TWI814030B - 研磨用組成物、研磨方法、及基板之製造方法 - Google Patents
研磨用組成物、研磨方法、及基板之製造方法 Download PDFInfo
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- TWI814030B TWI814030B TW110125539A TW110125539A TWI814030B TW I814030 B TWI814030 B TW I814030B TW 110125539 A TW110125539 A TW 110125539A TW 110125539 A TW110125539 A TW 110125539A TW I814030 B TWI814030 B TW I814030B
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- Taiwan
- Prior art keywords
- polishing
- silicon
- acid
- polishing composition
- abrasive grains
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 140
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims description 22
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- 229910052710 silicon Inorganic materials 0.000 claims abstract description 50
- 239000010703 silicon Substances 0.000 claims abstract description 50
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- 238000000227 grinding Methods 0.000 claims abstract description 27
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- 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
-
- 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
- C09K3/1409—Abrasive particles per se
-
- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/7684—Smoothing; Planarisation
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28035—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本發明提供可以更高研磨速度研磨單體矽之研磨用組成物。
本發明之研磨用組成物係於研磨包含單體矽與單體矽以外之含矽化合物之研磨對象物之用途所使用之研磨用組成物,其包含研磨粒及分散介質,前述研磨粒之每單位表面積之矽醇基數為超過0個/nm2且2.0個/nm2以下。
Description
本發明係關於研磨用組成物。
近年來,隨著LSI(Large Scale Integration,大型積體)之高積體化、高性能化而開發新的微細加工技術。化學機械研磨(chemical mechanical polishing;CMP)法亦為其一,係於LSI製造步驟尤其是多層配線形成步驟之層間絕緣膜之平坦化、金屬栓柱形成、嵌埋配線(鑲嵌配線)形成中被頻繁利用之技術。
該CMP已應用於半導體製造中之各步驟,作為其一樣態,舉例為應用於例如電晶體製作中之閘極形成步驟。製作電晶體時,係研磨矽、多晶矽(polysilicon)或矽氮化物(氮化矽)之含Si材料,因電晶體之構造,而要求控制各含Si材料之研磨速率。
例如於日本特開2013-41992號公報、國際公開第2008/105223號(相當於美國專利申請公開第2010/0001229號說明書)及日本特開2006-344786號公報中,揭示有以包含研磨粒、界面活性劑等之研磨劑研磨多
晶矽之技術。
然而,上述專利文獻中記載之研磨用組成物對多晶矽等之單體矽之研磨速度提高並不充分,而要求進一步改善。
因此,本發明之目的在於提供可以更高研磨速度研磨單體矽之研磨用組成物。
為解決上述課題,本發明人重複積極研究。其結果,發現藉由於研磨用組成物中所含之研磨粒之每單位表面積之矽醇基數落於特定範圍之研磨用組成物可解決上述課題。因此,基於上述見解而完成本發明。
亦即,本發明係一種研磨用組成物,其係於研磨包含單體矽與單體矽以外之含矽化合物之研磨對象物之用途所使用之研磨用組成物,其包含研磨粒及分散介質,前述研磨粒之每單位表面積之矽醇基數為超過0個/nm2且2.0個/nm2以下。
本發明係一種研磨用組成物,其係於研磨包含單體矽與單體矽以外之含矽化合物之研磨對象物之用途所使用之研磨用組成物,其包含研磨粒及分散介質,前述研磨粒之每單位表面積之矽醇基數為超過0個/nm2且2.0個/nm2以下。具有此等構成之本發明之研磨用組成物可以更高研磨
速度研磨單體矽。
使用本發明之研磨用組成物時,可提高單體矽之研磨速度之詳細理由雖不明確,但認為係如下理由。又,本發明不限於下述者。
亦即,藉由使研磨粒之每單位表面積之矽醇基數(以下亦簡稱為矽醇基數)為超過0個/nm2且2.0個/nm2以下,可提高研磨粒表面之疏水性,且與同樣具有疏水性表面之單體矽之相互作用變強。其結果,認為可提高單體矽之研磨速度者。
以往,研磨粒表面之矽醇基數減少時,由於研磨粒彼此及/或研磨粒表面之結合更為強固,結果使研磨粒硬度變高,故不管研磨對象物之材料種類如何,均見到研磨速度之提高。
然而,本發明發現到藉由使研磨粒之每單位表面積之矽醇基數設為特定範圍,可使研磨粒表面之疏水性提高,使同樣具有疏水性表面之單體矽與研磨粒之相互作用變強,此係迄今未知之作用機制,並發現可解決上述問題者。此外,藉由使用本發明之研磨用組成物,可獲得提高單體矽之研磨速度,同時可維持或抑制單體矽以外之含矽化合物之研磨速度之效果,亦即亦可獲得提高單體矽之研磨速度相對於單體矽以外之含矽化合物之研磨速度之比(選擇比)之效果。
以下,詳細說明本發明。
〔研磨對象物〕
本發明之研磨對象物包含單體矽與單體矽以外之含矽化合物。作為單體矽之例,舉例為多晶矽(Poly Si)、單晶矽、無定型矽等。
作為單體矽以外之含矽化合物之例,舉例為例如氧化矽(SiO2)、氮化矽(SiN)、原矽酸四乙酯(TEOS)等。該等含矽化合物可單獨使用亦可組合2種以上使用。
其次,針對本發明之研磨用組成物之構成詳細說明。
〔研磨粒〕
研磨用組成物中所含之研磨粒具有機械研磨研磨對象物之作用,且提高研磨用組成物對研磨對象物之研磨速度。
本發明所使用之研磨粒若為具有矽醇基者則無特別限制。作為其具體例,舉例為例如由氧化矽、氧化鋁、氧化鋯、氧化鈦等之金屬氧化物所成之粒子。該研磨粒可單獨使用或混合2種以上或亦可為該等之複合物而使用。且,該研磨粒可使用市售品亦可使用合成品。
該等研磨粒中,較好為氧化矽,更好為發煙氧化矽、膠體氧化矽,最好為膠體氧化矽。膠體氧化矽之製造方法舉例為矽酸鈉法、溶膠-凝膠法,以任一製造方法製造之膠體氧化矽均可較好地使用作為本發明之研磨粒。然而,基於減低金屬雜質之觀點,較好藉由可以高純度製造之溶膠凝膠法製造之膠體氧化矽。
再者,研磨粒只要每單位表面積之矽醇基數滿足上述範圍,則亦可經表面修飾。其中最好為固定化有機酸之膠體氧化矽。有機酸對研磨用組成物中所含之膠體氧化矽之表面之固定化係例如藉由使有機酸之官能基化學鍵結於膠體氧化矽表面而進行。僅使膠體氧化矽與有機酸單純共存,無法發揮有機酸對膠體氧化矽之固定化。若將有機酸之一種的磺酸固定化於膠體氧化矽,則可以例如“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”Chem.Commun.246-247(2003)所記載之方法進行。具體而言,將3-巰基丙基三甲氧基矽烷等之具有硫醇基之矽烷偶合劑偶合於膠體氧化矽後,以過氧化氫使硫醇基氧化,可獲得於表面固定化磺酸之膠體氧化矽。或者,若將羧酸固定化於膠體氧化矽,則可藉由例如“Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”,Chemistry Letters,3,228-229(2000)所記載之方法進行。具體而言,將包含光反應性2-硝基苄基酯之矽烷偶合劑偶合至膠體氧化矽後藉由光照射,可獲得於表面固定化有羧酸之膠體氧化矽。
本發明之研磨用組成物中所含之研磨粒中,研磨粒之每單位表面積之矽醇基數為超過0個/nm2且2.0個/nm2以下之範圍。研磨粒表面不具有矽醇基時,亦即上述矽醇基數為每單位表面積0個/nm2時,研磨粒彼此凝集,而使單體矽之研磨速度降低。另一方面,超過2.0個/nm2時,研
磨粒表面之親水基數變多而使與研磨對象物之疏水性相互作用減低,故使單體矽之研磨速度降低。研磨粒之每單位表面積之矽醇基數較好為0.5個/nm2以上且2.0個/nm2以下。
研磨粒之每單位表面積之矽醇基數可藉由G.W.Sears之Analytical Chemistry,vol.28,No.12,1956,1982~1983中記載之使用中和滴定之Sears法算出。矽醇基數之計算式係由以下之式計算。
ρ:矽醇基數〔個/nm2〕
c:滴定所用之氫氧化鈉溶液濃度〔mol/L〕
a:pH4-9之氫氧化鈉溶液之滴加量〔ml〕
NA:亞佛加厥數(6.022×1023〔個/mol〕)
C:氧化矽質量〔g〕
S:BET比表面積〔nm2/g〕
研磨粒之每單位表面積之矽醇基數可藉由選擇研磨粒之製造方法而控制。
研磨粒之平均二次粒徑之下限較好為5nm以上,更好為7nm以上,進而較好為10nm以上。且,研磨粒之平均二次粒徑之上限較好為500nm以下,更好為300nm以下,又更好為200nm以下。若為此等範圍,可提高研磨用組成物對單體矽之研磨速度。
又,可更抑制使用研磨用組成物研磨後之研磨對象物
表面產生凹陷。又,研磨粒之平均二次粒徑可藉由例如動態光散射法算出。
研磨用組成物中之研磨粒含量之下限較好為0.002質量%以上,更好為0.02質量%以上,又更好為0.1質量%以上。又,研磨用組成物中之研磨粒含量之上限較好為10質量%以下,更好為8質量%以下,又更好5質量%以下。若為此等範圍,可抑制成本,獲得高的研磨速度且可有效地加工。
〔水〕
本發明之研磨用組成物包含用以分散各成分之分散介質。作為分散介質較好為水。基於抑制阻礙其他成分作用之觀點,較好為儘可能不含雜質之水。具體而言,較好為以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。
〔研磨用組成物之pH〕
本發明之研磨用組成物之pH並未特別限制,在廣範圍之pH範圍內亦可發揮提高單體矽之研磨速度之效果。然而,基於研磨粒之分散安定性之觀點,pH之下限較好為pH1.0以上,更好為pH2.0以上。且,pH之上限較好為pH12以下,更好為pH10.5以下。
該pH可藉由適量添加pH調節劑而調整。用以將研磨用組成物之pH調整至期望值所必要使用之pH調整劑
可為酸及鹼之任一者,且亦可為無機化合物及有機化合物之任一者。酸之具體例舉例為例如硫酸、硝酸、硼酸、碳酸、次磷酸、亞磷酸及磷酸等之無機酸;甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正戊酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸及乳酸等之羧酸,以及甲烷磺酸、乙烷磺酸及羥乙基磺酸等之有機硫酸,植酸、羥基亞乙基二膦酸等之有機磷系之酸等之有機酸等。鹼之具體例舉例為氫氧化鉀等之鹼金屬之氫氧化物、氨、乙二胺及哌啶等之胺,以及四甲基銨及四乙基銨等之4級銨鹽。該等pH調節劑可單獨使用亦可混合2種以上使用。
〔其他成分〕
本發明之研磨用組成物根據需要亦可進而含有氧化劑、金屬防腐蝕劑、防腐劑、防黴劑、水溶性高分子、用以溶解難溶性有機物之有機溶劑等之其他成分。以下針對較佳之其他成分的氧化劑、金屬防腐蝕劑、防腐劑及防黴劑加以說明。
〔氧化劑〕
可添加於研磨用組成物之氧化劑具有使研磨對象物之
表面氧化之作用,且提高研磨用組成物對研磨對象物之研磨速度。
可使用之氧化劑舉例為過氧化氫、過氧化鈉、過氧化鋇、臭氧水、銀(II)鹽、鐵(III)鹽、過錳酸、鉻酸、重鉻酸、過氧代二硫酸、過氧磷酸、過氧硫酸、過氧硼酸、過甲酸、過乙酸、過苯甲酸、過鄰苯二甲酸、次氯酸、次溴酸、次碘酸、氯酸、亞氯酸、過氯酸、溴酸、碘酸、過碘酸、過硫酸、二氯異氰尿酸及該等之鹽等。該等氧化劑可單獨使用或可混合2種以上使用。
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,進而較好為3g/L以上。隨著氧化劑含量變多,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,進而較好為40g/L以下。隨著氧化劑含量減少,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。又,亦可見到因氧化劑引起研磨對象物表面之過度氧化。
〔金屬防腐蝕劑〕
藉由於研磨用組成物中添加金屬防腐蝕劑,可更抑制使用研磨用組成物研磨之配線邊緣產生凹陷。且,可更抑制使用研磨用組成物研磨後之研磨對象物表面產生凹陷。
可使用之金屬防腐蝕劑並未特別限制,較好為雜環式化合物或界面活性劑。雜環式化合物中之雜環員數並未特
別限制。且,雜環式化合物可為單環化合物,亦可為具有縮合環之多環化合物。該金屬防腐蝕劑可單獨使用或可混合2種以上使用。且該金屬防腐蝕劑可使用市售品亦可使用合成品。
可作為金屬防腐劑使用之雜環化合物之具體例舉例為例如吡咯化合物、吡唑化合物、咪唑化合物、三唑化合物、四唑化合物、吡啶化合物、哌啶化合物、嗒嗪化合物、吡啶化合物、吲哚嗪化合物、吲哚化合物、異吲哚化合物、吲唑化合物、嘌呤化合物、喹嗪化合物、喹啉化合物、異喹啉化合物、萘啶化合物、酞嗪化合物、喹喔啉化合物、喹唑啉化合物、噌啉化合物、喋啶化合物、噻唑化合物、異噻唑化合物、噁唑化合物、異噁唑化合物、呋咱化合物等之含氮雜環化合物。
〔防腐劑及防黴劑〕
本發明所用之防腐劑及防黴劑舉例為例如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。
〔研磨用組成物之製造方法〕
本發明之研磨用組成物之製造方法並未特別限制,例如可藉由將研磨粒及根據需要之其他成分於水中攪拌混合而得。
混合各成分時之溫度並未特別限制,較好為10~40℃,為了提高溶解速度亦可加熱。且混合時間亦未特別限制。
〔研磨方法及基板之製造方法〕
如上述,本發明之研磨用組成物尤其較好地使用於包含單體矽與單體矽以外之含矽化合物之研磨對象物之研磨。因此,本發明提供以本發明之研磨用組成物研磨包含單體矽與單體矽以外之含矽化合物之研磨對象物之研磨方法。又,本發明提供基板之製造方法,其包含以前述研磨方法研磨包含單體矽與單體矽以外之含矽化合物之研磨對象物之步驟。
作為研磨裝置,可使用安裝有保持具有研磨對象物之基板等之固持器與可變更轉數之馬達等之具有可貼附研磨墊(研磨布)之研磨壓盤之一般研磨裝置。
作為前述研磨墊,可無特別限制地使用一般不織布、聚胺基甲酸酯、及多孔質氟樹脂等。研磨墊上較好施以可積存研磨液之槽加工。
研磨條件亦未特別限制,例如研磨壓盤之旋轉速度較好為10~500rpm,施加於具有研磨對象物之基板之壓力(研磨壓力)較好為0.5~10psi。對研磨墊供給研磨用組成物之方法亦未特別限制,例如可採用泵等連續供給之方法。其供給量並未限制,較好研磨墊表面總是由本發明之研磨用組成物覆蓋。
研磨結束後,使基板於流水中洗淨,藉由旋轉乾燥器
等將附著於基板上之水滴甩落並乾燥,藉此獲得具有含有金屬或含矽材料之層之基板。
〔實施例〕
本發明將使用以下實施例及比較例進一步詳細說明。惟,本發明之技術範圍不僅限制於以下之實施例。
又,研磨粒之每單位表面積之矽醇基數(單位:個/nm2)係藉由以下之測定方法或計算方法,測定或算出各參數後,藉由下述方法算出。且研磨粒之平均二次粒徑係以動態光散射式之粒徑測定裝置測定。
<矽醇基數之算出方法>
研磨粒之每單位表面積之矽醇基數可藉由G.W.Sears之Analytical Chemistry,vol.28,No.12,1956,1982~1983中記載之使用中和滴定之Sears法算出。矽醇基數之計算式係由以下之式計算。
ρ:矽醇基數〔個/nm2〕
c:滴定所用之氫氧化鈉溶液濃度〔mol/L〕
a:pH4-9之氫氧化鈉溶液之滴加量〔ml〕
NA:亞佛加厥數(6.022×1023〔個/mol〕)
C:氧化矽質量〔g〕
S:BET比表面積〔nm2/g〕
〔於pH4之研磨〕
(實施例1-1)
將作為研磨粒之矽醇基數為1.5個/nm2之膠體氧化矽(平均二次粒徑:67nm,以溶膠凝膠法合成)以成為0.1質量%之濃度之方式與水混合(混合溫度:25℃,混合時間:10分鐘),進而添加作為pH調整劑之硝酸調整pH,調製研磨用組成物。研磨用組成物之pH藉由pH計確認為4。
(實施例1-2)
除了將研磨用組成物中之研磨粒濃度變更為4質量%以外,與實施例1-1同樣調製研磨用組成物。
(實施例1-3)
將作為研磨粒之矽醇基數為1.6個/nm2之膠體氧化矽(以矽酸鈉法合成)以成為4質量%之濃度之方式與水混合(混合溫度:25℃,混合時間:10分鐘),進而添加作為pH調整劑之硝酸調整pH,調製研磨用組成物。研磨用組成物之pH藉由pH計確認為4。
(實施例1-4)
將作為研磨粒之矽醇基數為1.9個/nm2之發煙氧化矽以成為1質量%之濃度之方式與水混合(混合溫度:25
℃,混合時間:10分鐘),進而添加作為pH調整劑之硝酸調整pH,調製研磨用組成物。研磨用組成物之pH藉由pH計確認為4。
(比較例1-1)
除了使用矽醇基數為5.7個/nm2之膠體氧化矽(商品名:SS-3P,扶桑化學工業股份有限公司製,平均二次粒徑:70nm,以溶膠凝膠法合成者)作為研磨粒以外,與實施例1-1同樣,調製研磨用組成物。
(比較例1-2)
除了使用矽醇基數為5.7個/nm2之膠體氧化矽(商品名:SS-3P,扶桑化學工業股份有限公司製,平均二次粒徑:70nm,以溶膠凝膠法合成者)作為研磨粒以外,與實施例1-2同樣,調製研磨用組成物。
(比較例1-3)
除了使用不具有矽醇基之α-氧化鋁作為研磨粒以外,與實施例1-1同樣,調製研磨用組成物。
(比較例1-4)
除了使用不具有矽醇基之γ-氧化鋁作為研磨粒以外,與實施例1-1同樣,調製研磨用組成物。
(評價)
<研磨粒之真密度>
研磨粒之真密度係藉由下述式表示之比重瓶法計算。
Sg:研磨粒之真密度
Wa:比重瓶之質量
Wb:試料與比重瓶之質量
Wc:試料與乙醇與比重瓶之質量
Wd:乙醇與比重瓶之質量
Ld:乙醇之比重
<研磨速度>
研磨速度係由以下之式計算。
針對Poly Si、SiN及TEOS,藉由光干涉式膜厚測定裝置求得膜厚,將其差除以研磨時間而評價。
實施例1-1~1-4及比較例1-1~1-4之研磨用組成物之評價結果示於下述表1。又,表1~3中之選擇比之欄中,「Poly Si/TEOS」之欄中,顯示將Poly Si之研磨速度除以TEOS之研磨速度之值,「Poly Si/SiN」之欄中,顯示將Poly Si之研磨速度除以SiN之研磨速度之值。
如上述表1所示,實施例1-1~1-4之研磨用組成物相較於比較例1-1~1-4之研磨用組成物,可知更提高多晶矽(Poly Si)之研磨速度。且,實施例1-1及實施例1-2中,多晶矽(Poly Si)之研磨速度相對於TEOS之研磨速度之比(選擇比)相較於比較例1-1~1-4更為提高。
〔於pH7之研磨〕
(實施例2-1)
除了使用硝酸及氫氧化鉀作為pH調整劑,將研磨用組成物之pH調整至7以外,與實施例1-2同樣調製研磨用組成物。
(比較例2-1)
除了使用硝酸及氫氧化鉀作為pH調整劑,將研磨用組成物之pH調整至7以外,與比較例1-2同樣調製研磨用組成物。
實施例2-1及比較例2-1之研磨用組成物之評價結果示於下述表2。
如上述表2所示,實施例2-1之研磨用組成物相較於比較例2-1之研磨用組成物,可知更提高多晶矽(Poly Si)之研磨速度。且,實施例2-1中,多晶矽(Poly Si)之研磨速度相對於TEOS之研磨速度之比(選擇比)及多晶矽(Poly Si)之研磨速度相對於SiN之研磨速度之比(選擇比)相較於比較例2-1更為提高。
〔於pH10之研磨〕
(實施例3-1)
除了使用氫氧化鉀作為pH調整劑,將研磨用組成物之pH調整至10以外,與實施例1-2同樣調製研磨用組成物。
(比較例3-1)
除了使用氫氧化鉀作為pH調整劑,將研磨用組成物之pH調整至10以外,與比較例1-2同樣調製研磨用組成物。
實施例3-1及比較例3-1之研磨用組成物之評價結果示於下述表3。
如上述表3所示,實施例3-1之研磨用組成物中,多晶矽(Poly Si)之研磨速度相對於TEOS之研磨速度之比(選擇比)及多晶矽(Poly Si)之研磨速度相對於SiN之研磨速度之比(選擇比)相較於比較例3-1更為提高。
又,本申請案係基於2015年2月10日申請之日本專利申請第2015-024377號,其揭示內容藉由參考全體加以引用。
Claims (3)
- 一種研磨用組成物,係於研磨包含單體矽與單體矽以外之含矽化合物之研磨對象物之用途所使用之研磨用組成物,其包含研磨粒及分散介質,前述研磨粒為藉由溶膠凝膠法製造之膠體氧化矽,前述研磨粒之每單位表面積之矽醇基數為1.5個/nm2以上且2.0個/nm2以下,前述研磨粒的含量為0.1質量%以上4質量%以下。
- 一種研磨方法,係以如請求項1之研磨用組成物研磨包含單體矽與單體矽以外之含矽化合物之研磨對象物。
- 一種基板之製造方法,其包含以如請求項2之研磨方法研磨包含單體矽與單體矽以外之含矽化合物之研磨對象物之步驟。
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