TWI609074B - 化學機械硏磨組成物及方法 - Google Patents
化學機械硏磨組成物及方法 Download PDFInfo
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- TWI609074B TWI609074B TW102136165A TW102136165A TWI609074B TW I609074 B TWI609074 B TW I609074B TW 102136165 A TW102136165 A TW 102136165A TW 102136165 A TW102136165 A TW 102136165A TW I609074 B TWI609074 B TW I609074B
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- mechanical polishing
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- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
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- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229920002396 Polyurea Polymers 0.000 description 1
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- 229920002125 Sokalan® Polymers 0.000 description 1
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
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- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000004094 surface-active agent 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
- 238000012360 testing method Methods 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Computer Hardware Design (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明一般係有關於化學機械研磨領域。更明確言之,本發明係有關於化學機械研磨組成物及用以研磨半導體晶圓之方法,其中在複數個欲被研磨的晶圓中之第110個經研磨晶圓的研磨後,於指定研磨墊的使用壽命期間低k介電材料的移除速率維持穩定。
半導體產業在積體電路的製造上逐漸地仰賴銅電氣互連。積體電路的典型製法係在鑲嵌型結構中使用銅。在此製造過程期間,實質上過量的銅典型地沈積於晶圓的表面上。一般而言,採用多步驟式銅製程,其涉及初步移除及平坦化步驟,其中,化學機械平坦化係用以移除銅裝載過多(亦即步驟1銅CMP製程),接著為障壁層CMP製程(亦即步驟2 CMP製程)。於步驟1銅CMP製程期間,唯一積極暴露於CMP製程的材料是銅。據此,製造商典型地利用針對步驟1銅CMP製程呈現高銅移除速率的銅漿料。但於步驟2 CMP製程期間,除了銅以外之存在於或變成存在於基材表面之其它材料積極暴露於CMP製程。據
此,製造商利用針對步驟2 CMP製程的障壁漿料。
由於不同的積體電路晶片設計及製程原故,不同製造商針對用在步驟2的障壁漿料有不同的移除速率要求。亦即,有大量材料製品用於積體電路(亦即半導體晶圓)的生產上。但典型地,在步驟2CMP製程期間存在有三種材料,亦即:傳導層材料(例如銅);黏著/障壁層材料(例如:鉭、氮化鉭、鉭-氮化矽、鈦、氮化鈦、鈦-氮化矽、鈦-氮化鈦、鈦-鎢、鎢、氮化鎢及鎢-氮化矽);及介電材料(例如TEOS及低k材料諸如碳摻雜氧化物)。據此,提供多種材料於步驟2期間積極暴露於CMP製程中,要緊地須採用具有移除速率與移除速率選擇性經適當調整組合的障壁漿料,以提供期望的研磨結果。
在互連金屬及介電質存在下,用於步驟2 CMP製程以移除障壁材料的一種研磨組成物係揭示於核發給Liu等人的美國專利案第7,300,602號。Liu等人揭示在互連金屬及介電質存在下,用於移除障壁材料的一種研磨溶液,包含:0.1至10重量百分比之過氧化氫,選自於由硝酸、硫酸、鹽酸及磷酸所組成群組中之至少一種pH調節劑,以調整該研磨溶液的pH值至小於3,0.25至1.7重量百分比之苯并三唑抑制劑,以減低互連金屬的移除速率,0至10重量百分比之界面活性劑,0.01至10重量百分比之具有小於50奈米(nm)的平均粒徑之膠體二氧化矽,及餘量為水及附帶的雜質,並且以垂直晶圓測得為小於15kPa的研磨墊壓力來測量,研磨溶液具有至少3:1
之氮化鉭對銅選擇性及至少3:1之氮化鉭對TEOS選擇性。
儘管如此,仍然持續需要有用在步驟2 CMP製程的額外化學機械研磨組成物,該組成物相對於互連金屬及介電質(包含低k介電材料)能夠選擇性地移除障壁材料。
本發明提出一種化學機械研磨組成物,其主要係以下列作為起始成分所組成:水;0.01至0.5wt%之唑抑制劑,其中,該唑抑制劑係選自於由苯并三唑(BTA)、巰基苯并三唑(MBT)、甲苯基三唑(TTA)、咪唑及其組合物所組成之群組;0.01至0.5wt%之錯合劑,其中,該錯合劑係選自於由檸檬酸、乳酸、蘋果酸、順丁烯二酸、丙二酸、草酸、酒石酸及葡萄糖酸所組成之群組;0至1.0wt%之鹵化銨,其中,該鹵化銨係選自於由氯化銨、溴化銨及氟化銨所組成之群組;0.01至1wt%之含磷劑,其中,該含磷劑為磷酸;0.05至1.0wt%之增溶劑,其中,該增溶劑係選自於由苯磺酸酯、C1-4烷基苯磺酸酯、二-C1-4烷基苯磺酸酯、C5-10烷磺酸酯及其鹽類所組成之群組;0.1至40wt%之膠體二氧化矽研磨劑;0至5.0wt%之氧化劑;0.005至1.0wt%之聚乙烯基烷基醚;0至0.01wt%之殺生物劑,其中,該殺生物劑為噻唑啉衍生物;及pH調節劑;其中,該化學機械研磨組成物具有經設計用於研磨之8至12的pH;及其中,該化學機械研磨組成物呈現穩定的製造低k介電材料移除速率。
本發明提出一種化學機械研磨組成物,其主要係以下列作為起始成分所組成:水;0.02至0.04wt%之唑抑制劑,其中,該唑抑制劑係為苯并三唑;0.1至0.4wt%之錯合劑,其中,該錯合劑係為檸檬酸;0.1至0.3wt%之鹵化銨,其中該鹵化銨係為氯化銨;0.05至0.1wt%之含磷劑,其中,該含磷劑係為磷酸;0.3至0.8wt%之增溶劑,其中,該增溶劑係依據下式:H3C-(CH2)7-SO3Na;20至30wt%之膠體二氧化矽研磨劑,其中,該膠體二氧化矽具有100奈米的平均粒徑;0.1至0.5wt%之氧化劑,其中,該氧化劑為H2O2;0.008至0.03wt%之聚乙烯基烷基醚;及0.001至0.009wt%之殺生物劑,其中,該殺生物劑為噻唑啉衍生物;其中,該化學機械研磨組成物具有經設計用於研磨之8至12的pH;及其中,該化學機械研磨組成物呈現穩定的製造低k介電材料移除速率。
本發明提出一種用於複數個基材之化學機械研磨方法,該方法係包含:提供具有欲研磨之表面的至少150個分開半導體晶圓基材,其中,該欲研磨表面包含低k介電材料;提供化學機械研磨墊,其中,該化學機械研磨墊係包含聚胺甲酸酯;提供化學機械研磨組成物,其中,該化學機械研磨組成物主要係以下列作為起始成分所組成:水;0.01至0.5wt%之唑抑制劑,其中,該唑抑制劑係選自於由苯并三唑(BTA)、巰基苯并三唑(MBT)、甲苯基三唑(TTA)、咪唑及其組合物所組成之群組;0.01至0.5wt%
之錯合劑,其中,該錯合劑係選自於由檸檬酸、乳酸、蘋果酸、順丁烯二酸、丙二酸、草酸、酒石酸及葡萄糖酸所組成之群組;0至1.0wt%之鹵化銨,其中,該鹵化銨係選自於由氯化銨、溴化銨及氟化銨所組成之群組;0.01至1wt%之含磷劑,其中,該含磷劑係為磷酸;0.05至1.0wt%之增溶劑,其中,該增溶劑係選自於由苯磺酸酯、C1-4烷基苯磺酸酯、二-C1-4烷基苯磺酸酯、C5-10烷磺酸酯及其鹽類所組成之群組;0.1至40wt%之膠體二氧化矽研磨劑;0至5.0wt%之氧化劑;0.005至1.0wt%之聚乙烯基烷基醚;0至0.01wt%之殺生物劑,其中,該殺生物劑為噻唑啉衍生物;及pH調節劑;其中,該化學機械研磨組成物具有8至12之pH;連續地於該化學機械研磨墊與該至少150個分開半導體晶圓基材中之各者間之界面產生動態接觸;及分配該化學機械研磨組成物至該化學機械研磨墊上之該化學機械研磨墊與該至少150個分開半導體晶圓基材中之各者間之界面或接近該界面處,以促進該至少150個分開半導體晶圓基材中之各者的欲研磨表面的研磨,而提供至少150個經研磨晶圓;其中,該低k介電材料中之至少部分係從該至少150個分開半導體晶圓基材中之各者的欲研磨表面移除,以提供至少150個經研磨晶圓;其中,該低k介電材料從該至少150個分開半導體晶圓基材中之各者的欲研磨表面移除以提供至少150個經研磨晶圓的速率界定該至少150個經研磨晶圓中之各者的低k介電材料移除速率;其中,該至少150個經研磨晶圓的低k介電材料移除
速率起始地從該至少150個經研磨晶圓中之第一個經研磨晶圓往該至少150個經研磨晶圓中之各個後續經研磨晶圓幅值衰減,直到該至少150個經研磨晶圓中之過渡點經研磨晶圓之關聯低k介電材料移除速率係高於該至少150個經研磨晶圓中之最後一個先前經研磨晶圓之關聯低k介電材料移除速率;其中,該過渡點經研磨晶圓係在等至少150個經研磨晶圓中之第100個經研磨晶圓被研磨之前經研磨;及其中,在該至少150個經研磨晶圓中之第110個經研磨晶圓之該欲研磨表面的研磨後,與該至少150個經研磨晶圓關聯的低k介電材料移除速率維持穩定。
本發明提出一種用於複數個基材之化學機械研磨方法,該方法係包含:提供具有欲研磨之表面的至少150個分開半導體晶圓基材,其中,該欲研磨表面包含低k介電材料;提供化學機械研磨墊,其中,該化學機械研磨墊係包含聚胺甲酸酯;提供化學機械研磨組成物,其中,該化學機械研磨組成物主要係以下列作為起始成分所組成:水;0.02至0.04wt%之唑抑制劑,其中,該唑抑制劑係為苯并三唑;0.1至0.4wt%之錯合劑,其中,該錯合劑係為檸檬酸;0.1至0.3wt%之鹵化銨,其中,該鹵化銨係為氯化銨;0.05至0.1wt%之含磷劑,其中,該含磷劑係為磷酸;0.3至0.8wt%之增溶劑,其中,該增溶劑係依據下式:H3C-(CH2)7-SO3Na;20至30wt%之膠體二氧化矽研磨劑,其中,該膠體二氧化
矽具有100奈米的平均粒徑;0.1至0.5wt%之氧化劑,其中,該氧化劑係為H2O2;0.008至0.03wt%之聚乙烯基烷基醚;及0.001至0.009wt%之殺生物劑,其中,該殺生物劑為噻唑啉衍生物;及pH調節劑;其中,該化學機械研磨組成物具有8至12之pH;連續地於該化學機械研磨墊與該至少150個分開半導體晶圓基材中之各者間之界面產生動態接觸;及分配該化學機械研磨組成物至該化學機械研磨墊上之該化學機械研磨墊與該至少150個分開半導體晶圓基材中之各者間之界面或接近該界面處,以促進該至少150個分開半導體晶圓基材中之各者的欲研磨表面的研磨,而提供至少150個經研磨晶圓;其中,該低k介電材料中之至少部分係從該至少150個分開半導體晶圓基材中之各者的欲研磨表面移除,以提供至少150個經研磨晶圓;其中,該低k介電材料從該至少150個分開半導體晶圓基材中之各者的欲研磨表面移除以提供至少150個經研磨晶圓的速率係界定該至少150個經研磨晶圓中之各者的低k介電材料移除速率;其中,該至少150個經研磨晶圓的低k介電材料起始地從該至少150個經研磨晶圓中之第一個經研磨晶圓往該至少150個經研磨晶圓中之各個後續經研磨晶圓幅值衰減,直到該至少150個經研磨晶圓中之過渡點經研磨晶圓之關聯低k介電材料移除速率係高於該至少150個經研磨晶圓中之最後一個先前經研磨晶圓之關聯低k介電材料移除速率;其中,該過渡點經研磨晶圓係在該至少150個經研磨晶圓中之第100個經研磨晶圓被研
磨之前經研磨;及其中,在該至少150個經研磨晶圓中之第110個經研磨晶圓之該欲研磨表面的研磨後,與該至少150個經研磨晶圓關聯的低k介電材料移除速率維持穩定。
典型地,晶圓製造商偏好使用障壁研磨漿料配方,該配方呈現小於1000埃/分鐘的低k介電材料移除速率(於實施例中列舉的條件下量測)。滿足針對指定步驟2 CMP製程其它移除速率要求的障壁研磨漿料配方也呈現非期望地高的低k介電材料移除速率。曾經建議一種達成期望的低k介電材料移除速率而不影響步驟2 CMP製程期間存在的其它層(例如TEOS)的移除速率的一種方式,係將聚乙烯基烷基醚併入障壁研磨漿料。不幸地,單純添加聚乙烯基烷基醚至指定的障壁研磨漿料導致研磨配方呈現不穩定的低k材料移除速率。更明確言之,低k材料移除速率隨著研磨而減低,使得各後續晶圓研磨的低k材料移除速率係低於先前經研磨晶圓的低k材料移除速率。
發明人出乎意外地發現聚乙烯基烷基醚非期望地與用在典型步驟2 CMP製程的聚胺甲酸酯研磨墊的研磨表面交互作用。發明人發現於此種聚乙烯基烷基醚與研磨墊的研磨表面之間的交互作用導致研磨多個連續晶圓,隨著時間低k材料移除速率出現非期望的衰減。習知研磨墊調理技術不足以恢復研磨墊之研磨表面至會於該研
磨墊的有用使用壽命(例如1000個晶圓)期間促進穩定的低k材料移除速率的情況。
也出乎意外地發現於含有聚乙烯基烷基醚的鹼性障壁研磨配方中併入選自於下列所組成的群組之增溶劑:苯磺酸酯、C1-4烷基苯磺酸酯(例如甲苯磺酸酯、異丙苯磺酸酯)、二C1-4烷基苯磺酸酯(例如二甲苯磺酸酯、異丙苯磺酸酯)、C5-10烷磺酸酯及其鹽類的增溶劑改變研磨墊之研磨表面與聚乙烯基烷基醚間之交互作用,使得所得化學機械研磨組成物呈現穩定製造低k介電材料移除速率。
如本文及隨附之申請專利範圍使用「穩定製造低k介電材料移除速率」術語表示對於後續於第110個連續經研磨半導體晶圓基材之於化學機械研磨墊的剩餘壽命期間經研磨之所有連續經研磨半導體晶圓基材而言,使用本發明之化學機械研磨組成物組合上化學機械研磨墊研磨之連續經研磨半導體晶圓基材之關聯低k介電材料移除速率偏離第110個連續經研磨半導體晶圓基材關聯低k介電材料移除速率係小於12%。
本發明之化學機械研磨組成物較佳含有唑抑制劑作為起始成分,以藉由靜態蝕刻或其它移除機轉而調整非鐵金屬(例如銅)互連的移除。調整抑制劑濃度可藉由保護金屬免於靜態蝕刻而調整互連金屬移除速率。較佳地,化學機械研磨組成物含有0.01至0.5wt%,更佳0.01至0.1wt%,最佳0.02至0.04wt%之唑抑制劑。更佳地,
唑抑制劑係選自於由苯并三唑(BTA)、巰基苯并三唑(MBT)、甲苯基三唑(TTA)、咪唑及其組合物所組成的群組。唑抑制劑之組合物可提高或降低銅移除速率。最佳地,抑制劑為BTA,BTA乃銅及銀互連的特別有效抑制劑。視需要地,抑制劑包含唑抑制劑之混合物。
本發明之化學機械研磨組成物較佳含有非鐵金屬之錯合劑作為起始成分。較佳地,該化學機械研磨組成物含有0.01至至1.0wt%(更佳地0.01至0.5wt%,最佳地0.1至0.4wt%)之選自於下列所組成之群組之錯合劑作為起始成分:檸檬酸、乳酸、蘋果酸、順丁烯二酸、丙二酸、草酸、酒石酸及葡萄糖酸。較佳地,錯合劑係選自於由檸檬酸、乳酸、蘋果酸及順丁烯二酸所組成之群組。最佳地,錯合劑為檸檬酸。
本發明之化學機械研磨組成物較佳含有鹵化銨作為起始成分。較佳地,該化學機械研磨組成物含有0至0.1wt%(更佳地0.01至0.05wt%,最佳地0.1至0.03wt%)之選自於氯化銨、溴化銨、及氟化銨所組成的群組中之氯化銨作為起始成分。最佳地,鹵化銨為氯化銨。
本發明之化學機械研磨組成物較佳含有含磷劑作為起始成分。較佳地,化學機械研磨組成物包含0.01至1.0wt%(更佳地0.01至0.1wt%;最佳地0.05至0.1wt%)之含磷劑,其中,該含磷劑為磷酸。
本發明之化學機械研磨組成物較佳含有選自於由下列所組成之群組之增溶劑作為起始成分:苯磺酸
酯、C1-4烷基苯磺酸酯(例如甲苯磺酸酯、異丙苯磺酸酯)、二C1-4烷基苯磺酸酯(例如二甲苯磺酸酯、異丙苯磺酸酯)、C5-10烷磺酸酯及其鹽類。較佳地,該化學機械研磨組成物含有0.05至1wt%(更佳地0.1至1wt%,最佳地0.3至0.8wt%)之增溶劑作為起始成分。較佳地,該增溶劑係選自於由甲苯磺酸鈉、二甲苯磺酸鈉及C5-10烷磺酸鈉所組成的群組。最佳地,該增溶劑係根據下式:H3C-(CH2)7-SO3Na。
本發明之化學機械研磨組成物較佳含有0.1至40wt%之膠體二氧化矽研磨劑作為起始成分。更佳地,本發明之化學機械研磨組成物含有5至30wt%(最佳地20至30wt%)之膠體二氧化矽研磨劑作為起始成分。所使用的膠體二氧化矽研磨劑較佳具有100奈米(更佳地10至100奈米;最佳地25至60奈米)的平均粒徑。
本發明之化學機械研磨組成物視需要含有氧化劑作為起始成分。該化學機械研磨組成物較佳含有0至5wt%(更佳地0.1至5wt%,又更佳地0.1至1.0wt%,最佳地0.1至0.5wt%)之氧化劑作為起始成分。較佳地,該氧化劑係選自過氧化氫(H2O2)、單過硫酸鹽類、碘酸鹽類、過氧酞酸鎂(magnesium perphthalate)、過乙酸及其它過酸類、過硫酸鹽類、溴酸鹽類、過碘酸鹽類、硝酸鹽類、鐵鹽、銫鹽、錳(III)鹽、錳(IV)鹽及錳(VI)鹽、銀鹽、銅鹽、鉻鹽、鈷鹽、鹵素、次氯酸鹽、及其混合物。更佳地,氧化劑為過氧化氫。當該化學機械研磨組成物係調配成含有
不穩定的氧化劑諸如過氧化氫時,較佳係在使用時才併入氧化劑至化學機械研磨組成物。
本發明之化學機械研磨組成物較佳含有聚乙烯基烷基醚作為起始成分。較佳地,該化學機械研磨組成物含有0.005至1wt%(更佳地0.005至0.1wt%,最佳地0.008至0.03wt%)之聚乙烯基烷基醚作為起始成分。較佳地,聚乙烯基烷基醚為聚乙烯基C1-4烷基醚。更佳地,聚乙烯基烷基醚係選自於由聚乙烯基甲基醚、聚乙烯基乙基醚、及聚乙烯基丙基醚所組成的群組。又更佳地,聚乙烯基烷基醚係選自於由聚乙烯基甲基醚及聚乙烯基乙基醚所組成的群組。最佳地,聚乙烯基烷基醚為聚乙烯基甲基醚。
本發明之化學機械研磨組成物視需要含有殺生物劑諸如噻唑啉衍生物作為起始成分。較佳的噻唑啉衍生物殺生物劑包括柯戴克TM(KordekTM)MLX(9.5至9.9%之甲基-4-異噻唑啉-3-酮,89.1至9.5%之水及1.0%之相關反應產物)及含有活性成分2-甲基-4-異噻唑啉-3-酮及5-氯-2-甲基-4-異噻唑啉-3-酮的卡松TM(KathonTM)ICP III,各自係由羅門哈斯公司(Rohm and Haas Company)製造,(KathonTM及KordekTM皆為羅門哈斯公司的商標)。較佳地,該化學機械研磨組成物含有0至0.01wt%(更佳地0.0001至0.01wt%;最佳地0.001至0.009wt%)之殺生物劑作為起始成分。
本發明之化學機械研磨組成物較佳地在使用時呈現8至12之pH(更佳地9至11,又更佳地10至11,
最佳地10至10.5)。適合調整本發明之化學機械研磨組成物之pH的酸類包括例如硝酸、硫酸及鹽酸。適合用以調整本發明之化學機械研磨組成物之pH的鹼類包括例如氫氧化銨、氫氧化鎂、氫氧化鋰及氫氧化鉀。
本發明之化學機械研磨組成物中所含的水較佳為經去離子且經蒸餾以限制附帶雜質中之至少一者。
本發明之化學機械研磨組成物較佳含有<0.01ppm之與化合物形成包含下述結構的有機銨陽離子鹽,
其中,R1、R2、R3及R4為基團;及其中,R1具有2至25個碳原子之碳鏈。此種有機銨陽離子鹽已知提高碳摻雜氧化物之移除速率。應避免將提高碳摻雜氧化物之移除速率的化合物諸如有機銨陽離子鹽添加至本發明之化學機械研磨組成物。
本發明之化學機械研磨組成物較佳含有<1ppm聚乙烯基吡咯啶酮。
本發明之用於複數個基材之化學機械研磨方法包含:提供至少150個(較佳至少200個,更佳至少500個,最佳至少1,000個)具有欲研磨表面的分開半導體晶圓基材,其中,該欲研磨表面包含低k介電材料(較佳具有3.3之介電常數之低k碳摻雜氧化物介電材料,諸如得自應用
材料公司(Applied Materials)之黑鑽®(Black Diamond®)及得自諾維勒斯系統公司(Novellus Systems)的可羅®(Coral®);提供化學機械研磨組成物,其中,該化學機械研磨墊包含聚胺甲酸酯;提供化學機械研磨組成物,其中,該化學機械研磨組成物主要以下列作為起始成分所組成:水(較佳為蒸餾水及去離子水中之至少一者);唑抑制劑;錯合劑;鹵化銨;含磷劑;增溶劑;研磨劑;氧化劑;聚乙烯基烷基醚;殺生物劑;及pH調節劑;其中,該化學機械研磨組成物具有8至12之pH(較佳地9至11之pH;更佳地10至11之pH;最佳地10至10.5之pH);連續地於該化學機械研磨墊與該至少150個分開半導體晶圓基材中之各者間之界面產生動態接觸;及分配該化學機械研磨組成物至該化學機械研磨墊上於該化學機械研磨墊與該至少150個分開半導體晶圓基材中之各者間該界面或接近該界面處,以促進該至少150個分開半導體晶圓基材中之各者的欲研磨表面的研磨,而提供至少150個經研磨晶圓;其中,該低k介電材料中之至少部分係從該至少150個分開半導體晶圓基材中之各者的欲研磨表面移除,以提供至少150個經研磨晶圓;其中,該低k介電材料從該至少150個分開半導體晶圓基材中之各者的欲研磨表面移除以提供至少150個經研磨晶圓的速率界定該至少150個經研磨晶圓中之各者的低k介電材料移除速率;其中,該至少150個經研磨晶圓的低k介電材料移除速率起始地從該至少150個經研磨晶圓中之第一個經研磨晶圓往該至少150個經研磨晶圓中之
各個後續經研磨晶圓幅值衰減,直到該至少150個經研磨晶圓中之過渡點經研磨晶圓之關聯低k介電材料移除速率係高於該至少150個經研磨晶圓中之最後一個先前經研磨晶圓之關聯低k介電材料移除速率;其中該過渡點經研磨晶圓係在該至少150個經研磨晶圓中之第100個經研磨晶圓被研磨之前經研磨;及其中,在該至少150個經研磨晶圓中之第110個經研磨晶圓之該欲研磨表面的研磨後,與該至少150個經研磨晶圓關聯的低k介電材料移除速率維持穩定。
用於本文及於隨附之申請專利範圍關於低k介電材料移除速率所使用的「穩定」術語表示對於後續於第110個連續經研磨半導體晶圓基材(於實施例中列舉之條件下)之使用本發明方法於所提供的化學機械研磨墊之剩餘壽命(較佳至少1000個連續經研磨半導體晶圓基材)期間研磨之各個半導體晶圓基材之低k介電材料之移除速率係與第110個連續經研磨半導體晶圓基材所呈現的低k介電材料移除速率相差12%以內(更佳地,10%以內;最佳地,7%以內)。
較佳地,於本發明方法中,至少150(較佳至少200,更佳至少500,最佳至少1000)個所提供的分開半導體晶圓基材具有欲研磨表面,其中,該欲研磨表面包含導電材料(較佳為銅);黏合/障壁材料(較佳係選自於鉭、氮化鉭、鉭-氮化矽、鈦、氮化鈦、鈦-氮化矽、鈦-氮化鈦、鈦-鎢、鎢、氮化鎢及鎢-氮化矽所組成之群組;更佳為氮
化鉭);及具有3.3之介電常數的低k碳摻雜氧化物介電材料(例如得自應用材料公司的黑鑽®及得自諾維勒斯系統公司的可羅®)。
於本發明方法中提供的化學機械研磨墊較佳包含衍生自可硬化材料之研磨層。較佳地,該可硬化材料包含液體預聚物。更佳地,該可硬化材料包含液體預聚物及複數個微元件,其中複數個微元件係均勻分散於該液體預聚物內。
液體預聚物較佳係聚合(亦即硬化)而形成包含聚(胺甲酸酯)的材料。如本文及於隨附之申請專利範圍使用「聚(胺甲酸酯)」術語涵蓋衍生自二官能或多官能異氰酸酯(包含以異氰酸基為端基的預聚物)與含活性氫基之化合物(包括但非限於多元醇類、二醇類、胺類、水或其組合)反應所衍生的產物。此等反應產物之實施例包括但非僅限於聚胺甲酸酯類、聚脲類、聚胺甲酸酯脲類、聚醚胺甲酸酯類、聚酯胺甲酸酯類、聚醚脲類、聚酯脲類、聚異氰尿酸酯類(polyisocyanurate)、其共聚物及其混合物。最佳地,液體預聚物聚合而形成包含聚胺甲酸酯之材料。最佳地,液體預聚物聚合(硬化)而形成聚胺甲酸酯。
較佳地,液體預聚物包含含有聚異氰酸酯之材料。更佳地,液體預聚物包含聚異氰酸酯(例如二異氰酸酯)與含羥基材料之反應產物。
較佳地,聚異氰酸酯係選自亞甲基雙4,4’-環己基-異氰酸酯;環己基二異氰酸酯;二異氰酸異佛爾酮
酯;六亞甲基二異氰酸酯;伸丙基-1,2-二異氰酸酯;四亞甲基-1,4-二異氰酸酯;1,6-六亞甲基-二異氰酸酯;十二烷-1,12-二異氰酸酯;環丁烷-1,3-二異氰酸酯;環己烷-1,3-二異氰酸酯;環己烷-1,4-二異氰酸酯;1-異氰酸基-3,3,5-三甲基-5-異氰酸基甲基環己烷;甲基伸環己基二異氰酸酯;六亞甲基二異氰酸酯之三異氰酸酯;2,4,4-三甲基-1,6-己烷二異氰酸酯之三異氰酸酯;六亞甲基二異氰酸酯之縮脲二酮(urtdione);伸乙基二異氰酸酯;2,2,4-三甲基六亞甲基二異氰酸酯;2,4,4-三-甲基六亞甲基二異氰酸酯;二環己基甲烷二異氰酸酯;及其組合。最佳地,多異氰酸酯為脂肪族及具有少於14%未反應的異氰酸基。
較佳地,用於本發明之含羥基材料為多元醇。例示性多元醇包括例如聚醚多元醇、以羥基為端基之聚丁二烯(包括部分及完全氫化衍生物)、聚酯多元醇、聚己內酯多元醇、聚碳酸酯多元醇、及其混合物。
較佳多元醇包括聚醚多元醇。聚醚多元醇之例子包括聚四亞甲基醚二醇(「PTMEG」)、聚乙二醇丙二醇、聚氧伸丙基二醇及其混合物。烴鏈可具有飽和鍵或不飽和鍵及經取代之或未經取代之芳香族基及環狀基團。較佳地,本發明之多元醇包括PTMEG。適當的聚酯多元醇包括但非僅限於聚己二酸乙二醇酯二醇;聚己二酸丁二醇酯二醇;聚己二酸乙二醇丙二醇酯二醇;鄰苯二甲酸-1,6-己二醇;聚(己己二醇二酸酯)二醇;及其混合物。烴鏈可具有飽和鍵或不飽和鍵,或經取代之或未經取代之芳香族
基及環狀基。適當聚己內酯多元醇包括但不限於1,6-己二醇起始之聚己內酯;二乙二醇起始之聚己內酯;三羥甲基丙烷起始之聚己內酯;新戊二醇起始之聚己內酯;1,4-丁二醇起始之聚己內酯;PTMEG起始之聚己內酯;及其混合物。該烴鏈可具有飽和鍵或不飽和鍵,或經取代之或未經取代之芳香族基及環狀基。適當的聚碳酸酯包括但非僅限於聚鄰苯二甲酸碳酸酯及聚(碳酸己二醇酯)二醇。
較佳地,複數個微元件係選自於被捕捉的氣泡、中空核心聚合性材料(亦即微球)、經液體填充的中空核心聚合性材料、水溶性材料(例如環糊精)及不可溶相材料(例如礦油)。較佳地,複數個微元件為微球,諸如:聚乙烯醇類、果膠、聚乙烯基吡咯啶酮、聚丙烯腈、聚(二氯亞乙烯)、羥基乙基纖維素、甲基纖維素、羥基丙基甲基纖維素、羧基甲基纖維素、羥基丙基纖維素、聚丙烯酸類、聚丙烯醯胺類、聚乙二醇、聚羥基醚丙烯酸酯(polyhydroxyetheracrylite)、澱粉類、順丁烯二酸共聚物、聚環氧乙烷、聚胺甲酸酯類、環糊精及其組合物(例如伊斯邦索TM(ExpancelTM)得自瑞典桑斯沃艾克佐諾貝爾公司(Akzo Nobel))。微球可經化學改質,藉例如分支、封阻及交聯而改變溶解度、溶脹性及其它性質。較佳地,微球具有小於150微米之平均直徑,及更佳地,小於50微米之平均直徑。最佳地,微球48具有小於50微米之平均直徑。注意,微球之平均直徑可經改變及可使用不同微球48之不同尺寸或混合物。微球之最佳材料為丙烯腈與二氯亞乙烯
基(vinylidene dichloride)之共聚物(例如伊斯班索®(Expancel®)得自艾克佐諾貝爾公司)。
液體預聚物視需要地進一步包含硬化劑。較佳硬化劑包括二胺。適當聚二胺包括初級胺及二級胺。較佳聚二胺包括但非僅限於二乙基甲苯二胺(「DETDA」);3,5-二甲基硫基-2,4-甲苯二胺及其異構物;3,5-二乙基甲苯-2,4-二胺及其異構物(例如3,5-二乙基甲苯-2,6-二胺);4,4’-雙-(第二丁基胺基)-二苯基甲烷;1,4-雙-(第二丁基胺基)-苯;4,4’-亞甲基-雙-(2-氯苯胺);4,4’-亞甲基-雙-(3-氯-2,6-二乙基苯胺)(「MCDEA」);聚四亞甲基氧化物-二-對胺基苯甲酸酯;N,N’-二烷基二胺基二苯基甲烷;p,p’-亞甲基二苯胺(「MDA」);間伸苯基二胺(「MPDA」);亞甲基-雙2-氯苯胺(「MBOCA」);4,4’-亞甲基-雙-(2-氯苯胺)(「MOCA」);4,4’-亞甲基-雙-(2,6-二乙基苯胺)(「MDEA」);4,4’-亞甲基-雙-(2,3-二氯苯胺)(「MDCA」);4,4’-二胺基-3,3’-二乙基-5,5’-二甲基二苯基甲烷、2,2’,3,3’-四氯-二胺基二苯基甲烷;二-對-胺基苯甲酸三亞甲基二醇酯;及其混合物。較佳地,二胺硬化劑係選自3,5-二甲基硫基-2,4-甲苯二胺及其異構物。
硬化劑也可包括二元醇類、三元醇類、四元醇類及以羥基封端之硬化劑。適當二元醇、三元醇、及四元醇群組包括乙二醇;二乙二醇;聚乙二醇;丙二醇;聚丙二醇;低分子量聚四亞甲基醚二醇;1,3-雙(2-羥基乙氧基)苯;1,3-雙-[2-(2-羥基乙氧基)乙氧基]苯;1,3-雙-
{2-[2-(2-羥基乙氧基)乙氧基]乙氧基}苯;1,4-丁二醇;1,5-戊二醇;1,6-己二醇;間苯二酚-二-(β-羥基乙基)醚;對苯二酚-二-(β-羥基乙基)醚;及其混合物。較佳以羥基封端之硬化劑包括1,3-雙(2-羥基乙氧基)苯;1,3-雙-[2-(2-羥基乙氧基)乙氧基]苯;1,3-雙-{2-[2-(2-羥基乙氧基)乙氧基]乙氧基}苯;1,4-丁二醇;及其混合物。以羥基封端及二胺硬化劑可包括一或多個飽和、不飽和、芳香族、及環狀基。此外,以羥基封端及二胺硬化劑可包括一或多個鹵素基。
現在將於下列實施例中進一步詳細描述本發明之若干實施例。
用於比較研磨例PC1至PC3及研磨實施例1的化學機械研磨組成物(亦即分別為化學機械研磨組成物C1至C3及1)係經由以表1列舉之量組合成分,餘量為去離子水,及使用氫氧化鉀將組成物之pH調整至表1列舉之最終pH而製備。
可羅®覆氈性晶圓移除速率研磨測試係使用根據比較例C1至C3及實施例1所製備的化學機械研磨組成物進行。更明確言之,提供多個閒置晶圓可羅®覆氈性晶圓被混入作為第10、第25、第50、第75、第100個等晶
圓。然後此等晶圓接受連續研磨,且針對如表1識別的化學機械研磨組成物C1至C3及1各者測量可羅®移除速率。應用材料公司里菲松(Reflexion)300毫米研磨機器裝配有ISRM檢測器系統,使用維真派(VisionPadTM)3100聚胺甲酸酯研磨墊(具有1010+A24溝槽圖案)(商業上得自羅門哈斯電子材料CMP公司),於1.5psi(10.3kPa)之向下力條件,350cc/min研磨溶液流速,93RPM平台速度及87RPM載具速度。使用戴雅格®(Diagrid®)AD3BS-211250-3FN鑽石墊調理器(商業上得自齊尼克公司(Kinik Company))以調理晶圓間的研磨墊。使用KLA坦柯(Tencor)ASET F5X計量學工具測定可羅®移除速率。針對連續編號的晶圓之移除速率實驗結果提供於表2。
Claims (10)
- 一種化學機械研磨組成物,其主要係以下列作為起始成分所組成:水;0.01至0.5wt%之唑抑制劑,其中,該唑抑制劑係選自於由苯并三唑(BTA)、巰基苯并三唑(MBT)、甲苯基三唑(TTA)、咪唑及其組合物所組成之群組;0.01至0.5wt%之錯合劑,其中,該錯合劑係選自於由檸檬酸、乳酸、蘋果酸、順丁烯二酸、丙二酸、草酸、酒石酸及葡萄糖酸所組成之群組;0至1.0wt%之鹵化銨,其中,該鹵化銨係選自於由氯化銨、溴化銨及氟化銨所組成之群組;0.01至1wt%之含磷劑,其中,該含磷劑係為磷酸;0.05至1.0wt%之增溶劑,其中,該增溶劑係選自於由苯磺酸酯、C1-4烷基苯磺酸酯、二-C1-4烷基苯磺酸酯、C5-10烷磺酸酯及其鹽類所組成之群組;0.1至40wt%之膠體二氧化矽研磨劑;0至5.0wt%之氧化劑;0.005至1.0wt%之聚乙烯基烷基醚;0至0.01wt%之殺生物劑,其中,該殺生物劑為噻唑啉衍生物;及pH調節劑;其中,該化學機械研磨組成物具有經設計用於研磨之8至12的pH;及 其中,該化學機械研磨組成物呈現穩定的製造低k介電材料移除速率。
- 如申請專利範圍第1項所述之化學機械研磨組成物,其中,該膠體二氧化矽研磨劑係具有100奈米(nm)之平均粒徑;及其中,該氧化劑係選自過氧化氫(H2O2)、單過硫酸鹽類、碘酸鹽類、過氧酞酸鎂、過乙酸及其它過酸類、過硫酸鹽類、溴酸鹽類、過碘酸鹽類、硝酸鹽類、鐵鹽、銫鹽、錳(III)鹽、錳(IV)鹽及錳(VI)鹽、銀鹽、銅鹽、鉻鹽、鈷鹽、鹵素、次氯酸鹽、及其混合物。
- 如申請專利範圍第2項所述之化學機械研磨組成物,其中,該化學機械研磨組成物的主要係以下列作為起始成分所組成:0.01至1.0wt%之該鹵化銨;及0.0001至0.01wt%之該殺生物劑。
- 如申請專利範圍第3項所述之化學機械研磨組成物,其中,該化學機械研磨組成物的主要係以下列作為起始成分所組成:水;0.02至0.04wt%之該唑抑制劑;0.1至0.4wt%之該錯合劑;0.1至0.3wt%之該鹵化銨;0.05至0.1wt%之該含磷劑;0.3至0.8wt%之該增溶劑; 20至30wt%之該膠體二氧化矽研磨劑;0.1至0.5wt%之該氧化劑;0.008至0.03wt%之該聚乙烯基烷基醚;及0.001至0.009wt%之該殺生物劑。
- 如申請專利範圍第3項所述之化學機械研磨組成物,其中,該化學機械研磨組成物主要係以下列作為起始成分所組成:水;0.02至0.04wt%之該唑抑制劑,其中,該唑抑制劑係為苯并三唑;0.1至0.4wt%之該錯合劑,其中,該錯合劑係為檸檬酸;0.1至0.3wt%之該鹵化銨,其中,該鹵化銨係為氯化銨;0.05至0.1wt%之該含磷劑,其中,該含磷劑係為磷酸;0.3至0.8wt%之該增溶劑,其中,該增溶劑係依據下式:H3C-(CH2)7-SO3Na;20至30wt%之該膠體二氧化矽研磨劑,其中,該膠體二氧化矽具有100奈米的平均粒徑;0.1至0.5wt%之該氧化劑,其中,該氧化劑係為H2O2;0.008至0.03wt%之該聚乙烯基烷基醚;及 0.001至0.009wt%之該殺生物劑。
- 一種用於複數個基材之化學機械研磨方法,該方法係包含:提供具有欲研磨之表面的至少150個分開半導體晶圓基材,其中,該欲研磨之表面包含低k介電材料;提供化學機械研磨墊,其中,該化學機械研磨墊係包含聚胺甲酸酯;提供化學機械研磨組成物,其中,該化學機械研磨組成物主要係以下列作為起始成分所組成:水;0.01至0.5wt%之唑抑制劑,其中,該唑抑制劑係選自於由苯并三唑(BTA)、巰基苯并三唑(MBT)、甲苯基三唑(TTA)、咪唑及其組合物所組成之群組;0.01至0.5wt%之錯合劑,其中,該錯合劑係選自於由檸檬酸、乳酸、蘋果酸、順丁烯二酸、丙二酸、草酸、酒石酸及葡萄糖酸所組成之群組;0至1.0wt%之鹵化銨,其中,該鹵化銨係選自於由氯化銨、溴化銨及氟化銨所組成之群組;0.01至1wt%之含磷劑,其中,該含磷劑為磷酸;0.05至1.0wt%之增溶劑,其中,該增溶劑係選自於由苯磺酸酯、C1-4烷基苯磺酸酯、二-C1-4烷基苯磺酸酯、C5-10烷磺酸酯及其鹽類所組成之群組;0.1至40wt%之膠體二氧化矽研磨劑;0至5.0wt%之氧化劑; 0.005至1.0wt%之聚乙烯基烷基醚;0至0.01wt%之殺生物劑,其中,該殺生物劑為噻唑啉衍生物;及pH調節劑;其中,該化學機械研磨組成物具有8至12之pH;連續地於該化學機械研磨墊與至少150個分開半導體晶圓基材中之各者之間之界面產生動態接觸;及分配該化學機械研磨組成物至該化學機械研磨墊上該化學機械研磨墊與該至少150個分開半導體晶圓基材中之各一者間之該界面或接近該界面處,以促進該至少150個分開半導體晶圓基材中之各一者的欲研磨表面的研磨,而提供至少150個經研磨晶圓;其中,該低k介電材料中之至少部分係從該至少150個分開半導體晶圓基材中之各者的欲研磨表面移除,以提供至少150個經研磨晶圓;其中,該低k介電材料從該至少150個分開半導體晶圓基材中之各者的欲研磨表面移除以提供至少150個經研磨晶圓的速率係界定該至少150個經研磨晶圓中之各者的低k介電材料移除速率;其中,該至少150個經研磨晶圓的低k介電材料移除速率起始地從該至少150個經研磨晶圓中之第一個經研磨晶圓往該至少150個經研磨晶圓中之各個後續經研磨晶圓幅值衰減,直到該至少150個經研磨晶圓中之過渡點經研磨晶圓之關聯低k介電材料移除速率係 高於該至少150個經研磨晶圓中之最後一個先前經研磨晶圓之關聯低k介電材料移除速率;其中,該過渡點經研磨晶圓係在該至少150個經研磨晶圓中之第100個經研磨晶圓被研磨之前經研磨;及其中,在該至少150個經研磨晶圓中之第110個經研磨晶圓之該欲研磨表面的研磨後,與該至少150個經研磨晶圓關聯的該低k介電材料移除速率維持穩定。
- 如申請專利範圍第6項所述之方法,其中,該膠體二氧化矽研磨劑係具有100奈米之平均粒徑;及其中,該氧化劑係選自過氧化氫(H2O2)、單過硫酸鹽類、碘酸鹽類、過氧酞酸鎂、過乙酸及其它過酸類、過硫酸鹽類、溴酸鹽類、過碘酸鹽類、硝酸鹽類、鐵鹽、銫鹽、錳(III)鹽、錳(IV)鹽及錳(VI)鹽、銀鹽、銅鹽、鉻鹽、鈷鹽、鹵素、次氯酸鹽、及其混合物。
- 如申請專利範圍第7項所述之方法,其中,該所提供的化學機械研磨組成物主要係以下列作為起始成分所組成:0.01至1.0wt%之該鹵化銨;及0.0001至0.01wt%之該殺生物劑。
- 如申請專利範圍第8項所述之方法,其中該所提供的化學機械研磨組成物主要係以下列作為起始成分所組成:水; 0.02至0.04wt%之該唑抑制劑;0.1至0.4wt%之該錯合劑;0.1至0.3wt%之該鹵化銨;0.05至0.1wt%之該含磷劑;0.3至0.8wt%之該增溶劑;20至30wt%之該膠體二氧化矽研磨劑;0.1至0.5wt%之該氧化劑;0.008至0.03wt%之該聚乙烯基烷基醚;及0.001至0.009wt%之該殺生物劑。
- 如申請專利範圍第7項所述之方法,其中,該所提供的化學機械研磨組成物主要係以下列作為起始成分所組成:水;0.02至0.04wt%之該唑抑制劑,其中,該唑抑制劑係為苯并三唑;0.1至0.4wt%之該錯合劑,其中。該錯合劑係為檸檬酸;0.1至0.3wt%之該鹵化銨,其中,該鹵化銨係為氯化銨;0.05至0.1wt%之該含磷劑,其中,該含磷劑係為磷酸;0.3至0.8wt%之該增溶劑,其中,該增溶劑係依據下式:H3C-(CH2)7-SO3Na; 20至30wt%之該膠體二氧化矽研磨劑,其中,該膠體二氧化矽具有100奈米的平均粒徑;0.1至0.5wt%之該氧化劑,其中,該氧化劑為H2O2;0.008至0.03wt%之該聚乙烯基烷基醚;及0.001至0.009wt%之該殺生物劑。
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2012
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2013
- 2013-10-07 TW TW102136165A patent/TWI609074B/zh active
- 2013-10-08 CN CN201310756790.1A patent/CN103773248B/zh active Active
- 2013-10-08 KR KR1020130120026A patent/KR102125229B1/ko active IP Right Grant
- 2013-10-08 FR FR1359750A patent/FR2996558B1/fr active Active
- 2013-10-08 JP JP2013211007A patent/JP6239923B2/ja active Active
- 2013-10-09 DE DE102013016780.9A patent/DE102013016780B4/de active Active
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Also Published As
Publication number | Publication date |
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CN103773248A (zh) | 2014-05-07 |
KR20140045891A (ko) | 2014-04-17 |
TW201435069A (zh) | 2014-09-16 |
JP2014095072A (ja) | 2014-05-22 |
KR102125229B1 (ko) | 2020-06-22 |
FR2996558A1 (fr) | 2014-04-11 |
JP6239923B2 (ja) | 2017-11-29 |
US8545715B1 (en) | 2013-10-01 |
DE102013016780A1 (de) | 2014-04-10 |
DE102013016780B4 (de) | 2023-03-30 |
CN103773248B (zh) | 2015-08-12 |
FR2996558B1 (fr) | 2017-06-23 |
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