WO2017034157A1 - Composition de suspension de pmc pour film organique, son procédé de préparation, et procédé de polissage d'un film organique l'utilisant - Google Patents
Composition de suspension de pmc pour film organique, son procédé de préparation, et procédé de polissage d'un film organique l'utilisant Download PDFInfo
- Publication number
- WO2017034157A1 WO2017034157A1 PCT/KR2016/007937 KR2016007937W WO2017034157A1 WO 2017034157 A1 WO2017034157 A1 WO 2017034157A1 KR 2016007937 W KR2016007937 W KR 2016007937W WO 2017034157 A1 WO2017034157 A1 WO 2017034157A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organic film
- cmp slurry
- group
- substituted
- unsubstituted
- Prior art date
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- 239000002002 slurry Substances 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims description 101
- 238000005498 polishing Methods 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007800 oxidant agent Substances 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- OPFTUNCRGUEPRZ-QLFBSQMISA-N Cyclohexane Natural products CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 claims 1
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- 125000003118 aryl group Chemical group 0.000 description 28
- 125000000524 functional group Chemical group 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
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- 229920000642 polymer Polymers 0.000 description 10
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
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- 0 *1c(c*(C=CCC2)c2c2)c2-c2c1cccc2 Chemical compound *1c(c*(C=CCC2)c2c2)c2-c2c1cccc2 0.000 description 8
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
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- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 6
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- 125000003342 alkenyl group Chemical group 0.000 description 6
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- 125000004404 heteroalkyl group Chemical group 0.000 description 5
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- MCVVDMSWCQUKEV-UHFFFAOYSA-N (2-nitrophenyl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1[N+]([O-])=O MCVVDMSWCQUKEV-UHFFFAOYSA-N 0.000 description 1
- DLDWUFCUUXXYTB-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 DLDWUFCUUXXYTB-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 1
- CPPFVJLHDNOVTN-UHFFFAOYSA-N 1-Methoxypyrene Chemical compound C1=C2C(OC)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 CPPFVJLHDNOVTN-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- NJQJGRGGIUNVAB-UHFFFAOYSA-N 2,4,4,6-tetrabromocyclohexa-2,5-dien-1-one Chemical compound BrC1=CC(Br)(Br)C=C(Br)C1=O NJQJGRGGIUNVAB-UHFFFAOYSA-N 0.000 description 1
- NXKOSHBFVWYVIH-UHFFFAOYSA-N 2-n-(butoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound CCCCOCNC1=NC(N)=NC(N)=N1 NXKOSHBFVWYVIH-UHFFFAOYSA-N 0.000 description 1
- KFVIYKFKUYBKTP-UHFFFAOYSA-N 2-n-(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCNC1=NC(N)=NC(N)=N1 KFVIYKFKUYBKTP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001451794 Cerus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
Definitions
- the present invention relates to a CMP slurry composition for an organic film, a method for producing the same, and an organic film polishing method using the same. More specifically, the present invention relates to a CMP slurry composition suitable for polishing an organic film formed on the surface of an abrasive, such as a semiconductor wafer, a method for producing the same, and an organic film polishing method using the same.
- a technique of using a hydrocarbon-based organic film that can be exclusively etched with an inorganic film such as a silicon oxide film or a silicon nitride film formed on a semiconductor has been developed.
- a gap for forming an inorganic film such as a silicon oxide film or a silicon nitride film on a patterned silicon wafer and then filling via-holes formed in the inorganic film with an organic film material by spin coating.
- Filling (gap-filling) processes are being applied. After such a gap-fill process, a planarization process of removing the excess organic film through a chemical mechanical polishing (CMP) process is performed.
- CMP chemical mechanical polishing
- Korean Patent Publication No. 2007-0057009 discloses a technique of using polymer particles having functional groups on the surface of the CMP slurry instead of inorganic particles to solve the above problems.
- the CMP slurry using the polymer particles as the abrasive particles as described above has a problem in that a sufficient polishing amount cannot be obtained when polishing the organic film having a high film density or a high degree of curing.
- the organic film has various film qualities according to the film composition
- the organic film is formed by reacting various compounds, it is difficult to predict polishing characteristics according to the composition of the CMP slurry unlike the inorganic film. Therefore, at present, a slurry having a specific composition is prepared, and then the wafer coated with the organic film to be actually polished is used, and then the film thickness and film characteristics are monitored to monitor the suitability of the composition. Development of CMP slurry for membranes is underway. However, the slurry development through the above method has a high cost and time input, there is a problem inefficient.
- An object of the present invention is to provide a CMP slurry composition for organic membranes having an excellent polishing effect on organic membranes.
- Still another object of the present invention is to provide a method for polishing an organic film using the CMP slurry composition for organic films having an excellent polishing effect on the organic film.
- the present invention provides a CMP slurry for an organic film comprising an oxidizing agent and a solvent to provide.
- the change amount ⁇ W of the water contact angle represented by the following formula (1) is about 5 ° to About 90 °, specifically about 5 ° to about 70 °, more specifically about 10 ° to about 50 °.
- Equation (1) ⁇ 1 is a water contact angle measured by dropping DI WATER on the surface of the organic film before immersing the organic film-coated wafer in a CMP slurry, and ⁇ 2 is the organic film coated It is a water contact angle measured by immersing the wafer in a CMP slurry for about 10 hours and then dropping DI water on the surface of the organic film.
- the oxidizing agent is Fe 3 +, Ce 4 +, Ce 3 +, Cu 2 + , and can include one or more of Ag +, as required, may further include a hydrogen peroxide.
- the oxidizing agent is Fe 3+ , Cu 2 +, The Ce 3 + or Ce 4 + It may be one containing inclusive, or Ce 4 +, Ce 3 +, Cu 2 +, and Ag + 1 mixture of types of metal ions and hydrogen peroxide or more of which.
- the oxidizing agent may include a metal salt including Ce and hydrogen peroxide in a weight ratio of about 1: 1.5 to about 1: 3.
- the oxidant may be included in about 0.001% to about 5% by weight based on the total weight of the CMP slurry composition.
- the CMP slurry composition for organic films of the present invention may further include an abrasive comprising at least one of silica, alumina, ceria, titania, and zirconia.
- the abrasive may be included in about 0.01% to about 5% by weight based on the total weight of the CMP slurry composition.
- the CMP slurry composition for organic membranes of the present invention has a contact angle with respect to cyclohexane represented by the following formula (2) when the wafer coated with the organic film to be polished is immersed in the CMP slurry for about 10 hours.
- the amount of change ⁇ n may be about 1 ° to about 50 °, specifically about 1 ° to about 20 °, more specifically about 1 ° to about 10 °.
- Equation (2) ⁇ 3 is a contact angle measured by dropping cyclohexane onto an organic film surface before immersing the organic film-coated wafer in a CMP slurry, and ⁇ 4 is a wafer coated with the organic film. After immersing in a CMP slurry for about 10 hours, the contact angle was measured by dropping cyclohexane on the surface of the organic film.
- the organic film to be polished may have a carbon content of about 50 wt% to about 95 wt%.
- the CMP slurry composition for organic films has a polishing rate of about 500 kW / min to about 10,000 kW / min, specifically about 1000 kW / min to about 8000 kW / min, and more specifically about 1500 kW / min to the organic film. About 5000 mW / min.
- the present invention provides a method for producing a CMP slurry for an organic film comprising a step of mixing an oxidant and a solvent, wherein the step of mixing the oxidant and the solvent is a wafer coated with an organic film to be subjected to the organic
- the change amount ⁇ W of the water contact angle represented by the above formula (1) is performed to be about 5 ° to about 90 °.
- the present invention provides an organic film polishing method comprising the step of polishing the organic film using the CMP slurry composition for organic films according to the present invention described above.
- the CMP slurry composition for organic membranes of the present invention has excellent polishing rate for organic films and provides optimized polishing properties for various organic films.
- 1 is a schematic diagram of an organic film polishing method of an embodiment of the present invention.
- the CMP slurry composition for organic membranes of the present invention comprises a solvent and an oxidizing agent, the amount of change in the water contact angle represented by the following formula (1) measured after immersing the wafer coated with the organic film to be polished in the CMP slurry for 10 hours ⁇ W is about 5 ° to about 90 °.
- the amount of change ⁇ W of the water contact angle represented by the following formula (1) measured after immersing the wafer coated with the organic film to be polished in the CMP slurry for 10 hours is about 5 °, 6 °, 7 °, 8 °, 9 °, 10 °, 11 °, 12 °, 13 °, 14 °, 15 °, 16 °, 17 °, 18 °, 19 °, 20 °, 21 °, 22 °, 23 °, 24 ° , 25 °, 26 °, 27 °, 28 °, 29 °, 30 °, 31 °, 32 °, 33 °, 34 °, 35 °, 36 °, 37 °, 38 °, 39 °, 40 °, 41 °, 42 °, 43 °, 44 °, 45 °, 46 °, 47 °, 48 °, 49 °, 50 °, 51 °, 52 °, 53 °, 54 °, 55 °, 56
- the change amount ⁇ W of the water contact angle may be in the range of at least one of the above values and at most one of the above values. Specifically, the change amount ⁇ W of the water contact angle is About 5 ° to about 70 °, more specifically about 10 ° to about 50 °.
- Equation (1) ⁇ 1 is a water contact angle measured by dropping DI WATER on the surface of the organic film before immersing the organic film-coated wafer in a CMP slurry, and ⁇ 2 is the organic film coated It is a water contact angle measured by immersing the wafer in a CMP slurry for about 10 hours and then dropping DI water on the surface of the organic film.
- the organic film forms a film through various chemical reactions, the film structure is complicated and it is impossible to predict polishing properties in advance.
- the inventors have found out that, after diligent research, the amount of change in the water contact angle measured after immersing the wafer coated with the organic film to be polished in the CMP slurry composition correlates with the polishing property of the organic film.
- the amount of change in the water contact angle measured after immersing the object to be polished in the CMP slurry composition is about 5 ° to about 90 °, for example, about 5 ° to about 70 °, or about 10 ° to about 50 °.
- the amount of change in the water contact angle was less than about 5 degrees or more than about 90 degrees, the polishing rate for the organic film was significantly lowered.
- the organic film-coated wafer used in the water contact angle measurement may be prepared by coating an organic film on a silicon oxide wafer.
- the silicon oxide wafer may be, for example, on a standard silicon wafer having a diameter of about 200 mm or about 300 mm, and a silicon oxide film having a thickness of about 2,000 to 12,000 mm 3 is uniformly within about 10% of the relative standard deviation with respect to the thickness.
- the wafer may be formed, but is not limited thereto.
- the organic film-coated wafer may be manufactured by applying the composition for forming an organic film on the silicon oxide wafer as described above.
- the coating of the organic layer is not limited thereto, but may be performed through a multi-step process having different rotation rates.
- the coating of the organic layer may be performed by applying a three-step spincoating process performed under the following conditions:
- 1st stage about 1000rpm, about 2 seconds
- Stage 2 about 1500 rpm, about 20 seconds
- Step 3 about 1000 rpm, about 2 seconds
- the rotary coating may be used general and standard equipment, such as MS-A200 from Mikasa.
- the organic film is cured by baking on a hot plate or the like.
- the baking may be performed in air for about 2 minutes on a hot plate of about 400 degrees, and may be cooled by about 10 minutes at room temperature to form an organic film after baking. .
- the organic film having an average thickness of about 2,000 to 3,000 ⁇ can be uniformly formed within about 5% of the relative standard deviation with respect to the thickness.
- the relative standard deviation with respect to the average thickness and thickness of the organic film can be obtained by measuring a thickness of about 30 points at equal intervals along the diameter of the surface of the organic film coated wafer.
- the thickness at each point is obtained using a standard spectrometer such as K-MAC, but the calibration is performed based on the SEM image of the wafer cut surface. It should be within 5%.
- the water contact angle measurement is performed by cutting the entire organic film-coated wafer prepared by the above method or the wafer coated with the organic film into a size of about 2 cm or more and about 2 cm or more within the range of no damage to the organic film. It can be measured using the specimen. At this time, the measurement of the water contact angle should of course be applied to the surface coated with the organic film.
- the oxidizing agent is for oxidizing the surface layer of the organic film to facilitate polishing of the organic film, and to improve the planarization degree by making the surface of the organic film even.
- the oxidizing agent used in the present invention may be one containing at least one of Fe 3 + , Ce 4 + , Ce 3 + , Cu 2 + and Ag + .
- the oxidizing agent in terms of polishing rate Fe 3 + , Cu 2 +, Ce 3+, and it may include at least one of Ce + 4.
- the oxidizing agent may be a metal salt including the metal ions as described above, for example, ceric ammonium nitrate, ceric sulfate, cupric chloride, cupric It may include at least one of cupric nitride, ferric nitride, ferric chloride, cerous nitrate, and silver nitrate. .
- the oxidant may further include hydrogen peroxide together with the metal ions.
- hydrogen peroxide is additionally included in the oxidizing agent, there is an effect of further improving the polishing rate by improving the oxidizing power.
- the oxidizing agent may be one containing Ce 4 +, Ce 3 +, Cu 2 +, and Ag + 1 mixture of types of metal ions and hydrogen peroxide or more of.
- the oxidizing agent may be about 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5% by weight based on the total weight of the CMP slurry composition.
- the oxidant may also be in the range of about one or more of the above values and about one or less of the above values relative to the total weight of the CMP slurry composition.
- the oxidizing agent may be included in about 0.001 to about 5% by weight, for example about 0.01 to about 3% by weight, or about 0.05 to about 3% by weight relative to the total weight of the CMP slurry composition.
- the oxidizing agent may include a metal salt including Ce and hydrogen peroxide in a weight ratio of about 1: 1.5 to about 1: 3. In this range, the polishing rate is further improved.
- the solvent is to reduce the friction between the abrasive and the organic film when polishing the organic film, for example, water, ultrapure water, organic amine, organic alcohol, organic alcohol amine, organic ether, organic ketone, etc. Can be.
- the solvent may be included in the balance in the CMP slurry composition.
- the CMP slurry composition for organic films of the present invention may include an abrasive.
- the abrasive may be a metal oxide abrasive.
- the abrasive is intended to enable polishing of the organic film with a high polishing amount, and may include, for example, one or more of silica, alumina, ceria, titania, and zirconia.
- the abrasive may include one or more of silica having excellent dispersion stability and ceria having an excellent polishing speed improving effect.
- the abrasive may be spherical particles having an average particle diameter of about 10 to about 150 nm, for example, about 30 to about 70 nm. Within this range, it is possible to achieve a sufficient polishing rate with respect to the organic film to be polished of the present invention, prevent scratches from occurring, and increase flatness.
- the abrasive may be about 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 weight percent based on the total weight of the CMP slurry composition.
- the abrasive may range from about one or more of the above values and about one or less of the above values relative to the total weight of the CMP slurry composition.
- the abrasive may be included in about 0.01 to about 5% by weight, for example about 0.01 to about 3% by weight based on the total weight of the CMP slurry composition.
- the content of the abrasive satisfies the above range, it is possible to achieve a sufficient polishing rate with respect to the organic film to be polished of the present invention, prevent scratches from occurring, and excellent dispersion stability. Specifically, by increasing the average particle diameter of the abrasive, but lowering the content in the slurry composition, it is possible to implement an improved polishing rate for the organic film, a lower polishing rate for the inorganic film.
- the mixing ratio of the abrasive and the oxidant is about 100: 1 to about 1: 500 by weight ratio, and specifically, the mixing ratio of the abrasive and the oxidant is about 10: 1 to about by weight ratio. 1: 100.
- the CMP slurry composition of the present invention may be acidic.
- the CMP slurry is acidic, the polishing selectivity of the organic film to the inorganic film is increased, and the polishing amount per unit time and the flatness of the polishing surface to the organic film are improved.
- the CMP slurry composition of the present invention may have a pH of about 7 or less, specifically about 6 or less, more specifically about 1 to about 5.
- the CMP slurry composition of one embodiment of the present invention can be adjusted to the pH in the above-described range.
- the pH adjusting agent may include at least one of an inorganic acid, such as nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid, and may include an organic acid, for example, an organic acid having a p K a value of about 5 or less, for example acetic acid, But may not include one or more of citric acid.
- an inorganic acid such as nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid
- organic acid for example, an organic acid having a p K a value of about 5 or less, for example acetic acid, But may not include one or more of citric acid.
- the CMP slurry composition according to the present invention may further include an additive.
- the additive is to assist physical properties of the CMP slurry, and may be, for example, an abrasive accelerator.
- a polishing accelerator By further including a polishing accelerator, the polishing rate for the inorganic film can be suppressed to increase the polishing selectivity for the inorganic film.
- the polishing promoter may include one or more of an organic acid, for example malic acid, citric acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, malonic acid.
- the polishing accelerator may be included in about 0.01% to about 1% by weight of the CMP slurry composition, and may have no adverse effect on the polishing rate, dispersion stability of the slurry, and surface characteristics of the organic carbon film in the above range.
- the CMP slurry composition for organic films of the present invention the amount of change in contact angle with respect to cyclohexane represented by the following formula (2) measured after immersing the wafer coated with the organic film to be polished in the CMP slurry for about 10 hours ⁇ n is approximately 1 °, 2 °, 3 °, 4 °, 5 °, 6 °, 7 °, 8 °, 9 °, 10 °, 11 °, 12 °, 13 °, 14 °, 15 °, 16 °, 17 °, 18 °, 19 °, 20 °, 21 °, 22 °, 23 °, 24 °, 25 °, 26 °, 27 °, 28 °, 29 °, 30 °, 31 °, 32 °, 33 °, 34 °, 35 °, 36 °, 37 °, 38 °, 39 °, 40 °, 41 °, 42 °, 43 °, 44 °, 45 °
- the change amount ⁇ n of the contact angle with respect to the cyclohexane may be in the range of at least one of the above values and at most one of the above values.
- the amount of change ⁇ n of the contact angle with respect to cyclohexane may be about 1 ° to about 50 °, specifically about 1 ° to about 20 °, more specifically about 1 ° to about 10 °.
- ⁇ 3 is a contact angle measured by dropping cyclohexane onto an organic film surface before immersing the organic film-coated wafer in a CMP slurry
- ⁇ 4 is a wafer coated with the organic film. Is a contact angle measured by dropping cyclohexane onto the surface of an organic film after immersing in a CMP slurry for about 10 hours. In this case, the wafer coated with the organic film used for measuring the contact angle is the same as that used for the above-described water contact angle measurement.
- the CMP slurry composition for organic membranes of the present invention has a polishing rate of about 500 mW / min to about 10,000 mW / min, specifically about 1000 mW / min to about 8000 mW / min, more specifically about 1500 mW for the organic film. Very good from dl / min to about 5000 dl / min.
- the CMP slurry composition for an organic film according to the present invention may be prepared by mixing the oxidizing agent and a solvent, wherein the oxidizing agent and the solvent are mixed with the organic film coated wafer to be subjected to polishing to the CMP slurry for the organic film.
- the change amount ⁇ W of the water contact angle represented by the above formula (1) is performed so that it is about 5 ° to about 90 °.
- the step of mixing the oxidant and the solvent may further comprise the step of mixing the abrasive.
- the mixing of the oxidant and the solvent may further include mixing an additive such as an abrasive promoter.
- substituted in “substituted or unsubstituted” means that at least one hydrogen atom of the functional group is a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, an amino group, a C1 to C30 alkyl group, a C2 to C30 alkenyl group , C2 to C30 alkynyl group, C3 to C30 cycloalkyl group, C3 to C30 cycloalkenyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C30 heterocycloalkyl group, C2 to C30 heterocyclo Alkenyl group, C2 to C30 heteroaryl group, C2 to C30 heteroarylalkyl group, C1 to C20 alkylamine group, C1 to C30 alkoxy group, C6 to
- the "functional group including P” may be represented by the following Chemical Formula A
- the “functional group including B” may be represented by the following Chemical Formula B:
- n is 0 or 1
- m is an integer of 0 to 10
- R a , R b , R c and R d are each independently hydrogen, hydroxyl, substituted or Unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 haloalkyl group, substituted or unsubstituted C1 to C20 alkylsulfonate group, substituted or unsubstituted C1 to C20 alkylsulfonyl group, substituted or unsubstituted C2 to C20 alkylamide group, substituted or unsubstituted C3 to C20 alkyl ester group, substituted or Unsubstituted C2 to C20 cyanoalkyl group,
- the "functional group including B” is a functional group including B and O, for example,- B (OH) 2 , -B (H) (CH 3 ), or -B (CH 2 CH 3 ) 2 , and the like.
- the organic film has a carbon content of about 50 to about 95% by weight, specifically, 65 to 95% by weight or 70 to 92% by weight, for example, about 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94 or 95% by weight.
- the polishing amount may be high during polishing, no scratches may occur, and the flatness of the polishing surface may also be high.
- the organic film may have a film density of about 0.5 to about 2.5 g / cm 3 , specifically, about 1.0 to about 2.0 g / cm 3 or about 1.2 to about 1.6 g / cm 3 , for example about 0.5 , 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5 g / cm 3 .
- the polishing amount may be high during polishing, no scratch may occur, and the flatness of the polishing surface may be high.
- the organic layer may have a hardness of about 0.4 GPa or more, specifically about 1.0 GPa or more, or about 1.3 GPa or more, for example, about 1.0 to about 1.5 GPa, for example, about 0.4, 0.5, 0.6, 0.7, It may be 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 GPa.
- the polishing amount may be high, the scratch may not occur, and the flatness of the polishing surface may be high.
- the organic film to be polished of the present invention may have an acid value of about 0 mgKOH / g substantially.
- the "substantially” includes not only when the acid value is about 0mgKOH / g, but also a slight error is added or subtracted at about 0mgKOH / g.
- the polishing rate is further improved.
- the organic film to be polished of the present invention may be formed by a composition comprising a compound having a substituted or unsubstituted aromatic group, and more specifically a composition comprising a compound having a substituted or unsubstituted aromatic group.
- a composition comprising a compound having a substituted or unsubstituted aromatic group
- thermal curing at a high temperature, for example, about 200 to about 400.
- the aromatic group may have a single ring structure having 6 to 100 carbon atoms, for example, 6 to 50 carbon atoms or a polycyclic structure in which two or more rings are fused.
- the following Chemical Formula 1 It may include a compound represented by -1 to 1-26.
- composition for organic film formation containing the compound which has a substituted or unsubstituted aromatic group is demonstrated in detail.
- the composition for forming an organic layer may include a material having a unit represented by the following Formula 2 as a compound having a substituted or unsubstituted aromatic group:
- a is 1 ⁇ a ⁇ 190
- R 1 is hydrogen, hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 To C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or Unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or un
- R 2 is hydrogen, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, -NR h R i (where R h and R i Are independently substituted or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C10 aryl group), hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted Substituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cyclo
- R 3 is substituted or unsubstituted
- R 2 may be a substituted or unsubstituted C1 to C10 alkoxy group.
- the material including Chemical Formula 2 may increase carbon content, film density, and hardness after thermal curing of the composition for forming an organic film, and refer to Korean Patent No. 10-0866015 for a more detailed manufacturing method thereof.
- the composition of the first embodiment may further include at least one of a crosslinking component, an acid catalyst, and an organic solvent, in addition to the material containing the unit represented by Formula 2 above. Specifically, about 1 to about 20 wt% of the material represented by Formula 2, about 0.1 to about 5 wt% of the crosslinking component, about 0.001 to about 0.05 wt% of the acid catalyst, and about 75 to about 98.8 wt% of the organic solvent. Can be.
- the crosslinking component may be a melamine resin (for example, N-methoxymethyl-melamine resin, N-butoxymethylmelamine resin), methylated or butylated urea resin, amino resin, glycoluril derivative represented by the following Chemical Formula 3, It may include one or more of the bisepoxy compound represented by the formula (4), the melamine derivative represented by the following formula (5):
- the acid catalyst is composed of p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate and eutechonic acid. It may include one or more of the alkyl esters.
- the organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility in a compound having a substituted or unsubstituted aromatic group, and examples thereof include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, and the like.
- composition for forming an organic film of the first embodiment is coated to a thickness of about 500 kPa to about 4,000 kPa, specifically about 2,000 to 3,000 kPa, and thermally cured at about 200 to about 400 for about 10 seconds to about 10 minutes to form an organic film. You can, but are not limited to this.
- the composition for forming an organic film may include a compound represented by the following Chemical Formula 6 as a compound having a substituted or unsubstituted aromatic group:
- R 4 to R 9 and X 1 to X 6 are each independently hydrogen, a hydroxy group, a halogen atom, an allyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, Substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted
- R 4 to R 9 are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or It may be an unsubstituted C3 to C20 cycloalkenyl group, a functional group including P or a functional group including B.
- X 1 to X 6 may be each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkylamine group, an amino group, a functional group including P, a functional group including B.
- composition for forming an organic film according to the second embodiment is a compound having a substituted or unsubstituted aromatic group, except that the material represented by the formula (6) instead of the material containing the unit represented by the formula (2) Is substantially the same as the composition for forming an organic film of the first embodiment. Therefore, hereinafter, only the substance represented by Chemical Formula 6 will be described.
- the aromatic group compound of Chemical Formula 6 may have a weight average molecular weight of about 500 to about 4000, and may implement a thickness or good thin film of the organic film in the above range.
- the material represented by Chemical Formula 6 may be prepared by a conventional method, for example, it may be prepared by reacting and reducing acetyl chloride, benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited.
- acetyl chloride benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited.
- benzoyl chloride e.g., benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited.
- For more detailed manufacturing method refer to Korea Patent Registration No. 10-1311942.
- the composition for forming an organic film including the material represented by Chemical Formula 6 When the organic film is formed using the composition for forming an organic film including the material represented by Chemical Formula 6, carbon content, film density, and hardness may be increased after thermosetting.
- the composition for forming an organic film including the material represented by Chemical Formula 6 includes an aromatic ring having strong absorption in a short wavelength region (for example, about 193 nm and about 248 nm), even though a special catalyst is not used. Since the crosslinking reaction proceeds at a temperature, it is possible to prevent contamination by catalysts, especially acids.
- the composition for forming an organic film of the present invention may be represented by Chemical Formula 6, and may include a mixture of two or more compounds having different positions of substituents.
- the composition for forming an organic film may include an aromatic group-containing polymer selected from (i), (ii) and (iii) as a compound having an unsubstituted or unsubstituted aromatic group:
- R 10 is substituted or unsubstituted
- R is any substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C3 to Cycloalkenyl group of C20),
- R 11 is hydrogen, a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or Unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or
- R 12 and R 14 are each independently substituted or unsubstituted
- R 13 is substituted or unsubstituted
- R is any substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C3 to Cycloalkenyl group of C20),
- R 15 is substituted or unsubstituted
- R is any substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C3 to Cycloalkenyl group of C20),
- R in R 10 , R 13 and R 15 are each independently hydrogen, hydroxy group, halogen atom, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 to C30 alkyl group, substituted Or an unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substitute
- composition for forming an organic film according to the third embodiment is a compound having a substituted or unsubstituted aromatic group, except that the composition includes the aromatic group-containing polymer instead of the material including the unit represented by Formula 2 above. It is substantially the same as the composition for organic film formation of a specific example.
- the aromatic group-containing polymer can increase carbon content, film density and hardness after thermosetting the composition for forming an organic film, and can be produced by a conventional method.
- the composition for forming an organic film is a compound having an unsubstituted or unsubstituted aromatic group material comprising a unit represented by the formula (2); A substance represented by Chemical Formula 6; It may contain two or more of the aromatic group-containing polymers selected from the above (i), (ii) and (iii).
- the composition for forming an organic film according to the fourth embodiment is substantially the same as the composition of the first embodiment, except for including two or more compounds having a substituted or unsubstituted aromatic group.
- the organic film polishing method of the present invention includes the step of polishing the organic film using the organic film CMP slurry composition, wherein the organic film CMP slurry composition is the organic film CMP slurry composition of the present invention described above.
- FIG. 1A illustrates a lamination state of a silicon wafer, an inorganic film, and an organic carbon film before polishing an organic film, and the silicon wafer 100 is intaglio patterned to be locally concave. An addition is formed.
- the inorganic film 110 is deposited on the silicon wafer 100, the organic carbon film 120 is coated on the inorganic film, and manufactured by thermal curing at about 200 to about 400.
- T represents an imaginary polishing stop line.
- a 2000 ml three-necked flask equipped with a thermometer, a condenser, a mechanical stirrer, and a dropping funnel was prepared, and then immersed in an oil bath at 140 ° C. Heating and stirring by magnets were performed on a hotplate and the cooling water temperature of the condenser was fixed at 40 ° C. 220 g of 1 mol of 1-methoxypyrene was added to the reactor, and 138 g of 1.0 mol of 1,4-bismethoxymethylbenzene was added and then dissolved in 656 g of propylene glycol monomethyl ether acetate. Then 4.6 g of 0.03 mol of diethylsulfate were added.
- the temperature of the reactor was maintained at 130 ° C.
- the molecular weight was measured at regular time intervals to determine the completion time of the reaction.
- the sample for measuring the molecular weight was prepared by diluting 1 g of the reactant, quenching to room temperature, 0.02 g of the sample was diluted to 4% by weight using tetrahydrofuran as a solvent.
- 0.03 mol of triethanolamine 4.48 g was added to the reactor as a neutralizing agent and terminated.
- the reaction was then slowly cooled to room temperature.
- the reaction was diluted with 500 g of propylene glycol monomethyl ether acetate.
- the solvent was then added to a 2000 ml separatory funnel.
- the molecular weight and the dispersity of the obtained copolymer were measured by GPC under tetrahydrofuran, and as a result, a polymer containing a unit represented by the following formula (11) having a weight average molecular weight of 4000 dispersion of 2.3 was obtained.
- the organic film-forming composition prepared according to Preparation Example 1 was formed on the surface of a silicon oxide wafer on which a silicon oxide film was formed on a silicon wafer having a diameter of 200 mm, using a MS-A200 manufactured by Mikasa for 2 seconds at 1000 rpm (1 step) and 20 at 1500 rpm. Second (stage 2), spin coating at 1000 rpm for 2 seconds (stage 3).
- a CMP slurry composition was prepared comprising ultra pure water and the components of Table 1 below.
- Distilled water and apolar solvent were added dropwise to the organic membrane surface of the specimen prepared in Preparation Example 2 to measure the contact angle ⁇ 1 and the contact angle ⁇ 3 with respect to the nonpolar solvent before immersion. Then, the specimens were immersed in the CMP slurry compositions of Examples and Comparative Examples for 10 hours and then taken out and dried, and after immersion, the water contact angle ⁇ 2 and the contact angle ⁇ 4 for the nonpolar solvent were measured. The amount of change in water contact angle before and after dipping and the amount of change in contact angle of the nonpolar solvent were calculated.
- the contact angle was measured by the angle between the tangent at the contact point of the drop of the solvent and the surface of the organic film and the surface of the organic film.
- the measurement results are shown in the following [Table 1].
- the organic film-coated wafer prepared in Preparation Example 2 was polished using the CMP slurry compositions of Examples and Comparative Examples.
- FUJIBO's H0800 CMP pad was used as the polishing pad.
- polishing was performed for 30 seconds at a lower pressure of 1.0 psi, a slurry flow rate of 200 mL / minute, platen speed of 60 rpm, and head speed of 55 rpm. The amount was measured using a Cay Mac thickness meter. The measurement results are shown in Table 1 below.
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Abstract
La présente invention concerne une suspension de PMC pour film organique comprenant un oxydant et un solvant. La suspension de PMC pour film organique de la présente invention présente un ΔθW, d'approximativement 5 à 90°, qui est la quantité de changement au niveau de l'angle de contact avec l'eau, représenté par la formule (1), et mesuré après qu'une galette, enduite d'un film organique et à polir, a été immergée dans la suspension de PMC durant 10 heures.
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CN201680047980.8A CN107922819B (zh) | 2015-08-21 | 2016-07-21 | 用于有机膜的化学机械研磨研浆组成物、其制备方法以及使用其的研磨有机膜的方法 |
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KR10-2015-0118245 | 2015-08-21 | ||
KR1020150118245A KR101900540B1 (ko) | 2015-08-21 | 2015-08-21 | 유기막용 cmp 슬러리 조성물, 그 제조방법, 및 이를 이용한 유기막 연마 방법 |
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KR20040030350A (ko) * | 2002-10-02 | 2004-04-09 | 가부시끼가이샤 도시바 | 수지 입자를 이용한 반도체 기판 상의 유기막의 연마방법과 슬러리 |
US6830503B1 (en) * | 2002-01-11 | 2004-12-14 | Cabot Microelectronics Corporation | Catalyst/oxidizer-based CMP system for organic polymer films |
KR20070057009A (ko) * | 2005-11-30 | 2007-06-04 | 제이에스알 가부시끼가이샤 | 유기막 연마용 화학적 기계적 연마 슬러리, 화학적 기계적연마 방법, 및 반도체 장치의 제조 방법 |
US20140209566A1 (en) * | 2013-01-30 | 2014-07-31 | Cabot Microelectronics Corporation | Chemical-mechanical polishing composition containing zirconia and metal oxidizer |
KR20140125316A (ko) * | 2013-04-17 | 2014-10-28 | 제일모직주식회사 | 유기막 cmp 슬러리 조성물 및 이를 이용한 연마방법 |
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US6589100B2 (en) * | 2001-09-24 | 2003-07-08 | Cabot Microelectronics Corporation | Rare earth salt/oxidizer-based CMP method |
WO2014171766A1 (fr) * | 2013-04-17 | 2014-10-23 | 제일모직 주식회사 | Composition de suspension de cmp de film organique et procédé de polissage l'utilisant |
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US6830503B1 (en) * | 2002-01-11 | 2004-12-14 | Cabot Microelectronics Corporation | Catalyst/oxidizer-based CMP system for organic polymer films |
KR20040030350A (ko) * | 2002-10-02 | 2004-04-09 | 가부시끼가이샤 도시바 | 수지 입자를 이용한 반도체 기판 상의 유기막의 연마방법과 슬러리 |
KR20070057009A (ko) * | 2005-11-30 | 2007-06-04 | 제이에스알 가부시끼가이샤 | 유기막 연마용 화학적 기계적 연마 슬러리, 화학적 기계적연마 방법, 및 반도체 장치의 제조 방법 |
US20140209566A1 (en) * | 2013-01-30 | 2014-07-31 | Cabot Microelectronics Corporation | Chemical-mechanical polishing composition containing zirconia and metal oxidizer |
KR20140125316A (ko) * | 2013-04-17 | 2014-10-28 | 제일모직주식회사 | 유기막 cmp 슬러리 조성물 및 이를 이용한 연마방법 |
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TWI618791B (zh) | 2018-03-21 |
CN107922819B (zh) | 2020-10-23 |
CN107922819A (zh) | 2018-04-17 |
KR20170023362A (ko) | 2017-03-03 |
TW201715015A (zh) | 2017-05-01 |
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