TWI482789B - Chemical mechanical polishing pad - Google Patents
Chemical mechanical polishing pad Download PDFInfo
- Publication number
- TWI482789B TWI482789B TW098123685A TW98123685A TWI482789B TW I482789 B TWI482789 B TW I482789B TW 098123685 A TW098123685 A TW 098123685A TW 98123685 A TW98123685 A TW 98123685A TW I482789 B TWI482789 B TW I482789B
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- Prior art keywords
- polishing pad
- density
- isocyanate
- polymer matrix
- polishing
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims description 96
- 239000000126 substance Substances 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims description 81
- 239000002245 particle Substances 0.000 claims description 42
- -1 polytetramethylene Polymers 0.000 claims description 35
- 238000000227 grinding Methods 0.000 claims description 31
- 239000011159 matrix material Substances 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000004814 polyurethane Substances 0.000 claims description 17
- 229920002635 polyurethane Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- 230000007547 defect Effects 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003989 dielectric material Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 2
- 239000008187 granular material Substances 0.000 claims 2
- 229910052707 ruthenium Inorganic materials 0.000 claims 2
- 239000000779 smoke Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 32
- 239000012948 isocyanate Substances 0.000 description 22
- 235000012431 wafers Nutrition 0.000 description 21
- 238000009472 formulation Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 18
- 150000002513 isocyanates Chemical class 0.000 description 13
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 13
- 239000004005 microsphere Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000009966 trimming Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- BSYVFGQQLJNJJG-UHFFFAOYSA-N 2-[2-(2-aminophenyl)sulfanylethylsulfanyl]aniline Chemical compound NC1=CC=CC=C1SCCSC1=CC=CC=C1N BSYVFGQQLJNJJG-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- VIOMIGLBMQVNLY-UHFFFAOYSA-N 4-[(4-amino-2-chloro-3,5-diethylphenyl)methyl]-3-chloro-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C(=C(CC)C(N)=C(CC)C=2)Cl)=C1Cl VIOMIGLBMQVNLY-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 1
- DVPHIKHMYFQLKF-UHFFFAOYSA-N 4-tert-butyl-2-methylbenzene-1,3-diamine Chemical compound CC1=C(N)C=CC(C(C)(C)C)=C1N DVPHIKHMYFQLKF-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229940064734 aminobenzoate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QCLQZCOGUCNIOC-UHFFFAOYSA-N azanylidynelanthanum Chemical compound [La]#N QCLQZCOGUCNIOC-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000005380 borophosphosilicate glass Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- POAHJTISJZSSFK-UHFFFAOYSA-N chloro(phenyl)methanediamine Chemical compound NC(N)(Cl)C1=CC=CC=C1 POAHJTISJZSSFK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 150000003673 urethanes Chemical class 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
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/28—Resins or natural or synthetic macromolecular compounds
- B24D3/32—Resins or natural or synthetic macromolecular compounds for porous or cellular structure
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本說明書係關於適用於研磨或平面化半導體基板之研磨墊。This specification relates to polishing pads suitable for use in grinding or planarizing semiconductor substrates.
半導體之製備典型係涵蓋若干化學機械研磨(CMP)製程。於各CMP製程中，研磨墊與研磨溶液(如含有研磨劑之研磨漿料或不含研磨劑之反應性液體)之組合會以平面化或保持用於接收後續層之平整度的方式移除過量材料。此等層之積疊係以形成積體電路之方式組合。由於對具有更高操作速度、更低漏電流及降低能耗有要求，此等半導體裝置之製造持續變得更複雜。於裝置構造方面，可說是為對更精細之特徵幾何學及增加金屬化表面有要求。此等愈加嚴格之裝置設計要求造成越來越小之線間距及相應增加之圖案密度。裝置之小型化及增加之複雜度已經導致對於CMP消耗品(如研磨墊及研磨溶液)有更大需求。此外，隨著積體電路之特徵的尺寸下降，由CMP引致之缺陷(如擦傷，變成更大問題。再者，降低積體電路之膜厚度係要求改善缺陷並同時為晶片基板提供可接受之形貌；此等形貌之要求係需要愈加嚴格之平面性、線凹陷(line dishing)以及小特徵陣列侵蝕研磨規格。Semiconductor fabrication typically involves several chemical mechanical polishing (CMP) processes. In each CMP process, the combination of the polishing pad with the grinding solution (eg, abrasive slurry containing abrasive or reactive liquid without abrasive) is removed in a manner that is planarized or maintained to receive the flatness of subsequent layers. Excess material. The stacks of these layers are combined in such a way as to form an integrated circuit. The manufacture of such semiconductor devices continues to become more complex due to the requirements for higher operating speeds, lower leakage currents, and lower power consumption. In terms of device construction, it can be said that there is a requirement for finer feature geometry and increased metallization surface. These increasingly stringent device designs have resulted in smaller and smaller line spacings and correspondingly increased pattern densities. The miniaturization and increased complexity of the device has led to greater demand for CMP consumables such as polishing pads and grinding solutions. In addition, as the size of the features of the integrated circuit decreases, defects caused by CMP (such as scratches become a larger problem. Further, lowering the film thickness of the integrated circuit requires improvement of defects and at the same time providing acceptable for the wafer substrate. Morphology; the requirements of these topography require more stringent planarity, line dishing, and small feature array erosion grinding specifications.
歷史上，澆鑄之聚胺酯研磨墊已經對用以製造積體電路之大部份研磨操作提供機械完整性及化學抗性。舉例而言，聚胺酯研磨墊具有足以抵抗撕裂之拉伸強度及延長性；用於避免研磨過程中磨損問題之抗研磨性；以及用於抵抗由強酸性及強鹼性研磨溶液造成之腐蝕的安定性。不幸的是，有助於改善平面化的澆鑄硬聚胺酯研磨墊也助長缺陷的增加。Historically, cast polyurethane polishing pads have provided mechanical integrity and chemical resistance to most of the grinding operations used to make integrated circuits. For example, polyurethane abrasive pads have tensile strength and elongation sufficient to resist tearing; abrasion resistance to avoid wear problems during grinding; and resistance to corrosion caused by strong acidic and strongly alkaline grinding solutions. Stability. Unfortunately, cast hard polyurethane abrasive pads that help improve planarization also contribute to the increase in defects.
M.J.Kulp於美國專利案第7,169,030號中揭露具有高拉伸模數之聚胺酯研磨墊家族。此等研磨墊係向若干研磨墊及研磨漿料之組合提供傑出的平面化及缺陷。舉例而言，此等研磨墊可為研磨氧化矽/氮化矽(如用於直接淺溝槽隔離(shallow trench isolation,STI)研磨)之應用的含有氧化鈰之研磨漿料提供傑出研磨效能(performance)。為了本說明書之目的，氧化矽係指適用於形成半導體裝置之介電材料之氧化矽(silica)、氧化矽化合物以及經摻雜氧化矽配方；而氮化矽係指適用於半導體應用之氮化矽、氮化矽化合物及經摻雜氮化矽配方。不幸的是，此等墊對於以用於現今及未來半導體晶片中所含有之多層基板層之所有研磨漿料改善研磨效能並不具有普遍適用性。再者，隨著半導體裝置之成本下降，仍需要不斷進一步增加研磨效能。A family of polyurethane abrasive pads having a high tensile modulus is disclosed in U.S. Patent No. 7,169,030. These polishing pads provide outstanding planarization and defects to a combination of abrasive pads and abrasive slurries. For example, such polishing pads can provide excellent polishing performance for cerium oxide-containing abrasive slurries for abrasive yttria/tantalum nitride (such as for shallow trench isolation (STI) milling) applications ( Performance). For the purposes of this specification, yttria refers to the cerium oxide, yttria compound, and doped yttrium oxide formulations suitable for forming dielectric materials for semiconductor devices; and lanthanum nitride refers to nitridation for semiconductor applications. Bismuth, tantalum nitride compounds and doped tantalum nitride formulations. Unfortunately, such pads do not have general applicability for improving the abrasive performance of all abrasive slurries used in multilayer substrate layers contained in current and future semiconductor wafers. Furthermore, as the cost of semiconductor devices declines, there is still a need to continuously increase the polishing efficiency.
增加研磨墊之移除速度可增加產量，而降低半導體製造廠之設備檯面面積及財政支出。因為這種用於增加效能之需求，仍對具有增加之效能之用以移除基板層之研磨墊有需求。舉例而言，氧化物介電材料之移除速度對於層問介電材料(inter-layer dielectric,ILD)或金屬間介電材料(inter-metallic dielectric,IMD)之研磨過程中移除介電材料係重要者。所使用之介電氧化物之具體類型包括 下列者：BPSG、自四乙氧基矽酸酯之分解形成之TEOS、高密度電漿(high-density plasma,HDP)以及低壓化學氣相沈積物(sub-atmospheric chemical vapor deposition,SACVD)。目前存在對於具有增加之移除速度以及可接受之缺陷效能與晶片一致性之研磨墊的需要。更具體地，對具有加快之氧化物移除速度以及可接受之平面化與缺陷研磨效能之適用於ILD研磨之研磨墊有需求。Increasing the removal rate of the polishing pad can increase production and reduce the equipment floor area and financial expenses of the semiconductor manufacturing plant. Because of this need to increase performance, there is still a need for abrasive pads for removing substrate layers with increased performance. For example, the removal rate of the oxide dielectric material removes the dielectric material during the grinding process of the inter-layer dielectric (ILD) or the inter-metallic dielectric (IMD). It is important. The specific types of dielectric oxides used include The following are: BPSG, TEOS formed from the decomposition of tetraethoxyphthalate, high-density plasma (HDP), and sub-atmospheric chemical vapor deposition (SACVD). There is currently a need for a polishing pad with increased removal speed and acceptable defect performance and wafer uniformity. More specifically, there is a need for abrasive pads suitable for ILD milling with accelerated oxide removal rates and acceptable planarization and defect grinding performance.
本發明係提供一種適用於研磨含有至少下列之一者之圖形化半導體基板的研磨墊：銅、介電材料、阻擋物以及鎢，其中該研磨墊係包括聚合物基質及位於該聚合物基質內之中空聚合物顆粒，該聚合物基質係NH2
對NCO之化學計量比率為80%至97%之固化劑與異氰酸酯封端之聚四伸甲基醚二醇之聚胺酯反應產物，該異氰酸酯封端之聚四伸甲基醚二醇具有8.75重量%至9.05重量%範圍之未反應NCO，該固化劑含有將該異氰酸酯封端之聚四伸甲基醚二醇固化以形成該聚合物基質之固化胺；以及該中空聚合物顆粒具有2至50μm之平均直徑，及如下式所示之形成該研磨墊之成份的wt%b
及密度b
：
其中，『密度a 』等於60g/L之平均密度，『密度b 』係5g/L至500g/L之平均密度，『wt%a 』係3.25重量%至4.25重量%， 該研磨墊具有30體積%至60體積%之孔隙率，以及位於該聚合物基質內之閉合單元結構，該聚合基質形成環繞該閉合單元結構之連續網。Wherein, "density a " is equal to an average density of 60 g/L, "density b " is an average density of 5 g/L to 500 g/L, "wt% a " is 3.25 wt% to 4.25 wt%, and the polishing pad has 30 volumes. From 0.0 to 60% by volume porosity, and a closed cell structure within the polymer matrix, the polymeric matrix forms a continuous web surrounding the closed cell structure.
本發明之另一具體實施例係提供一種適用於研磨含有至少下列之一者之圖形化半導體基板的研磨墊：銅、介電材料、阻擋物以及鎢，其中該研磨墊係包括聚合物基質及位於該聚合物基質內之中空聚合物顆粒，該聚合物基質係NH2
對NCO之化學計量比率為80%至97%之固化劑與異氰酸酯封端之聚四伸甲基醚二醇之聚胺酯反應產物，該異氰酸酯封端之聚四伸甲基醚二醇具有8.75重量%至9.05重量%範圍之未反應NCO，該固化劑含有將該異氰酸酯封端之聚四伸甲基醚二醇固化以形成該聚合物基質之固化胺；以及該中空聚合物顆粒具有2至50μm之平均直徑，及如下式所示之形成該研磨墊之成份的wt%b
及密度b
：
其中，『密度a 』等於60g/L之平均密度，『密度b 』係10g/L至300g/L之平均密度Among them, "density a " is equal to the average density of 60g / L, "density b " is the average density of 10g / L to 300g / L
『wt%a 』係3.25重量%至3.6重量%，該研磨墊具有35體積%至55體積%之孔隙率，以及位於該聚合物基質內之閉合單元結構，該聚合基質形成環繞該閉合單元結構之連續網。"wt% a " is from 3.25 wt% to 3.6% by weight, the polishing pad has a porosity of from 35 to 55% by volume, and a closed cell structure in the polymer matrix, the polymeric matrix forming a structure surrounding the closed cell Continuous network.
本發明係提供適用於平面化半導體、光學及磁性基板之至少一者的研磨墊，該研磨墊係包含聚合物基質。該研磨墊尤其適用於研磨及平面化層間介電材料(ILD)應用中之ILD介電材料，但也可用於研磨金屬如銅或鎢。該墊係提供較目前所用之墊增加的移除速度，尤其於研磨之最初30秒。於研磨之早期過程中該墊之加速回應使得藉由縮短自晶片表面移除特定量之材料所需時間來增加晶片產量成為可能。The present invention provides a polishing pad suitable for use in planarizing at least one of a semiconductor, an optical, and a magnetic substrate, the polishing pad comprising a polymer matrix. The polishing pad is particularly useful for grinding and planarizing ILD dielectric materials in interlayer dielectric (ILD) applications, but can also be used to polish metals such as copper or tungsten. This pad provides increased removal speed compared to currently used pads, especially for the first 30 seconds of grinding. The accelerated response of the pad during the early stages of grinding makes it possible to increase wafer throughput by reducing the time required to remove a certain amount of material from the wafer surface.
燻矽(fumed silica)之ILD研磨之30秒移除速度可超過3,750埃(Å)/分。再者，本發明可提供較IC1010TM 聚胺酯研磨墊於相同研磨測試中所給出之30秒移除速度高出至少10%之移除速度(IC1010係羅門哈斯公司或其附屬公司之商標)。有利的是，使用本發明之研磨墊並以含氧化矽之研磨劑研磨TEOS片狀晶片30秒之移除速度係等於或高於使用IC1000研磨墊並以含氧化矽之研磨劑研磨TEOS片狀晶片30秒之移除速度及60秒之移除速度。IC1000TM 可隨著研磨時間而增加TEOS移除速度，蓋因其係包含可賦予自該成份製作之零件熱塑性特點的脂肪族異氰酸酯(IC1010係羅門哈斯公司或其附屬公司之商標)。IC1000研磨墊之熱塑性特點似可促進該研磨墊與該晶片間之接觸隨著移除速度之增加而增加，直到某一最大移除速度出現為止。將墊對晶片之接觸面積增加至更高程度似乎使得移除速度降低，這是因為為部粗糙度對晶片接觸壓力的降低。同樣，由於交聯度或分子量之降低，不包含脂肪族異氰酸酯之配方將更具熱塑性特點；且其可顯示隨著研磨時間而增加更多之移除速度。然而，本發明之該墊具有足夠之孔隙度程度，以於該研磨製程非常早之時期最大化墊與晶片之接觸；且相對高度之交聯似可向該墊提供足夠之局部剛性，以促進該研磨製程。The 30-second removal rate of the IMD grinding of fumed silica can exceed 3,750 angstroms (Å) per minute. Furthermore, the present invention can provide a more IC1010 polyurethane polishing pad (TM) to the same abrasion test given in removal of 30 seconds faster than the removal rate (Trademark Department IC1010 of Rohm and Haas Company or its affiliates) at least 10% . Advantageously, the polishing pad of the present invention is used to grind the TEOS flake wafer with a cerium oxide-containing abrasive for 30 seconds at a removal rate equal to or higher than the use of the IC1000 polishing pad and polishing the TEOS flakes with a cerium oxide-containing abrasive. The removal speed of the wafer for 30 seconds and the removal speed of 60 seconds. As the milling time can IC1000 TM TEOS removal rate increases, because the cap can impart self-part system comprising the features of the thermoplastic composition of the produced aliphatic isocyanate (trademark of Rohm and Haas Company IC1010 lines or its subsidiaries). The thermoplastic nature of the IC1000 polishing pad appears to promote contact between the polishing pad and the wafer as the removal speed increases until a certain maximum removal rate occurs. Increasing the contact area of the pad to the wafer to a higher degree seems to cause a reduction in the removal speed because of the reduction in wafer contact pressure for the portion roughness. Also, due to the reduced degree of crosslinking or molecular weight, formulations that do not contain aliphatic isocyanates will be more thermoplastic; and they may show more removal speed as the milling time increases. However, the pad of the present invention has a sufficient degree of porosity to maximize pad-to-wafer contact at a very early stage of the polishing process; and relatively high cross-linking may provide sufficient local rigidity to the pad to facilitate The grinding process.
儘管移除速度可隨研磨劑含量而增加，與研磨劑無關之IC1010研磨墊移除速度的改善係表示研磨效能之重要進展。舉例而言，此促進以低缺陷增加移除速度並可降低漿料成本。除了移除速度外，晶片規格之不一致性亦為重要研磨效能之考量。典型地，因為經研磨晶片之一致性對於獲得最大數目之良好研磨的晶粒(die)係重要者，故該晶片規格之不一致性應低於6%。Although the removal rate can be increased with the abrasive content, the improvement in the polishing rate of the IC1010 polishing pad, which is independent of the abrasive, represents an important advance in the polishing performance. For example, this promotes increased removal speed with low defects and can reduce slurry costs. In addition to the removal speed, inconsistencies in wafer specifications are also important considerations for polishing performance. Typically, the wafer specification inconsistency should be less than 6% because the consistency of the ground wafer is important to obtain the largest number of well-ground dies.
為了本說明書之目的，『聚胺酯』係自雙官能異氰酸酯或多官能異氰酸酯所衍生之產物，如聚醚脲(polyetherureas)、聚異氰酸酯、聚胺酯、聚脲、聚胺酯脲、其共聚物及混合物。澆鑄聚胺酯研磨墊係適用於平面化半導體、光學及磁性基板。該墊之特殊研磨性能係部份源於預聚物二醇與多官能異氰酸酯之預聚物反應產物。該預聚物產物係以選自包含固化多胺、固化多元醇、固化醇胺及其混合物之群組之固化劑固化，以形成研磨墊。已經發現，控制該固化劑與該預聚物反應產物中未反應NCO之比例可改善研磨過程中多孔墊之缺陷效能。For the purposes of this specification, "polyurethane" is a product derived from a difunctional isocyanate or a polyfunctional isocyanate such as polyetherureas, polyisocyanates, polyurethanes, polyureas, polyurethanes, copolymers and mixtures thereof. The cast polyurethane polishing pad is suitable for planarizing semiconductor, optical and magnetic substrates. The special abrasive properties of the mat are derived in part from the prepolymer reaction product of the prepolymer diol and the polyfunctional isocyanate. The prepolymer product is cured with a curing agent selected from the group consisting of a cured polyamine, a cured polyol, a curative alcohol amine, and mixtures thereof to form a polishing pad. It has been discovered that controlling the ratio of unreacted NCO in the curing agent to the prepolymer reaction product improves the defect performance of the porous mat during milling.
胺甲酸酯之製備係涵蓋自多官能芳香異氰酸酯及預聚物多元醇製備異氰酸酯封端之胺甲酸酯預聚物。該預聚物多元醇係聚四伸甲基醚二醇(PTMEG)。該多官能芳香異氰酸酯之實例係包括2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4’-二苯甲烷二異氰酸酯、萘-1,5-二異氰酸酯、二異氰酸聯甲苯胺、對伸苯基二異氰酸酯、伸二甲苯基二異氰酸酯及其混合物。該多官能芳香異氰酸酯係含有少於20重量%之脂肪族異氰酸酯如4,4’-二環己基甲烷二異氰酸酯、異佛酮二異氰酸酯及環己烷二異氰酸酯。較佳者，該多官能芳香異氰酸酯係含有少於15重量%之脂肪族異氰酸酯，更佳者，含有少於12重量%之脂肪族異氰酸酯。The preparation of urethanes covers the preparation of isocyanate-terminated urethane prepolymers from polyfunctional aromatic isocyanates and prepolymer polyols. The prepolymer polyol is polytetramethylene glycol glycol (PTMEG). Examples of the polyfunctional aromatic isocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, diisocyanate Toluidine, p-phenylene diisocyanate, xylylene diisocyanate, and mixtures thereof. The polyfunctional aromatic isocyanate contains less than 20% by weight of an aliphatic isocyanate such as 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate and cyclohexane diisocyanate. Preferably, the polyfunctional aromatic isocyanate contains less than 15% by weight of aliphatic isocyanate, and more preferably less than 12% by weight of aliphatic isocyanate.
典型地，該預聚物反應產物係以固化胺(如多胺或含有多胺之混合物)反應或固化。舉例而言，可將該多胺與醇胺或單胺混合。為了本說明書之目的，多胺係包括二胺及其他多官能胺。固化多胺之實例係包括芳香二胺或多胺(如4,4’-亞甲基-雙-鄰-氯苯胺[MBCA]、4,4’-亞甲基-雙-(3-氯-2,6-二乙基苯胺)[MCDEA]；二甲基硫基甲苯二胺；三伸甲基二醇二-對-胺基苯甲酸酯；聚四伸甲基氧化物二-對-胺基苯甲酸酯；聚四伸甲基氧化物單-對-胺基苯甲酸酯；聚伸丙基氧化物二-對-胺基苯甲酸酯；聚伸丙基氧化物單-對-胺基苯甲酸酯；1,2-雙(2-胺基苯基硫基)乙烷；4,4’-亞甲基-雙-苯胺；二乙基甲苯二胺；5-第三丁基-2,4-甲苯二胺及3-第三丁基-2,6-甲苯二胺；5-第三戊基-2,4-甲苯二胺及3-第三戊基-2,6-甲苯二胺；以及氯甲苯二胺。此外，MBCA添加係表示較佳固化胺。視需要而定，可以避免使用預聚物而以單一混合步驟來製造用於研磨墊之胺甲酸酯。Typically, the prepolymer reaction product is reacted or cured with a solidified amine such as a polyamine or a mixture containing a polyamine. For example, the polyamine can be mixed with an alcohol amine or a monoamine. For the purposes of this specification, polyamines include diamines and other polyfunctional amines. Examples of cured polyamines include aromatic diamines or polyamines (eg, 4,4'-methylene-bis-o-chloroaniline [MBCA], 4,4'-methylene-bis-(3-chloro-) 2,6-diethylaniline)[MCDEA]; dimethylthiotoluenediamine; trimethylglycol di-p-aminobenzoate; polytetramethylene oxide di-pair Amino benzoate; polytetramethylene oxide mono-p-amino benzoate; poly propyl oxide di-p-amino benzoate; poly propyl oxide mono- p-Aminobenzoic acid ester; 1,2-bis(2-aminophenylthio)ethane; 4,4'-methylene-bis-aniline; diethyltoluenediamine; 5- Tributyl-2,4-toluenediamine and 3-tert-butyl-2,6-toluenediamine; 5-tripentyl-2,4-toluenediamine and 3-tripypentyl-2 , 6-toluenediamine; and chlorotoluenediamine. In addition, MBCA addition means better curing of the amine. If necessary, the use of the prepolymer can be avoided to produce the urethane for the polishing pad in a single mixing step. ester.
較佳係對用以作成該研磨墊之聚合物組成份作選擇，故所得墊之形態係安定且可輕易複製者。舉例而言，當混合4,4’-亞甲基-雙-鄰-氯苯胺[MBCA]與二異氰酸酯以形成聚胺酯聚合物時，控制單胺、二胺與三胺之量一般係有利者。控制單胺、二胺及三胺之比例可將該化學比例及所得聚合物分子量保持於一致的範圍。此外，一般來說控制添加劑(如抗氧化劑)及雜質(如水)對於一致的製造是重要的。舉例而言，因為水與異氰酸酯反應形成氣態二氧化碳，控制水濃度可影響於該聚合物基質內形成孔之二氧化碳氣泡的濃度。異氰酸酯與偶發的水反應還減少用於與鏈伸長劑反應之可用異氰酸酯，故除了交聯程度(如果存在過量異氰酸酯基)及所得聚合物之分子量之外，其改化學計量學。Preferably, the composition of the polymer used to form the polishing pad is selected so that the resulting mat is stable and readily replicable. For example, when 4,4'-methylene-bis-o-chloroaniline [MBCA] is mixed with a diisocyanate to form a polyurethane polymer, it is generally advantageous to control the amount of monoamine, diamine and triamine. Controlling the ratio of monoamine, diamine and triamine maintains the chemical ratio and the molecular weight of the resulting polymer in a consistent range. In addition, it is generally important to control additives such as antioxidants and impurities such as water for consistent manufacturing. For example, because water reacts with isocyanate to form gaseous carbon dioxide, controlling the water concentration can affect the concentration of carbon dioxide bubbles that form pores within the polymer matrix. The reaction of the isocyanate with the incidental water also reduces the available isocyanate for reaction with the chain extender, so it changes stoichiometry in addition to the degree of crosslinking (if excess isocyanate groups are present) and the molecular weight of the resulting polymer.
該聚胺酯聚合物材料較佳係自甲苯二異氰酸酯與聚四伸甲基醚二醇之預聚物及芳香二胺形成。該芳香二胺最佳係4,4’-亞甲基-雙-鄰-氯苯胺或4,4’-亞甲基-雙-(3-氯-2,6-二乙基苯胺)。未反應預聚物%NCO之較佳範圍係8.75至9.05。具有此未反應NCO範圍之適宜預聚物之具體實例係Chemtura製造之預聚物LF750D。此外，LF750D係表示低遊離(low-free)異氰酸酯預聚物，該預聚物中，遊離2,4 TDI及2,6 TDI單體各自係少於0.1重量%，且該預聚物係具有比傳統預聚物更一致之預聚物分子量分布。具有改善之預聚物分子量一致性及低遊離異氰酸酯單體之此『低遊離』預聚物促進更規則之聚合物結構且可改善研磨墊之一致性。除了控制未反應NCO之重量百分率外，該固化及預聚物反應產物中，OH或NH2 與未反應NCO的化學計量比典型係80%至97%，較佳係80%至90%；更佳者，OH或NH2 與未反應NCO的化學計量比係83%至87%。此化學計量學可藉由直接提供該化學計量程度之原料達成，亦或是故意或是曝露於偶發濕氣而間接藉由使某些NCO與水反應而達成。The polyurethane polymer material is preferably formed from a prepolymer of toluene diisocyanate and polytetramethylene glycol glycol and an aromatic diamine. The aromatic diamine is preferably 4,4'-methylene-bis-o-chloroaniline or 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline). The preferred range of unreacted prepolymer % NCO is 8.75 to 9.05. Specific examples of suitable prepolymers having this unreacted NCO range are manufactured by Chemtura Prepolymer LF750D. Further, LF750D represents a low-free isocyanate prepolymer in which free 2,4 TDI and 2,6 TDI monomers are each less than 0.1% by weight, and the prepolymer has A prepolymer molecular weight distribution that is more consistent than conventional prepolymers. This "low free" prepolymer having improved molecular weight consistency of the prepolymer and low free isocyanate monomer promotes a more regular polymer structure and improves the consistency of the polishing pad. In addition to controlling the weight percentage of unreacted NCO, the stoichiometric ratio of OH or NH 2 to unreacted NCO in the curing and prepolymer reaction product is typically from 80% to 97%, preferably from 80% to 90%; Preferably, the stoichiometric ratio of OH or NH 2 to unreacted NCO is between 83% and 87%. This chemometrics can be achieved by directly providing the stoichiometric amount of material, either indirectly or by exposure to incidental moisture, indirectly by reacting certain NCOs with water.
若該研磨墊係聚胺酯材料，則該完成之研磨墊之密度較佳係0.4至0.8公克(g)/平方公分(cm3 )。更佳者，完成之聚胺酯研磨墊之密度係0.5至0.75g/cm3 。以墊的總配方為基準計，中空聚合物顆粒負載密度(澆鑄前)為3.25重量%至4.25重量%、較佳3.25重量%至3.6重量%之公稱20μm孔或中空聚合物顆粒，可以產生具傑出研磨結果之該所欲密度。特別地，該中空聚合物顆粒於整個聚合物基質中提供隨機之孔分佈。特別地，該研磨墊具有閉合單元結構，且該聚合物基質形成環繞該閉合單元結構之連續網。儘管具有如此高之孔隙度，該研磨墊之蕭氏(Shore)D硬度典型係44至54。為了本說明書之目的，該蕭氏D硬度之測試係包括於測試前將墊樣本置於相對濕度50%之25℃環境中5天進行條件處理，並使用ASTM D2240略述之方法，以改善該硬度測試之再現性。If the polishing pad is a polyurethane material, the density of the finished polishing pad is preferably from 0.4 to 0.8 grams per square centimeter (cm 3 ). More preferably, the density of the finished polyurethane polishing pad is from 0.5 to 0.75 g/cm 3 . Based on the total formulation of the mat, the hollow polymer particles have a loading density (before casting) of from 3.25 wt% to 4.25 wt%, preferably from 3.25 wt% to 3.6 wt% of nominal 20 μm pores or hollow polymer particles, which can be produced The desired density of outstanding grinding results. In particular, the hollow polymer particles provide a random pore distribution throughout the polymer matrix. In particular, the polishing pad has a closed cell structure and the polymer matrix forms a continuous web surrounding the closed cell structure. Despite having such a high porosity, the Shore D hardness of the polishing pad is typically 44 to 54. For the purposes of this specification, the Shore D hardness test is performed by placing the pad sample in a 25 ° C environment at a relative humidity of 50% for 5 days prior to testing, and using the method outlined in ASTM D2240 to improve the Reproducibility of hardness testing.
中空聚合物顆粒之重量平均直徑係2至50微米(μm)。為了本說明書之目的，重量平均直徑係表示該中空聚合物顆粒於澆鑄前之平均直徑；且該顆粒可具有球狀或非球狀之形狀。該中空聚合物顆粒最佳係具有球狀形狀。該中空聚合物顆粒之重量平均直徑較佳係2至40μm。該中空聚合物顆粒之重量平均直徑最佳係10至30μm；此等中空聚合物顆粒典型係具有60g/公升(L)之平均密度。為了本說明書之目的，該中空聚合物顆粒之平均密度係表示於1公升體積內，該中空顆粒之緊密封裝未破碎密度(close-packed-non-crushed density)。平均直徑為35至50μm之中空顆粒典型係具有平均為42g/L之較低密度，蓋因其存在更多孔及更少壁材。不同尺寸及類型之中空顆粒可藉由下述方式而以等量孔體積加入：取一種尺寸之中空聚合物顆粒之質量除以其密度來確定孔之體積。此體積可隨後乘以其他種孔之密度，以確定該其他尺寸及類型之中空聚合物顆粒之質量，從而給出等量孔體積。舉例而言，如下述等式所顯示般The hollow polymer particles have a weight average diameter of 2 to 50 micrometers (μm). For the purposes of this specification, the weight average diameter refers to the average diameter of the hollow polymer particles prior to casting; and the particles may have a spherical or non-spherical shape. The hollow polymer particles preferably have a spherical shape. The hollow polymer particles preferably have a weight average diameter of from 2 to 40 μm. The hollow polymer particles preferably have a weight average diameter of 10 to 30 μm; such hollow polymer particles typically have an average density of 60 g/liter (L). For the purposes of this specification, the average density of the hollow polymer particles is expressed in a volume of 1 liter, which is a close-packed-non-crushed density. Hollow particles having an average diameter of 35 to 50 μm typically have a lower density of an average of 42 g/L, due to the presence of more pores and less wall material. Hollow particles of different sizes and types can be added in equal pore volumes by taking the mass of one size of hollow polymer particles divided by their density to determine the volume of the pores. This volume can then be multiplied by the density of the other species to determine the mass of the hollow polymer particles of the other size and type to give an equivalent pore volume. For example, as shown in the following equation
含有3重量%且密度為60g/L之20μm中空聚合物顆粒的配方將與2.1重量%且密度為40g/L之42μm中空聚合物顆粒等量。於形成本發明之研磨墊過程中，『密度a 』等於60g/L之平均密度，『密度b 』係5g/L至500g/L之平均密度以及『wt%a 』係3.25重量%至4.25重量%。較佳者，『密度b 』係10g/L至150g/L之平均密度以及『wt%a 』係3.25重量%至3.6重量%。A formulation containing 3% by weight and a density of 60 g/L of 20 μm hollow polymer particles would be equivalent to 2.1% by weight and a density of 40 g/L of 42 μm hollow polymer particles. In forming the polishing pad of the present invention, "density a " is equal to an average density of 60 g/L, "density b " is an average density of 5 g/L to 500 g/L, and "wt% a " is 3.25% to 4.25 weight. %. Preferably, the "density b " is an average density of from 10 g/L to 150 g/L and "wt% a " is from 3.25 wt% to 3.6% by weight.
膨脹之中空聚合物顆粒之重量平均直徑的公稱範圍係15至90μm。再者，高孔隙度與小孔尺寸之組合可具有減少缺陷之特殊益處。不過，如果該孔隙度程度變得過高，該研磨墊失去機械完整性及強度。舉例而言，加入構築研磨層30體積%至60體積%之重量平均直徑為2至50μm的中空聚合物顆粒，促進缺陷之減少。再者，將孔隙度保持於35體積%與55體積%之間，或更具體而言35體積%與50體積%之間，可促進移除速度之增加。為了本說明書之目的，體積%孔隙度係表示如下述方式決定之孔的體積百分率：1)自無孔隙度之聚合物公稱密度中減去所測量之該配方密度以確定自立方公分配方中『消失』之聚合物的質量；以及2)將『消失』之聚合物的質量除以無孔隙度之聚合物的公稱密度，以確定自cm3 配方中消失之聚合物的體積，再乘以100將其轉化為體積%孔隙度。或者，配方中孔體積百分率或體積%孔隙度可藉由下述方法決定之：1)自100g減去100g配方中該中空聚合物顆粒之質量以確定100g配方中聚合物基質之質量；2)將聚合物基質之質量除以該聚合物之公稱密度以確定100g配方中該聚合物之體積；3)將100g配方中該中空聚合物顆粒之質量除以該中空聚合物顆粒之公稱密度以確定100g配方中該中空聚合物顆粒之體積；4)將100g配方中該聚合物之體積加上100g配方中該中空聚合物顆粒或孔之體積，以確定100g配方之體積；以及5)將100g配方中該中空聚合物顆粒或孔之體積除以100g配方之總體積，再乘以100，給出該配方中孔之體積百分率或孔隙度。對於孔隙度或孔之體積%，兩種方法將得到相似值，儘管第二種方法將顯示較第一種方法低之孔隙度或孔之體積%，於第一種方法中，製程過程之參數如反映放熱量可造成中空聚合物顆粒或微球膨脹至超出其公稱『膨脹體積』。因為對於特定之孔或孔隙度程度而言，孔尺寸之下降傾向於增加研磨速度，故控制澆鑄過程之放熱量以防止該預膨脹之中空聚合物顆粒或微球的進一步膨脹係重要者。舉例而言，澆鑄入室溫模具、限制塊高度、降低預聚物溫度、降低固化胺溫度、減少NCO及限制遊離TDI單體全部可減少由異氰酸酯之反應產生的放熱量。The nominal range of the weight average diameter of the expanded hollow polymer particles is from 15 to 90 μm. Furthermore, the combination of high porosity and small pore size can have the particular benefit of reducing defects. However, if the degree of porosity becomes too high, the polishing pad loses mechanical integrity and strength. For example, hollow polymer particles having a weight average diameter of 2 to 50 μm, which constitutes 30 to 60% by volume of the abrasive layer, are added to promote the reduction of defects. Further, maintaining the porosity between 35 vol% and 55 vol%, or more specifically between 35 vol% and 50 vol%, may promote an increase in removal speed. For the purposes of this specification, vol% porosity refers to the volume fraction of pores determined as follows: 1) subtracting the measured density of the polymer from the nominal density of the non-porosity polymer to determine from the cubic distribution side. The mass of the disappearing polymer; and 2) dividing the mass of the "disappearing" polymer by the nominal density of the non-porous polymer to determine the volume of the polymer that has disappeared from the cm 3 formulation, multiplied by 100 It is converted to volume % porosity. Alternatively, the percent pore volume or volume percent porosity in the formulation can be determined by the following method: 1) subtracting the mass of the hollow polymer particles from the 100 g formulation from 100 g to determine the mass of the polymer matrix in the 100 g formulation; 2) Dividing the mass of the polymer matrix by the nominal density of the polymer to determine the volume of the polymer in the 100 g formulation; 3) dividing the mass of the hollow polymer particles in the 100 g formulation by the nominal density of the hollow polymer particles to determine The volume of the hollow polymer particles in a 100g formulation; 4) the volume of the polymer in 100g of the formulation plus 100g of the volume of the hollow polymer particles or pores in the formulation to determine the volume of the 100g formulation; and 5) the formulation of 100g The volume of the hollow polymer particles or pores is divided by the total volume of the 100 g formulation and multiplied by 100 to give the volume fraction or porosity of the pores in the formulation. For porosity or pore volume %, the two methods will give similar values, although the second method will show a lower porosity or pore volume % than the first method. In the first method, the parameters of the process If the exotherm is reflected, the hollow polymer particles or microspheres may expand beyond their nominal "expansion volume". Since the reduction in pore size tends to increase the rate of grinding for a particular pore or degree of porosity, controlling the exotherm of the casting process to prevent further expansion of the pre-expanded hollow polymer particles or microspheres is important. For example, casting into a room temperature mold, limiting the block height, lowering the prepolymer temperature, lowering the solidified amine temperature, reducing the NCO, and limiting the free TDI monomer all reduce the amount of heat generated by the reaction of the isocyanate.
如同大多數傳統有孔研磨墊一樣，研磨墊之修整(如鑽石盤修整)用於增加移除速度並改善晶片規格之非一致性。儘管修整可以週期方式(如各晶片修整30秒後)予以作用)或以連續方式予以作用，連續修整係提供建立穩態研磨條件的優點，以改善控制移除速度。修整典型係增加該研磨墊之移除速度並防止典型與研磨墊之表面磨損相關聯之移除速度的衰減。特別地，該研磨劑修整係形成可於研磨過程中捕獲燻矽顆粒之粗糙表面。第1圖至第3圖係氧化矽顆粒可於與該研磨墊之孔相鄰之該粗糙表面內積累之圖解。此氧化矽顆粒積累於該研磨墊內似可藉由導致高移除速度而增加該研磨墊之效率。除了修整外，槽及穿孔可對於漿料之分布、研磨一致性、碎屑之移除及基板之移除速度提供進一步之益處。As with most conventional perforated polishing pads, polishing pad conditioning (such as diamond disk conditioning) is used to increase removal speed and improve wafer specification inconsistency. Although the trimming can be effected in a periodic manner (e.g., after each wafer has been trimmed for 30 seconds) or in a continuous manner, continuous trimming provides the advantage of establishing steady-state grinding conditions to improve control removal speed. Trimming typically increases the removal rate of the polishing pad and prevents attenuation of the removal speed typically associated with surface wear of the polishing pad. In particular, the abrasive conditioning forms a rough surface that captures the smoked particles during the milling process. Figures 1 through 3 are diagrams showing the accumulation of cerium oxide particles in the rough surface adjacent to the pores of the polishing pad. The accumulation of such cerium oxide particles in the polishing pad may increase the efficiency of the polishing pad by causing a high removal rate. In addition to trimming, the grooves and perforations provide further benefits to slurry distribution, abrasive consistency, debris removal, and substrate removal speed.
對於本發明之實施例，該聚合物墊材料係藉由將作為胺甲酸酯預聚物之各種量之異氰酸酯(49℃，比較例包括43℃至63℃預聚物)與4,4’-亞甲基-雙-鄰-氯苯胺[MBCA](115℃)混合而製備之。特別地，特定甲苯二異氰酸酯[TDI]與聚四伸甲基醚二醇[PTMEG]預聚物提供具有不同性能之研磨墊。該胺甲酸酯/多官能胺混合物係與中空聚合物微球(AkzoNobel製造之551DE20d60或551DE40d42)於將該預聚物與鏈伸長劑混合之前或之後混合。該中空聚合物微球可於加入該多官能胺之前與該預聚物於60rpm混合，隨後將該混合物於4500rpm混合；或該中空聚合物微球可加入至位於3600rpm之混合頭內的該胺甲酸酯/多官能胺混合物中。該微球之重量平均直徑為15至50μm，其範圍為5至200μm。將最終混合物轉移至模具並准許其凝膠化約15分鐘。For the examples of the present invention, the polymer mat material is obtained by using various amounts of isocyanate as a urethane prepolymer (49 ° C, comparative examples including 43 ° C to 63 ° C prepolymer) and 4, 4' Prepared by mixing methylene-bis-o-chloroaniline [MBCA] (115 ° C). In particular, specific toluene diisocyanate [TDI] and polytetramethylene glycol diol [PTMEG] prepolymers provide polishing pads having different properties. The urethane/polyfunctional amine mixture is combined with hollow polymer microspheres (made by AkzoNobel) 551DE20d60 or 551DE40d42) is mixed before or after mixing the prepolymer with the chain extender. The hollow polymer microspheres may be mixed with the prepolymer at 60 rpm prior to the addition of the polyfunctional amine, and then the mixture may be mixed at 4500 rpm; or the hollow polymer microspheres may be added to the amine in a mixing head at 3600 rpm. In a formate/polyfunctional amine mixture. The microspheres have a weight average diameter of 15 to 50 μm and a range of 5 to 200 μm. The final mixture was transferred to a mold and allowed to gel for about 15 minutes.
隨後將該模具置於固化爐中，且以如下之循環固化：於30分鐘內自環境溫度均勻升溫至設定溫度104℃，於104℃保持15.5小時，再於2小時內自該設定溫度降溫至21℃。比較例F至比較例K使用更短之固化循環，於100℃保持約8小時。隨後將該模製件『切削』成薄片，且於室溫下於該表面上機械加工出大通道或槽；於較高溫度切削可改善表面粗糙度及片厚度一致性。如表中所示，樣本1至樣本2係表示本發明之研磨墊，而樣本A至樣本Z係表示比較例。The mold is then placed in a curing oven and cured in the following cycle: uniformly heated from ambient temperature to a set temperature of 104 ° C in 30 minutes, maintained at 104 ° C for 15.5 hours, and then cooled from the set temperature within 2 hours. 21 ° C. Comparative Examples F to Comparative K used a shorter curing cycle and were maintained at 100 ° C for about 8 hours. The molded part is then "cut" into a thin sheet and a large channel or groove is machined on the surface at room temperature; cutting at a higher temperature improves surface roughness and sheet thickness uniformity. As shown in the table, Samples 1 to 2 represent the polishing pads of the present invention, and Samples A to Z represent the comparative examples.
Adiprene LF600D、LF750D及Royalcast 2505係對應於甲苯二異氰酸酯與由Chemtura製造之PTMEG產品的混合物。LF600D及LF750D係低遊離異氰酸酯預聚物，而Royalcast 2505係具有高度之遊離異氰酸酯單體。Adiprene LF600D, LF750D and Royalcast 2505 correspond to a mixture of toluene diisocyanate and a PTMEG product manufactured by Chemtura. LF600D and LF750D are low free isocyanate prepolymers, while Royalcast 2505 has a high degree of free isocyanate monomer.
於來自應用材料公司(Applied Materials,Inc.)之研磨機上使用93rpm之檯板轉動速度、87rpm之晶片載體頭轉動速度以及5磅/平方英吋(psi)之下壓力研磨TEOS片狀晶片，從而測試各實施例之研磨墊。該研磨漿料係ILD3225與DI水之1:1混合物，並以150毫升(ml)/分鐘(min)之速度提供至該研磨墊之表面上。使用原位修整製程而使用AD3BG150855修整盤對該研磨墊進行鑽石修整。研磨TEOS片狀晶片30秒或60秒，使用實施例墊之各測試還包括使用IC1010墊之晶片作為基線。最重要者係相對於IC1010之30秒研磨速度，蓋因其將對降低該標準研磨墊之研磨時間具有最大效果。該研磨結果係顯示於下表2。From Applied Materials, Inc. The polishing pads of the various examples were tested on a grinder using a platen rotation speed of 93 rpm, a wafer carrier head rotation speed of 87 rpm, and a pressure-milled TEOS sheet wafer at 5 pounds per square inch (psi). The abrasive slurry was a 1:1 mixture of ILD3225 and DI water and was supplied to the surface of the polishing pad at a rate of 150 milliliters (ml) per minute (min). Use in-situ trimming process The polishing pad of the AD3BG150855 is trimmed with diamonds. The TEOS flake wafer was ground for 30 seconds or 60 seconds, and each test using the example pad also included the use of the IC1010 pad wafer as a baseline. The most important is the 30 second grinding speed relative to IC1010, which has the greatest effect on reducing the grinding time of the standard polishing pad. The results of this grinding are shown in Table 2 below.
此等數據說明，負載有3.36重量%之中空聚合物微球係提供未預期之移除速度的增加。特別地，樣本1及樣本2具有傑出之30秒移除速度及60秒移除速度。該樣本1及樣本2之30秒移除速度說明，該研磨墊於支援更高產量的縮短研磨製程的早期具有高移除速度。負載有3.01重量%(相同預聚物為2.94重量%)或3.66重量%或更多之中空聚合物微球的比較例得到較低之30秒移除速度及較低之整體移除速度。此外，第1圖至第3圖說明，該研磨墊之表面似可於研磨優勢位置處捕獲燻矽。此對於燻矽之親和性似乎導致研磨效能增加。These data demonstrate that 3.36 wt% of hollow polymer microspheres are loaded to provide an unexpected increase in removal rate. In particular, Sample 1 and Sample 2 have an outstanding 30 second removal speed and a 60 second removal speed. The 30 second removal speed of Sample 1 and Sample 2 indicates that the polishing pad has a high removal speed early in the shortening of the grinding process to support higher throughput. A comparative example with 3.01% by weight (2.94% by weight of the same prepolymer) or 3.66 % by weight or more of hollow polymeric microspheres resulted in a lower 30 second removal rate and a lower overall removal rate. In addition, Figures 1 through 3 illustrate that the surface of the polishing pad appears to capture smoker at a preferred location of the polishing. This affinity for smoked sputum seems to result in increased grinding performance.
表3係說明該中空聚合物微球達成超過每立方公分之墊配方中一百萬個微球的負載程度。Table 3 illustrates the extent to which the hollow polymeric microspheres achieve a loading of more than one million microspheres per cubic centimeter of the pad formulation.
下表4係顯示預聚物%NCO，並比較多個無填料或孔隙度之經MBCA-固化之彈性體的機械強度性能，該彈性體係自以ASTM D412方法測試之該實施例配方中所使用之預聚物作成者。所顯示之彈性性能係ASTM D1566-08A中定義。此外，表4係顯示如該預聚物製造商所報告之以MBCA固化之該預聚物的公稱密度。Table 4 below shows the prepolymer % NCO and compares the mechanical strength properties of a plurality of MBCA-cured elastomers without filler or porosity, which were used in the formulation of this example tested in accordance with the ASTM D412 method. Prepolymer producer. The elastic properties shown are defined in ASTM D1566-08A. In addition, Table 4 shows the nominal density of the prepolymer cured with MBCA as reported by the prepolymer manufacturer.
表4係說明，除了填料濃度外，該研磨墊之機械性能似乎亦可影響研磨效能。具體而言，使用LF600D之比較例R之該聚合物之剛性(藉由其100%模數作為最佳指示者)似乎不足以支援用於燻矽研磨之高移除速度；而使用2505準預聚物作成之比較例F至比較例K之剛性似乎超過支援燻矽研磨之高移除速度所需者。自Royalcast 2505澆鑄之聚胺酯材料係如此之脆，以至於其於達到100%延長之前即已破碎。Table 4 shows that in addition to the filler concentration, the mechanical properties of the polishing pad also appear to affect the polishing performance. In particular, the rigidity of the polymer using Comparative Example R of LF600D (with its 100% modulus as the best indicator) does not appear to be sufficient to support the high removal rate for the smoked mash; The rigidity of Comparative Example F to Comparative Example K made with 2505 quasi-prepolymer appeared to exceed the requirement for high removal speed to support the smoked mash. The polyurethane material cast from Royalcast 2505 is so brittle that it is broken before it reaches 100% elongation.
總之，該研磨墊係有效用於研磨銅、介電材料、阻擋物及鎢晶片。特別地，該研磨墊係適用於ILD研磨，尤其適用於燻矽之ILD研磨應用。該研磨墊係具有用以有效研磨之快速斜面(ramp)，該斜面於30秒提供高移除速度。本發明之研磨墊之30秒移除速度及60秒移除速度兩者均可超出IC1000研磨墊之30秒移除速度及60秒移除速度。本發明之墊之此種快速研磨回應促進高於傳統多孔研磨墊之晶片產量。In summary, the polishing pad is effective for polishing copper, dielectric materials, barriers, and tungsten wafers. In particular, the polishing pad is suitable for ILD grinding, and is particularly suitable for use in smoked ILD grinding applications. The polishing pad has a fast ramp for effective grinding that provides a high removal speed in 30 seconds. Both the 30 second removal speed and the 60 second removal speed of the polishing pad of the present invention can exceed the 30 second removal speed and 60 second removal speed of the IC1000 polishing pad. This rapid grinding response of the pad of the present invention promotes wafer throughput over conventional porous polishing pads.
第1圖係本發明之墊之研磨表面的250X放大之研磨後掃描電子顯微照片(post-polishing scanning electron photomicrograph)。Figure 1 is a 250X magnified post-polishing scanning electron photomicrograph of the abrasive surface of the pad of the present invention.
第2圖係本發明之墊之研磨表面的500X放大之研磨後掃描電子顯微照片。Figure 2 is a post-grinding scanning electron micrograph of a 500X magnification of the abrasive surface of the pad of the present invention.
第3圖係第1圖及第2圖中該研磨墊於第2圖相同區域之500X EDS圖像，係說明以含氧化矽之研磨漿料研磨後之高濃度矽。Fig. 3 is a 500X EDS image of the polishing pad in the same area as in Fig. 2 in Fig. 1 and Fig. 2, showing a high concentration enthalpy after polishing with a polishing slurry containing cerium oxide.
由於本案的圖皆為結果數據，並非適當的代表圖。故本案無指定代表圖。Since the figures in this case are all result data, they are not appropriate representative figures. Therefore, there is no designated representative map in this case.
Claims (8)
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| US12/221,581 US20100035529A1 (en) | 2008-08-05 | 2008-08-05 | Chemical mechanical polishing pad |
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| EP (1) | EP2151299B1 (en) |
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| US8257544B2 (en) | 2009-06-10 | 2012-09-04 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pad having a low defect integral window |
| US8551201B2 (en) * | 2009-08-07 | 2013-10-08 | Praxair S.T. Technology, Inc. | Polyurethane composition for CMP pads and method of manufacturing same |
| JP5528169B2 (en) | 2010-03-26 | 2014-06-25 | 東洋ゴム工業株式会社 | Polishing pad, method for manufacturing the same, and method for manufacturing a semiconductor device |
| JP5534907B2 (en) * | 2010-03-31 | 2014-07-02 | 富士紡ホールディングス株式会社 | Polishing pad and method of manufacturing polishing pad |
| US8257545B2 (en) | 2010-09-29 | 2012-09-04 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pad with light stable polymeric endpoint detection window and method of polishing therewith |
| US9211628B2 (en) * | 2011-01-26 | 2015-12-15 | Nexplanar Corporation | Polishing pad with concentric or approximately concentric polygon groove pattern |
| JP5738730B2 (en) * | 2011-09-22 | 2015-06-24 | 東洋ゴム工業株式会社 | Polishing pad |
| JP5738729B2 (en) * | 2011-09-22 | 2015-06-24 | 東洋ゴム工業株式会社 | Polishing pad |
| JP5738728B2 (en) * | 2011-09-22 | 2015-06-24 | 東洋ゴム工業株式会社 | Polishing pad |
| JP5738731B2 (en) * | 2011-09-22 | 2015-06-24 | 東洋ゴム工業株式会社 | Polishing pad |
| US9079289B2 (en) | 2011-09-22 | 2015-07-14 | Toyo Tire & Rubber Co., Ltd. | Polishing pad |
| US9144880B2 (en) * | 2012-11-01 | 2015-09-29 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Soft and conditionable chemical mechanical polishing pad |
| US9102034B2 (en) | 2013-08-30 | 2015-08-11 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Method of chemical mechanical polishing a substrate |
| US20150306731A1 (en) * | 2014-04-25 | 2015-10-29 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pad |
| TWI518176B (en) | 2015-01-12 | 2016-01-21 | 三芳化學工業股份有限公司 | Polishing pad and method for making the same |
| US10946495B2 (en) * | 2015-01-30 | 2021-03-16 | Cmc Materials, Inc. | Low density polishing pad |
| JP2017185563A (en) * | 2016-04-01 | 2017-10-12 | 富士紡ホールディングス株式会社 | Polishing pad |
| KR101853021B1 (en) * | 2017-01-12 | 2018-04-30 | 에스케이씨 주식회사 | Porous polyurethane polishing pad and preparation method thereof |
| KR102102973B1 (en) * | 2017-11-14 | 2020-04-22 | 에스케이씨 주식회사 | Polishing pad |
| KR102058877B1 (en) * | 2018-04-20 | 2019-12-24 | 에스케이씨 주식회사 | POROUS POLYURETHANE POLISHING PAD and PREPARATION METHOD THEREOF |
| KR102188525B1 (en) * | 2019-10-29 | 2020-12-08 | 에스케이씨 주식회사 | Polishing pad, preparation method thereof, and preparation method of semiconductor device using same |
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| MY114512A (en) * | 1992-08-19 | 2002-11-30 | Rodel Inc | Polymeric substrate with polymeric microelements |
| US6514301B1 (en) * | 1998-06-02 | 2003-02-04 | Peripheral Products Inc. | Foam semiconductor polishing belts and pads |
| ATE337137T1 (en) * | 1998-11-09 | 2006-09-15 | Toray Industries | POLISHING PAD AND POLISHING APPARATUS |
| US6777455B2 (en) * | 2000-06-13 | 2004-08-17 | Toyo Tire & Rubber Co., Ltd. | Process for producing polyurethane foam |
| US20050171224A1 (en) * | 2004-02-03 | 2005-08-04 | Kulp Mary J. | Polyurethane polishing pad |
| US7329174B2 (en) * | 2004-05-20 | 2008-02-12 | Jsr Corporation | Method of manufacturing chemical mechanical polishing pad |
| JP4475404B2 (en) * | 2004-10-14 | 2010-06-09 | Ｊｓｒ株式会社 | Polishing pad |
| US7445847B2 (en) * | 2006-05-25 | 2008-11-04 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pad |
| US7371160B1 (en) * | 2006-12-21 | 2008-05-13 | Rohm And Haas Electronic Materials Cmp Holdings Inc. | Elastomer-modified chemical mechanical polishing pad |
| US7569268B2 (en) * | 2007-01-29 | 2009-08-04 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pad |
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| US20100035529A1 (en) | 2010-02-11 |
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