TWI609948B - 硏磨用組成物 - Google Patents
硏磨用組成物 Download PDFInfo
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- TWI609948B TWI609948B TW102131287A TW102131287A TWI609948B TW I609948 B TWI609948 B TW I609948B TW 102131287 A TW102131287 A TW 102131287A TW 102131287 A TW102131287 A TW 102131287A TW I609948 B TWI609948 B TW I609948B
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- Prior art keywords
- polishing
- acid
- compound
- polishing composition
- indole
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- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960003080 taurine Drugs 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
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 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
- 150000003852 triazoles Chemical class 0.000 description 1
- BMCJATLPEJCACU-UHFFFAOYSA-N tricin Natural products COc1cc(OC)c(O)c(c1)C2=CC(=O)c3c(O)cc(O)cc3O2 BMCJATLPEJCACU-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
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- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C09G1/06—Other polishing compositions
- C09G1/14—Other polishing compositions based on non-waxy substances
- C09G1/18—Other polishing compositions based on non-waxy substances on other substances
-
- 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
- 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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
-
- 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]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係關於研磨用組成物。
近年來,隨著LSI之高積體化、高性能化已開發新的微細加工技術。化學機械研磨(以下亦簡稱為「CMP」)法亦為其一種,係於LSI製造步驟,尤其是多層配線形成步驟中之層間絕緣膜之平坦化、金屬柱塞形成、埋入配線(鑲嵌(damascene))形成中頻繁被利用之技術。
CMP之一般方法係將研磨墊貼附於圓形之研磨壓盤上,以研磨劑浸漬研磨墊表面,且壓抵向基板之形成金屬膜之面,於自其背面施加特定壓力(以下亦簡稱為研磨壓力)之狀態下旋轉研磨壓盤,且藉由研磨劑與金屬膜之凸部之機械摩擦,而去除凸部之金屬膜者。
另一方面,配線之銅或銅合金等之下層係形成鉭、鉭合金、或鉭化合物等作為用於防止銅對層間絕緣膜中之擴散之障壁層。因此,埋入銅或銅合金之配線部分以外,有必要藉由CMP去除露出之障壁層。
為了形成各配線層,一般係首先遍及一段或多段進行
去除以鍍敷法等盛滿之多餘部分之配線材之金屬膜的CMP(以下亦稱為「金屬膜CMP」),接著,進行去除藉此露出於表面之障壁層之CMP(以下亦稱為「障壁層CMP」)。然而,藉由金屬膜CMP,會引起配線部過度的研磨之所謂凹陷,或進而引起腐蝕而成為問題。
為減輕該凹陷,在金屬膜CMP之後進行之障壁層CMP時,被要求調整金屬配線部之研磨速度與障壁金屬部之研磨速度,以形成最終之凹陷或腐蝕等之階差較少之配線層。亦即,障壁層CMP在障壁層或絕緣膜之研磨速度相較於金屬配線部相對較小時,由於配線部快速研磨而成之凹陷,或產生其結果之腐蝕,故障壁層或絕緣膜之研磨速度宜適度較大。此係因為除了具有提高障壁層CMP之處理量之優點以外,實際上因金屬膜CMP發生凹陷之情況較多,基於如上述之理由亦期望要求相對提高障壁層或絕緣膜之研磨速度。
且最近,已使用更低介電率且強度小的絕緣磨(低-k膜)。此係由於最尖端之裝置其配線間之距離較近,使用介電率高之絕緣膜時會有配線間發生電性不良之情況之故。此種低-k膜由於強度非常小,故CMP加工時會有過度研削之問題。因此,要求研磨障壁層時對被研磨膜可維持高的研磨速度,且充分抑制對於低-k膜之研磨速度之技術。
至於該技術,例如特開2008-243997號公報中揭示用以研磨半導體積體電路之障壁層之研磨液,且係含有抗靜
電劑與特定之陽離子系化合物之研磨液。且,特開2010-028078號公報、特開2010-028079號公報(國際公開第2009/104465號)、特開2010-028080號公報、及特開2010-028081號公報(美國專利申請公開第2011/081780號說明書)中揭示含有二氧化矽粒子、有機酸、重量平均分子量為5萬以上100萬以下之水溶性高分子之研磨液。
然而,上述專利文獻中記載之研磨液對於障壁層及絕緣膜層之高研磨速度之維持,以及低介電率材料之研磨速度之抑制依然不足,而要求進一步改良。且,特開2010-028078號公報、特開2010-028079號公報(國際公開第2009/104465號)、特開2010-028080號公報、及特開2010-028081號公報(美國專利申請公開第2011/081780號說明書)中記載之研磨液均有使用研磨粒時,研磨粒凝聚而變得難以研磨之問題。
因此本發明之目的係提供一種可充分地維持對障壁層及絕緣膜之高的研磨速度,可充分抑制低介電率材料之研磨速度,且可防止研磨粒之凝聚之研磨用組成物。
為解決上述課題,本發明人等重複積極研究。結果發現使用包含氧化劑與重量平均分子量為1000以下之非離子性化合物之研磨用組成物可解決上述課題。因此,基於上述見解,因而完成本發明。
亦即,本發明係研磨具有障壁層、金屬配線層、及絕
緣膜之研磨對象物之用途中使用之研磨用組成物,其包含氧化劑、重量平均分子量為1000以下之非離子性化合物之研磨用組成物。
本發明係研磨具有障壁層、金屬配線層、及絕緣膜之研磨對象物之用途中使用之研磨用組成物,且係包含氧化劑、重量平均分子量為1000以下之非離子性化合物之研磨用組成物。藉由成為該構成,可充分地維持對於障壁層及絕緣膜之高的研磨速度,可充分抑制低介電率材料之研磨速度,且可防止研磨粒之凝聚。
藉由使用本發明之研磨用組成物而獲得如上述效果之詳細理由雖尚不清楚,但認為由於本發明中使用之非離子性化合物之分子量較低,故不會形成具有高分子量之非離子性化合物程度之厚保護膜,不會使障壁層及絕緣膜之研磨速度下降,而可抑制低介電率材料之研磨速度者。另外,本發明之低分子量之非離子性化合物雖對於研磨粒之表面具有作用,但複數個研磨粒凝聚之作用較弱,故認為是可防止研磨粒之凝聚者。又,上述機制為推測者,本發明並不受上述機制之任何限制。
本發明之研磨對象物具有障壁層、金屬配線層、及絕緣膜,且視需要具有低介電率材料。
障壁層中所含之材料並無特別限制,列舉為例如鉭、鈦、鎢、鈷;金、銀、鉑、鈀、銠、釕、銦、鋨等貴金屬。該等金屬亦可以合金或金屬化合物之形態包含於障壁層中。較好為鉭或貴金屬。該等金屬可單獨使用亦可組合2種以上使用。
另外,金屬配線層中所含之金屬並無特別限制,列舉為例如銅、鋁、鉿、鈷、鎳、鈦、鎢等。該等金屬亦可以合金或金屬化合物之形態包含於金屬配線層中。較好為銅或銅合金。該等金屬可單獨使用或組合2種以上使用。
絕緣膜中所含之材料列舉為TEOS(四乙氧基矽烷)等。
至於低介電率材料,具體而言列舉為比介電率為3.5至2.0左右之一般簡稱為低-k者。例如,碳化氧化矽(SiOC)(例如,Applied Material公司製之Black Diamond(註冊商標)等)、含氟矽氧化物(SiOF)、有機聚合物等。
接著,針對本發明之研磨用組成物之構成加以詳細說明。
本發明之氧化劑之具體例列舉為過氧化氫、過乙酸、過碳酸、過氧化脲、過氯酸;過硫酸鈉、過硫酸鉀、過硫酸銨等之過硫酸鹽等。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(濃度)之下限較好為0.01重量%以上,更好為0.05重量%以上,又更好為0.1重量%以上。氧化劑之含量增多時,有提高研磨用組成物之研磨速度之優點。
且,研磨用組成物中之氧化劑含量(濃度)之上限較好為10重量%以下,更好為5重量%以下,又更好為3重量%以下。氧化劑之含量減少時,除了可抑制研磨用組成物之材料成本以外,亦具有可減輕研磨使用之研磨用組成誤之處理亦即廢液處理之負荷之優點。另外,亦具有不易因氧化劑而引起研磨對象物表面之過度氧化之優點。
本發明之非離子性化合物之重量平均分子量為1000以下。重量平均分子量超過1000時,發生研磨粒凝聚,且,低介電率材料之研磨速度抑制變得困難。該重量平均分子量較好為950以下,更好為900以下。
該重量平均分子量之下限並無特別限制。然而,就對低介電率材料之研磨速度抑制效果之觀點而言,較好為200以上,更好為300以上。
又,該重量平均分子量可以聚苯乙烯作為標準物質利用凝膠滲透層析儀(GPC)測定。
非離子性化合物之具體例列舉為例如聚氧伸丙基聚氧乙二醇、聚氧伸丙基聚氧伸乙基烷基醚、聚氧伸乙基烷基
醚、聚氧伸乙基烷基烯丙基醚、聚氧伸乙基聚氧伸丙基醚衍生物、聚氧伸丙基甘油醚、聚乙二醇、聚丙二醇、甲氧基聚乙二醇、乙炔系二醇之氧基伸乙基加成物等之醚型界面活性劑;山梨糖醇酐脂肪酸酯、甘油硼酸酯脂肪酸酯等之酯型界面活性劑;聚氧伸乙基烷基胺等之胺基醚型界面活性劑;聚氧伸乙基山梨糖醇酐脂肪酸酯、聚氧伸乙基甘油硼酸酯脂肪酸酯、聚氧伸乙基烷酯等之醚酯型界面活性劑;脂肪酸烷醇醯胺、聚氧伸乙基脂肪酸烷醇醯胺等之烷醇醯胺型界面活性劑;乙炔系二醇之氧基伸乙基加成物、聚乙烯基吡咯烷酮、聚丙烯醯胺、聚二甲基丙烯醯胺、聚乙烯醇、羧甲基纖維素、洋菜、卡德蘭多糖(curdlan)、普魯蘭多糖等多糖類、聚天門冬胺酸、聚穀胺酸、聚離胺酸、聚蘋果酸、聚醯胺酸、聚醯胺酸銨鹽、聚醯胺酸鈉鹽、聚乙醛酸等聚羧酸及其鹽等。上述非離子性化合物可單獨使用亦可混合2種以上使用。另外,上述非離子性化合物可使用市售品亦可使用合成品。
該等非離子性化合物中,就對於低介電率材料之研磨速度之抑制效果之觀點而言,以具有烷基醚鏈之化合物較佳,前述烷基醚鏈較好為以下述化學式(1)或(2)表示之構造。
[化1]-(CH2CH2O)n- ...(1) -(CH2CH2CH2O)m- ...(2)
前述化學式(1)中,n為1~23之整數,前述化學式(2)中,m為1~15之整數。
更具體而言,較好為聚氧伸丙基聚氧伸乙二醇、聚氧伸乙基烷基醚、聚乙二醇、聚丙二醇。
研磨用組成物中之非離子性化合物之含量下限較好為0.01g/L以上,更好為0.05g/L以上,又更好為0.1g/L以上。非離子性化合物之含量較多時,具有對於低介電率材料之研磨速度抑制效果高之優點。
且,研磨用組成物中之非離子性化合物之含量上限較好為15g/L以下,更好為10g/L以下,又更好為5g/L以下。伴隨非離子性化合物之含量變少時,具有容易抑制研磨粒凝聚之優點。
本發明之研磨用組成物較好含有水作為用以使各成分分散或溶解之分散介質或溶劑。就抑制阻礙其他成分之作用之觀點而言,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。
本發明之研磨用組成物亦可視需要進一步含有研磨粒、錯化劑、金屬防腐蝕劑、防腐劑、防黴劑、氧化劑、
還原劑、水溶性高分子、界面活性劑、用以使難溶性之有機物溶解之有機溶劑等其他成分。以下針對較佳之其他成分的研磨粒、錯化劑及金屬防腐蝕劑加以說明。
研磨組成物中所含之研磨粒具有對研磨對象物進行機械研磨之作用,且提高研磨用組成物對研磨對象物之研磨速度。
使用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二氧化矽、氧化鋁、氧化鈰、氧化鈦等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。
該等研磨粒中以二氧化矽粒子較佳,最好為膠體二氧化矽。
研磨粒亦可經表面修飾。通常之膠體二氧化矽由於在酸性條件下之Zeta電位值接近於零,故在酸性條件下二氧化矽粒子彼此間不會互相靜電排斥而容易引起凝聚。相對於此,即使在酸性條件下具有Zeta電位較大之負值之經表面修飾之研磨粒,在酸性條件下相互間強烈排斥而成良好分散之結果,提高了研磨用組成物之保存安定性。如此之表面修飾研磨粒可藉由例如使鋁、鈦或鋯等金屬或該
等之氧化物與研磨粒混合而摻雜於研磨粒之表面而獲得。
其中,最好為固定化有機酸之膠體二氧化矽。有機酸對研磨用組成物中所含之膠體二氧化矽表面之固定化係藉由使有機酸之官能基化學鍵結於膠體二氧化矽表面而進行。僅單使膠體二氧化矽與有機酸共存,無法發揮有機酸朝膠體二氧化矽之固定化。若使有機酸之一種的磺酸固定化於膠體二氧化矽上,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膠體二氧化矽上後,以過氧化氫使硫醇基氧化,藉此可獲得磺酸固定化於表面之膠體二氧化矽。或者,若使羧酸固定化於膠體二氧化矽上,則可藉例如”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)中所記載之方法進行。具體而言,在將含有光反應性2-硝基苄酯之矽烷偶合劑偶合於膠體二氧化矽後,藉由光照射,可獲得使羧酸固定化於表面之膠體二氧化矽。
研磨粒之平均一次粒徑之下限較好為5nm以上,更好為7nm以上,又更好為10nm以上。且,研磨粒之平均一次粒徑之上限較好為500nm以下,更好為100nm以下,又更好為70nm以下。若為該範圍,則研磨用組成物
對研磨對象物之研磨速度獲得提高,且,可進一步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,研磨粒之平均一次粒徑係採用基於以BET法測定之研磨粒之比表面積算出。
研磨用組成物中之研磨粒之含量下限較好為0.005重量%以上,更好為0.5重量%以上,又更好為1重量%以上,最好為3重量%以上。另外,研磨用組成物中之研磨粒之含量上限較好為50重量%以下,更好為30重量%以下,又更好為15重量%以下。若在該範圍,則可提高研磨對象物之研磨速度,且可抑制研磨用組成物之成本,可進一步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。
研磨用組成物中所含之錯化劑為具有化學性蝕刻研磨對象物之作用,且提高研磨用組成物對研磨對象物之研磨速度。
可使用之錯化劑之例列舉為例如無機酸或其鹽、有機酸或其鹽、腈化合物、胺基酸、及螯合劑等。該等錯化劑可單獨使用或混合2種以上使用。另外,該錯化劑可使用市售品亦可使用合成品。
無機酸之具體例列舉為例如鹽酸、硫酸、硝酸、碳酸、硼酸、四氟硼酸、次磷酸、亞磷酸、磷酸、焦磷酸等。
有機酸之具體例列舉為甲酸、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、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、乳酸、乙醇酸、甘油酸、苯甲酸、水楊酸等一元羧酸;草酸、丙二酸、琥珀酸、戊二酸、葡糖酸、己二酸、庚二酸、馬來酸、鄰苯二甲酸、富馬酸、蘋果酸、酒石酸、檸檬酸等多元羧酸等羧酸。另外,亦可使用甲烷磺酸、乙烷磺酸及羥乙磺酸等磺酸。
至於錯化劑,亦可使用前述無機酸或前述有機酸之鹽。尤其,使用弱酸與強鹼之鹽、強酸與弱鹼之鹽、或弱酸與弱鹼之鹽時,可期待pH之緩衝作用。該鹽之例列舉為例如氯化鉀、硫酸鈉、硝酸鉀、碳酸鉀、四氟硼酸鉀、焦磷酸鉀、草酸鉀、檸檬酸三鈉、(+)-酒石酸鉀、六氟磷酸鉀等。
腈化合物之具體例列舉為例如乙腈、胺基乙腈、丙腈、丁腈、異丁腈、苄腈、戊二腈、甲氧基乙腈等。
胺基酸之具體例列舉為甘胺酸、α-丙胺酸、β-丙胺酸、N-甲基甘胺酸、N,N-二甲基甘胺酸、2-胺基丁酸、正纈胺酸、纈胺酸、亮胺酸、正亮胺酸、異亮胺酸、苯基丙胺酸、脯胺酸、肌胺酸、鳥胺酸、離胺酸、牛磺酸、絲胺酸、蘇胺酸、高絲胺酸、酪胺酸、N,N-二羥乙基甘胺酸(bicine)、N-參羥甲基甲基甘胺酸(tricin)、3,5-二碘酪胺酸、β-(3,4-二羥基苯基)-丙胺酸、甲狀腺素(thyroxin)、4-羥基-脯胺酸、半胱胺酸、甲硫胺酸、乙硫胺酸、羊毛硫
胺酸(lanthionine)、胱硫醚(cystathionine)、胱胺酸、磺基丙胺酸(cysteic acid)、天門冬胺酸、穀胺酸、S-(羧基甲基)-半胱胺酸、4-胺基丁酸、天冬醯胺、穀醯胺、氮雜絲胺酸(azaserine)、精胺酸、刀豆胺酸(canavanine)、瓜胺酸、δ-羥基-離胺酸、肌酸、組胺酸、1-甲基組胺酸、3-甲基組胺酸及色胺酸等。
螯合劑之具體例列舉為氮基三乙酸、二伸乙基三胺五乙酸、乙二胺四乙酸、N,N,N-三亞甲基膦酸、乙二胺-N,N,N’,N’-四亞甲基磺酸、反式環己烷二胺四乙酸、1,2-二胺基丙烷四乙酸、二醇醚二胺四乙酸、乙二胺鄰羥基苯基乙酸、乙二胺二琥珀酸(SS體)、N-(2-羧酸根乙基)-L-天門冬胺酸、β-丙胺酸二乙酸、2-膦醯丁烷-1,2,4-三羧酸、1-羥基亞乙基-1,1-二膦酸、N,N’-雙(2-羥基苄基)乙二胺-N,N’-二乙酸、1,2-二羥基苯-4,6-二磺酸等。
該等中,較好為選自由無機酸或其鹽、羧酸或其鹽、及腈化合物所組成群組之至少1種,就與貴金屬化合物之錯合構造之安定性之觀點而言,更好為無機酸或其鹽。
研磨用組成物中之錯化劑含量(濃度)之下限由於即使少量即可發揮效果故沒有特別限制,但較好為0.001g/L以上,更好為0.01g/L以上,又更好為1g/L以上。且,本發明之研磨用組成物中之錯化劑含量(濃度)之上限較好為20g/L以下,更好為15g/L以下,又更好為10g/L以下。若在該範圍,則可更有效地獲得本發明之效果。
藉由於研磨用組成物中添加金屬防腐蝕劑,可進一步抑制因使用研磨用組成物研磨而在配線之側邊產生凹陷。另外,可進一步抑制使用研磨用組成物研磨後在研磨對象物之表面產生凹陷。
可使用之金屬防腐蝕劑並無特別限制,但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之員數並無特別限制。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或混合2種以上使用。另外,該金屬防腐蝕劑可使用市售品,亦可使用合成品。
可作為金屬防腐蝕劑使用之雜環化合物之具體例列舉為例如吡咯化合物、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、吡嗪化合物、吲哚嗪(indolizine)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(quinolizine)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、呋咱化合物等含氮雜環化合物。
若進一步列舉具體例,則吡唑化合物之例列舉為例如1H-吡唑、4-硝基-3-吡唑羧酸、3,5-吡唑羧酸、3-胺基-5-苯基吡唑、5-胺基-3-苯基吡唑、3,4,5-三溴吡唑、3-胺基
吡唑、3,5-二甲基吡唑、3,5-二甲基-1-羥基甲基吡唑、3-甲基吡唑、1-甲基吡唑、3-胺基-5-甲基吡唑、4-胺基-吡唑并[3,4-d]嘧啶、異嘌呤醇(allopurinol)、4-氯-1H-吡唑并[3,4-D]嘧啶、3,4-二羥基-6-甲基吡唑并(3,4-B)吡啶、6-甲基-1H-吡唑并[3,4-b]吡啶-3-胺等。
咪唑化合物之具體例列舉為例如咪唑、1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-異丙基咪唑、苯并咪唑、5,6-二甲基苯并咪唑、2-胺基苯并咪唑、2-氯苯并咪唑、2-甲基苯并咪唑、2-(1-羥基乙基)苯并咪唑、2-羥基苯并咪唑、2-苯基苯并咪唑、2,5-二甲基苯并咪唑、5-甲基苯并咪唑、5-硝基苯并咪唑、1H-嘌呤等。
三唑化合物之例列舉為例如1,2,3-三唑(1H-BTA)、1,2,4-三唑、1-甲基-1,2,4-三唑、甲基-1H-1,2,4-三唑-3-羧酸酯、1,2,4-三唑-3-羧酸、1,2,4-三唑-3-羧酸甲酯、1H-1,2,4-三唑-3-硫醇、3,5-二胺基-1H-1,2,4-三唑、3-胺基-1,2,4-三唑-5-硫醇、3-胺基-1H-1,2,4-三唑、3-胺基-5-苄基-4H-1,2,4-三唑、3-胺基-5-甲基-4H-1,2,4-三唑、3-硝基-1,2,4-三唑、3-溴-5-硝基-1,2,4-三唑、4-(1,2,4-三唑-1-基)苯酚、4-胺基-1,2,4-三唑、4-胺基-3,5-二丙基-4H-1,2,4-三唑、4-胺基-3,5-二甲基-4H-1,2,4-三唑、4-胺基-3,5-二庚基-4H-1,2,4-三唑、5-甲基-1,2,4-三唑-3,4-二胺、1H-苯并三唑、1-羥基苯并三唑、1-胺基苯并三唑、1-羧基苯并三唑、5-氯-1H-苯并三唑、5-硝基-1H-苯并三唑、5-羧基-
1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-(1’,2’-二羧基乙基)苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑等。
四唑化合物之例列舉為例如1H-四唑、5-甲基四唑、5-胺基四唑、及5-苯基四唑等。
吲唑化合物之例列舉為例如1H-吲唑、5-胺基-1H-吲唑、5-硝基-1H-吲唑、5-羥基-1H-吲唑、6-胺基-1H-吲唑、6-硝基-1H-吲唑、6-羥基-1H-吲唑、3-羧基-5-甲基-1H-吲唑等。
吲哚化合物之具體例列舉為1H-吲哚、1-甲基-1H-吲哚、2-甲基-1H-吲哚、3-甲基-1H-吲哚、4-甲基-1H-吲哚、5-甲基-1H-吲哚、6-甲基-1H-吲哚、7-甲基-1H-吲哚、4-胺基-1H-吲哚、5-胺基-1H-吲哚、6-胺基-1H-吲哚、7-胺基-1H-吲哚、4-羥基-1H-吲哚、5-羥基-1H-吲哚、6-羥基-1H-吲哚、7-羥基-1H-吲哚、4-甲氧基-1H-吲哚、5-甲氧基-1H-吲哚、6-甲氧基-1H-吲哚、7-甲氧基-1H-吲哚、4-氯-1H-吲哚、5-氯-1H-吲哚、6-氯-1H-吲哚、7-氯-1H-吲哚、4-羧基-1H-吲哚、5-羧基-1H-吲哚、6-羧基-1H-吲哚、7-羧基-1H-吲哚、4-硝基-1H-吲哚、5-硝基-1H-吲哚、6-硝基-1H-吲哚、7-硝基-1H-吲哚、4-腈基-1H-吲哚、5-腈基-1H-吲哚、6-腈基-1H-吲哚、7-腈基-1H-吲哚、2,5-二甲基-1H-吲哚、1,2-二甲基-1H-吲哚、1,3-二甲
基-1H-吲哚、2,3-二甲基-1H-吲哚、5-胺基-2,3-二甲基-1H-吲哚、7-乙基-1H-吲哚、5-(胺基甲基)吲哚、2-甲基-5-胺基-1H-吲哚、3-羥基甲基-1H-吲哚、6-異丙基-1H-吲哚、5-氯-2-甲基-1H-吲哚等。
該等中較佳之雜環化合物為三唑化合物,最好為1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑、1,2,3-三唑、及1,2,4-三唑。該等雜環化合物由於對研磨對象物表面之化學或物理之吸附力高,故可在研磨對象物之表面形成更堅固之保護膜。此在使用本發明之研磨用組成物研磨後對於提高研磨對象物之表面平坦性有利。
且,使用作為金屬防腐蝕劑之界面活性劑列舉為陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑。
陰離子性界面活性劑之例列舉為聚氧伸乙基烷基醚乙酸、聚氧伸乙基烷基硫酸酯、烷基硫酸酯、聚氧伸乙基烷基醚硫酸、烷基醚硫酸、烷基苯磺酸、烷基磷酸酯、聚氧伸乙基烷基磷酸酯、聚氧伸乙基磺基琥珀酸、烷基磺基琥珀酸、烷基萘磺酸、烷基二苯基醚二磺酸、及該等之鹽等。
陽離子性界面活性劑之例列舉為例如烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲基銨鹽、及烷基胺鹽等。
兩性界面活性劑之例列舉為例如烷基甜菜鹼及烷基氧化胺等。
該等中較佳之界面活性劑為聚氧伸乙基烷基醚乙酸、聚氧伸乙基烷基醚硫酸鹽、烷基醚硫酸鹽、及烷基苯磺酸鹽。該等界面活性劑由於對於研磨對象物表面之化學或物理性吸附力高,故可在研磨對性物表面形成更堅固之保護膜。此對於提高使用本發明之研磨用組成物研磨後提高研磨對象物之表面之平坦性有利。
研磨用組成物中之金屬防腐蝕劑含量之下限較好為0.001g/L以上,更好為0.005g/L以上,又更好為0.01g/L以上。另一方面,研磨用組成物中之金屬防腐蝕劑含量之上限較好為10g/L以下,更好為5g/L以下,又更好為2g/L以下。若為該範圍,則可提高使用研磨用組成物研磨後之研磨對象物之表面平坦性,另外,可提高利用研磨用組成物對研磨對象物之研磨速度。
本發明之研磨用組成物之pH之下限較好為3以上。隨著研磨用組成物之pH變大,可減少因研磨用組成物引起研磨對象物表面之過度蝕刻之虞。
另外,研磨用組成物之pH上限較好為10以下。隨著研磨用組成物之pH減小,可進一步抑制因使用研磨用組成物研磨而形成之配線之側邊產生凹陷。
研磨用組成物之pH亦可使用pH調整劑調整至期望
之值。使用之pH調整劑可為酸及鹼之任一種,且可為無機及有機化合物之任一種。又,pH調節劑可單獨使用或混合2種以上使用。且,使用具有pH調整功能者(例如各種酸等)作為上述各種添加劑時,該添加劑亦可作為pH調整劑之至少一部份加以利用。
本發明之研磨用組成物之製造方法並未特別限制,可藉由例如在水中攪拌混合氧化劑、非離子性化合物及視需要之其他成分而得。
混合各成分時之溫度並無特別限制,較好為10~40℃,亦可加熱以提高溶解速度。又,混合時間亦無特別限制。
如上述,本發明之研磨用組成物係較好地使用於具有障壁層、金屬配線層、及絕緣膜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具有障壁層、金屬配線層、及絕緣層之研磨對象物之研磨方法。另外,本發明提供包含以前述方法研磨具有障壁層、金屬配線層、及絕緣膜之研磨對象物之步驟之基板製造方法。
研磨裝置可使用安裝有保持具有研磨對象物之基板等之載具與可改變轉數之馬達等,且具有可貼附研磨墊(研磨布)之研磨壓盤之一般研磨裝置。
前述研磨墊可無特別限制的使用一般之不織布、聚胺基甲酸酯、及多孔質氟樹脂等。研磨墊較好施以可使研磨液積存之溝槽加工。
研磨條件亦無特別限制,例如研磨壓盤之轉數較好為10~500rpm,對具有研磨對象物之基板施加之壓力(研磨壓力)較好為0.5~10psi。將研磨用組成物供給於研磨墊之方法亦無特別限制,例如可採用泵等連續供給之方法。其供給量並無限制,但較好隨時以本發明之研磨用組成物覆蓋研磨墊表面。
研磨結束後,在水流中洗淨基板,以旋轉乾燥機等甩掉附著於基板上之水滴予以乾燥,而獲得具有障壁層、金屬配線層、及絕緣層之基板。
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。另外,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倍以上而調製。
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。
使作為研磨粒之膠體二氧化矽(約70nm之平均二次粒徑(平均一次粒徑35nm,會合度2)10重量%、作為氧化劑
之過氧化氫0.6重量%、作為錯化劑之羥乙磺酸4.2g/L、作為金屬防腐蝕劑之1H-BTA 1.2g/L、及下表2所示之非離子性化合物1.5g/L以分別成為前述濃度之方式在水中攪拌混合(混合溫度:約25℃,混合時間:約10分鐘),而調製研磨用組成物。組成物之pH係藉由添加氫氧化鉀(KOH)予以調整,且以pH計確認。且,非離子性化合物之重量平均分子量係以聚苯乙烯作為標準物質,藉由GPC(凝膠滲透層析儀)測定。
研磨對象物係使用使Ta膜、Ru膜、TEOS膜及Black Diamond(註冊商標,BDIIx)膜成膜於矽基板上而成之12吋晶圓。
測定使用所得研磨用組成物,以下述表1所示之研磨條件對研磨對象物之表面研磨60秒時之研磨速度。研磨速度係使用以直流4探針法為原理之薄片電阻測定器測定之研磨前後之各膜厚度差除以研磨時間而求得。
[表1]研磨裝置:CMP單面研磨裝置研磨墊:聚胺基甲酸酯製研磨壓力:1psi(約6.9kPa)研磨壓盤之轉數:80rpm漿料流量:300ml/min研磨時間:60秒
另外,針對組成物中研磨粒之分散安定性,在43℃之
恆溫恆濕器保管研磨用組成物2個月後(相當於在室溫(25℃)下保存6個月),以目視觀察研磨粒之分散安定性。
評價結果示於下述表2。表2中,○表示未發生研磨粒之凝聚,×表示發生研磨粒之凝聚。
如上述表2所示可知,本發明之研磨用組成物(實施例1~7)相較於比較例1及5之不含非離子性化物之研磨用組成物,作為障壁層使用之鉭及釕、及作為絕緣膜使用之TEOS之研磨速度不會大幅降低,且做為低介電率材料之Black Diamond(註冊商標)膜之研磨速度則降低。
另外,本發明之研磨用組成物(實施例1~7)不會產生研磨粒之凝聚,但含有重量平均分子量在本發明範圍外之非離子性化合物之比較例2~4及比較例6~7之研磨用組成物則發生研磨粒凝聚。尤其,使用數平均分子量為25000之羥乙基纖維素的比較例3及7中,研磨粒凝聚嚴重,為無法研磨者。
又,可知比較例4之研磨用組成物雖僅進行低介電率材料及絕緣膜之研磨,但不會使低介電率材料之研磨速度降低。
又,本申請案係基於2012年9月14日提出申請之日本專利申請案第2012-203014號,其揭示內容藉由參照而全文予以援用。
Claims (6)
- 一種研磨用組成物,其係研磨具有障壁層、金屬配線層及絕緣膜之研磨對象物之用途中使用之研磨用組成物,其包含氧化劑、重量平均分子量為1000以下之非離子性化合物、與選自由甲烷磺酸、乙烷磺酸及羥乙磺酸(isethionic acid)所成群之至少一種之錯化劑。
- 如請求項1之研磨用組成物,其中前述非離子性化合物係選自由聚氧伸乙基烷基醚、聚乙二醇及聚丙二醇所成群之至少一種。
- 如請求項1或2之研磨用組成物,其中前述研磨對象物進一步包含低介電材料。
- 如請求項1或2之研磨用組成物,其中前述障壁層包含鉭或貴金屬。
- 一種研磨方法,其係以如請求項1~4中任一項之研磨用組成物研磨具有障壁層與金屬配線層之研磨對象物。
- 一種基板之製造方法,其包含以如請求項5之研磨方法研磨具有障壁層與金屬配線層之研磨對象物之步驟。
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EP3124569A4 (en) * | 2014-03-28 | 2017-03-15 | Fujimi Incorporated | Polishing composition, and polishing method using same |
WO2016031485A1 (ja) * | 2014-08-29 | 2016-03-03 | 株式会社フジミインコーポレーテッド | 研磨用組成物および研磨用組成物の製造方法 |
US9528030B1 (en) * | 2015-10-21 | 2016-12-27 | Cabot Microelectronics Corporation | Cobalt inhibitor combination for improved dishing |
KR102544643B1 (ko) * | 2015-12-23 | 2023-06-19 | 솔브레인 주식회사 | 연마 슬러리 조성물 및 이를 이용한 연마방법 |
EP3433327B1 (en) * | 2016-03-22 | 2020-05-20 | Basf Se | Use of a chemical mechanical polishing (cmp) composition for polishing of cobalt and / or cobalt alloy comprising substrates |
US10703936B2 (en) | 2016-03-30 | 2020-07-07 | Fujimi Incorporated | Polishing composition |
KR102405560B1 (ko) * | 2017-02-28 | 2022-06-07 | 후지필름 가부시키가이샤 | 연마액, 연마액의 제조 방법, 연마액 원액, 연마액 원액 수용체, 화학적 기계적 연마 방법 |
WO2018179064A1 (ja) | 2017-03-27 | 2018-10-04 | 日立化成株式会社 | スラリ及び研磨方法 |
WO2018179061A1 (ja) * | 2017-03-27 | 2018-10-04 | 日立化成株式会社 | 研磨液、研磨液セット及び研磨方法 |
TWI844518B (zh) * | 2017-09-26 | 2024-06-11 | 日商福吉米股份有限公司 | 研磨用組合物、研磨用組合物的製造方法、研磨方法及半導體基板的製造方法 |
WO2020021680A1 (ja) | 2018-07-26 | 2020-01-30 | 日立化成株式会社 | スラリ及び研磨方法 |
WO2019181013A1 (ja) * | 2018-03-22 | 2019-09-26 | 日立化成株式会社 | 研磨液、研磨液セット及び研磨方法 |
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JP4012180B2 (ja) * | 2004-08-06 | 2007-11-21 | 株式会社東芝 | Cmp用スラリー、研磨方法、および半導体装置の製造方法 |
JP5587620B2 (ja) * | 2010-01-25 | 2014-09-10 | 株式会社フジミインコーポレーテッド | 研磨用組成物及びそれを用いた研磨方法 |
DE112011103232T5 (de) * | 2010-09-27 | 2013-06-27 | Fujimi Incorporated | Oberflächenbehandlungszusammensetzung und Oberflächenbehandlungsverfahren unter Verwendung derselben |
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WO2014041991A1 (ja) | 2014-03-20 |
TW201418434A (zh) | 2014-05-16 |
JP2014060205A (ja) | 2014-04-03 |
KR20150055617A (ko) | 2015-05-21 |
US20150232705A1 (en) | 2015-08-20 |
SG11201501849RA (en) | 2015-04-29 |
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