨用組成物,測定藉以下研磨條件研磨研磨對象物時之研磨速度。
‧研磨條件
研磨機:200mm用單面CMP研磨機
研磨墊:聚胺基甲酸酯製之研磨墊
壓力:1.8psi
壓盤轉數:97rpm
載體轉數:92rpm
研磨用組成物之流量:200ml/min
研磨時間:1分鐘
研磨速度係由以下式計算。
研磨速度[Å/min]=研磨1分鐘時之膜厚變化量
膜厚測定器:光干涉式膜厚測定裝置
研磨速度之測定結果示於下表2。
如由上述表2之研磨速度(空白晶圓)之結果可知,使用實施例1~6之本發明研磨用組成物時,研磨對象物的氮化矽之研磨速度較高。且,可知可抑制多晶矽或原矽酸四乙酯之研磨速度。此亦可由研磨速度(圖型晶圓)之結果亦獲得支持。另外,實施例之研磨用組成物之保存安定性亦良好。
另一方面,比較例1、比較例3、比較例6、及比較例8~9之研磨用組成物,對多晶矽或TEOS之研磨速度之抑制不充分。比較例8~9之研磨用組成物對研磨對象物的氮化矽之研磨速度本身降低。使用超過2元之多元醇的聚乙烯醇之比較例2,多晶矽及TEOS之研磨速度之抑制亦不充分。且,比較例4~5之研磨用組成物中,2元醇作為固體析出,故無法進行研磨速度之評價。再者比較例7之研磨用組成物因引起研磨粒沉降,故無法進行研磨速度之評價。
又,本申請案係基於2012年11月15日申請之日本專利申請案編號第2012-251521號,其揭示內容全文併入本文供參考。
Claims (9)
- 一種研磨用組成物,其係包含於表面固定有有機酸之二氧化矽、分子量未達2萬之2元醇、與pH調整劑,且pH為6以下。
- 如請求項1之研磨用組成物,其中前述有機酸為磺酸或羧酸。
- 如請求項1或2之研磨用組成物,其中前述2元醇係以下述化學式(1)表示之化合物,
- 如請求項1~3中任一項之研磨用組成物,其中前述2元醇之分子量為5000以下。
- 如請求項1~4中任一項之研磨用組成物,其係用於研磨具有研磨對象物、及含有與前述研磨對象物不同之材料的層之被研磨材料。
- 如請求項5之研磨用組成物,其中前述研磨對象物為氮化矽,且含有與前述研磨對象物不同之材料的層為含有多晶矽及原矽酸四乙酯之至少一者。
- 如請求項1~6中任一項之研磨用組成物,其中前 述之於表面固定有有機酸之二氧化矽的含量為0.005重量%以上且1重量%以下。
- 一種研磨方法,其係包含使用如請求項1~7中任一項之研磨用組成物研磨具有研磨對象物及含有與前述研磨對象物不同之材料的層之被研磨材料之步驟。
- 一種基板之製造方法,其係包含以如請求項8之研磨方法研磨具有研磨對象物及與前述研磨對象物不同之材料之被研磨材料之步驟。
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