WO2011155407A1 - Chemical solution for formation of protective film - Google Patents
Chemical solution for formation of protective film Download PDFInfo
- Publication number
- WO2011155407A1 WO2011155407A1 PCT/JP2011/062798 JP2011062798W WO2011155407A1 WO 2011155407 A1 WO2011155407 A1 WO 2011155407A1 JP 2011062798 W JP2011062798 W JP 2011062798W WO 2011155407 A1 WO2011155407 A1 WO 2011155407A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chemical solution
- protective film
- wafer
- acid
- forming
- Prior art date
Links
- 239000000126 substance Substances 0.000 title claims abstract description 236
- 230000001681 protective effect Effects 0.000 title claims abstract description 199
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 239000002253 acid Substances 0.000 claims abstract description 159
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 133
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 82
- 239000005871 repellent Substances 0.000 claims abstract description 17
- VIYXXANHGYSBLY-UHFFFAOYSA-N trimethylsilyl 2,2,2-trifluoroacetate Chemical compound C[Si](C)(C)OC(=O)C(F)(F)F VIYXXANHGYSBLY-UHFFFAOYSA-N 0.000 claims abstract description 17
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- FOTBOKBDKNTVLX-UHFFFAOYSA-N dimethylsilyl 2,2,2-trifluoroacetate Chemical compound C[SiH](C)OC(=O)C(F)(F)F FOTBOKBDKNTVLX-UHFFFAOYSA-N 0.000 claims abstract description 10
- JDYXTZFZYGJYCU-UHFFFAOYSA-N [dimethyl(octyl)silyl] 2,2,2-trifluoroacetate Chemical compound CCCCCCCC[Si](C)(C)OC(=O)C(F)(F)F JDYXTZFZYGJYCU-UHFFFAOYSA-N 0.000 claims abstract description 9
- DPFCZRAGEMLFTN-UHFFFAOYSA-N dimethylsilyl trifluoromethanesulfonate Chemical compound C[SiH](C)OS(=O)(=O)C(F)(F)F DPFCZRAGEMLFTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- JYVPIEJECJXXKU-UHFFFAOYSA-N [butyl(dimethyl)silyl] 2,2,2-trifluoroacetate Chemical compound CCCC[Si](C)(C)OC(=O)C(F)(F)F JYVPIEJECJXXKU-UHFFFAOYSA-N 0.000 claims abstract description 8
- PEFNDUOLISEFNU-UHFFFAOYSA-N [dimethyl(octyl)silyl] trifluoromethanesulfonate Chemical compound CCCCCCCC[Si](C)(C)OS(=O)(=O)C(F)(F)F PEFNDUOLISEFNU-UHFFFAOYSA-N 0.000 claims abstract description 7
- OEGAMYZOUWNLEO-UHFFFAOYSA-N [butyl(dimethyl)silyl] trifluoromethanesulfonate Chemical compound CCCC[Si](C)(C)OS(=O)(=O)C(F)(F)F OEGAMYZOUWNLEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- QHIJPBGTYHXSSQ-UHFFFAOYSA-N [decyl(dimethyl)silyl] 2,2,2-trifluoroacetate Chemical compound CCCCCCCCCC[Si](C)(C)OC(=O)C(F)(F)F QHIJPBGTYHXSSQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- AQSDMBVSJLUVJX-UHFFFAOYSA-N [decyl(dimethyl)silyl] trifluoromethanesulfonate Chemical compound CCCCCCCCCC[Si](C)(C)OS(=O)(=O)C(F)(F)F AQSDMBVSJLUVJX-UHFFFAOYSA-N 0.000 claims abstract description 4
- KJUATNVXFLOMQN-UHFFFAOYSA-N [hexyl(dimethyl)silyl] 2,2,2-trifluoroacetate Chemical compound CCCCCC[Si](C)(C)OC(=O)C(F)(F)F KJUATNVXFLOMQN-UHFFFAOYSA-N 0.000 claims abstract description 4
- HHSPZBRBLBLYJV-UHFFFAOYSA-N [hexyl(dimethyl)silyl] trifluoromethanesulfonate Chemical compound CCCCCC[Si](C)(C)OS(=O)(=O)C(F)(F)F HHSPZBRBLBLYJV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims description 139
- 239000007788 liquid Substances 0.000 claims description 129
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 119
- 239000010703 silicon Substances 0.000 claims description 81
- 229940126062 Compound A Drugs 0.000 claims description 76
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000012535 impurity Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 125000000962 organic group Chemical group 0.000 claims description 18
- 238000005259 measurement Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- 239000007858 starting material Substances 0.000 claims description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000149 argon plasma sintering Methods 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000005406 washing Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 206
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 44
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 44
- 239000002904 solvent Substances 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 37
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 32
- 239000003960 organic solvent Substances 0.000 description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- 238000004381 surface treatment Methods 0.000 description 25
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 18
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 239000008155 medical solution Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 16
- 229910052581 Si3N4 Inorganic materials 0.000 description 15
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
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- CNNPULJFGORMOI-UHFFFAOYSA-N 1-[[[dimethyl(octyl)silyl]amino]-dimethylsilyl]octane Chemical compound CCCCCCCC[Si](C)(C)N[Si](C)(C)CCCCCCCC CNNPULJFGORMOI-UHFFFAOYSA-N 0.000 description 6
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- 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
Definitions
- the present invention relates to a substrate (wafer) cleaning technique for the purpose of improving the manufacturing yield of a device having a circuit pattern that is fine and has a high aspect ratio, particularly in the manufacture of semiconductor devices.
- the present invention relates to a water-repellent protective film-forming chemical solution and the like for the purpose of improving a cleaning process that easily induces a concavo-convex pattern collapse of a wafer having a fine concavo-convex pattern on the surface.
- This pattern collapse occurs when the wafer is pulled up from the cleaning liquid or the rinse liquid. This is said to be caused by a difference in residual liquid height between a portion where the aspect ratio of the pattern is high and a portion where the aspect ratio is low, thereby causing a difference in capillary force acting on the pattern.
- the magnitude of the capillary force is the absolute value of P obtained by the following formula. From this formula, it is expected that the capillary force can be reduced by reducing ⁇ or cos ⁇ .
- Patent Document 1 discloses a technique for substituting the cleaning liquid from water to 2-propanol before the gas-liquid interface passes through the pattern as a technique for reducing ⁇ and suppressing pattern collapse.
- a solvent such as 2-propanol having a small ⁇ tends to have a small normal contact angle and, as a result, tends to increase cos ⁇ . Therefore, it is said that there is a limit, for example, the aspect ratio of the pattern that can be handled is 5 or less.
- Patent Document 2 discloses a technique for a resist pattern as a technique for reducing cos ⁇ and suppressing pattern collapse. This method is a method of suppressing pattern collapse by setting cos ⁇ close to 0 and reducing the capillary force to the limit by setting the contact angle near 90 °.
- the disclosed technique since the disclosed technique is intended for a resist pattern, it modifies the resist itself, and can be finally removed together with the resist. Therefore, it is necessary to assume a method for removing the treatment agent after drying. Is not applicable to this purpose.
- Patent Document 3 discloses that a wafer surface on which a concavo-convex pattern is formed by a film containing silicon is surface-modified by oxidation or the like, and a water-repellent protective film is formed on the surface using a water-soluble surfactant or silane coupling agent.
- a cleaning method is disclosed that reduces the capillary force and prevents the pattern from collapsing.
- the water repellent used above may have an insufficient water repellency imparting effect.
- the wafer surface is a surface having a fine uneven pattern.
- throughput is impaired in a method of manufacturing a wafer having a fine uneven pattern on the surface and at least a part of the uneven pattern containing silicon element (hereinafter referred to as “silicon wafer” or simply “wafer”). It is an object of the present invention to provide a protective film-forming chemical solution for forming a water-repellent protective film on the surface of a concavo-convex pattern of a wafer for improving a cleaning process that easily induces pattern collapse.
- the chemical liquid for forming a protective film (hereinafter referred to as “chemical liquid for forming a protective film” or simply “chemical liquid”) for forming a water-repellent protective film on the surface of the uneven pattern of the wafer of the present invention has a fine uneven pattern on the surface.
- a water-repellent protective film (hereinafter referred to as “water-repellent protective film” or simply “protective film”) is formed on at least the concave surface of the concavo-convex pattern.
- a chemical solution for use in the treatment comprising a silicon compound A represented by the following general formula [1] and an acid A, wherein the acid A is trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethane Sulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trif Group consisting of oromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, and decyldimethylsilyl trifluoromethanesul
- R 1 s each independently contain a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms and a fluoroalkyl chain having 1 to 8 carbon atoms.
- X is at least one group selected from valent organic groups, X is each independently a monovalent organic group in which the element bonded to the Si element is nitrogen, a is an integer of 1 to 3, b Is an integer from 0 to 2, and the sum of a and b is 1 to 3.
- R 1 in the general formula [1] reduces the surface energy of the protective film, and interacts between water or other liquid and the surface of the protective film (interface), for example, hydrogen bond, intermolecular force. Etc.
- the effect of reducing the interaction with water is great, but it has the effect of reducing the interaction with a mixed liquid of water and a liquid other than water or a liquid other than water. Thereby, the contact angle of the liquid with respect to the article
- the protective film is formed by chemically bonding X in the general formula [1] with the Si element of the silicon wafer. Therefore, when the cleaning liquid is removed from the recess of the silicon wafer, that is, when it is dried, since the protective film is formed on the surface of the recess, the capillary force on the surface of the recess is reduced, and pattern collapse occurs. It becomes difficult.
- the protective film can be removed in a later step.
- Acid A namely trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethyl At least one selected from the group consisting of silyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, and decyldimethylsilyl trifluoromethanesulfonate is the silicon compound A and S of silicon wafer It is successful in promoting the reaction between the elements
- the speed at which the protective film is formed on the substrate surface is determined by the speed at which the component derived from the silicon compound A binds to the reaction site on the substrate surface. Is.
- the component derived from the silicon compound A can quickly react with silanol groups, which are reaction sites on the surface of the concave / convex pattern of the silicon wafer, so that sufficient water repellency is imparted to the substrate surface during the surface treatment. can do.
- the total amount of moisture in the starting material is 5000 ppm by mass or less based on the total amount of the starting material.
- the water content exceeds 5000 mass ppm, it is difficult to form the protective film in a short time.
- the smaller the total amount of water the more preferable, particularly 1000 ppm by mass or less, and even more preferable 500 ppm by mass or less.
- medical solution will fall easily when there are many amounts of water, the one where water content is small is preferable, 200 mass ppm or less, Furthermore, 100 mass ppm or less is preferable. In addition, 0.1 mass ppm or more may be sufficient as the moisture content in the raw material of the said chemical
- the Bronsted acid reacts with the silicon compound A to reduce the silicon compound A or to reduce the reactivity of the silicon compound A. There is. For this reason, the acid A is preferred.
- the acid A contained in the chemical solution for forming a protective film of the present invention may be obtained by a reaction.
- a reaction for example, at least one selected from the group consisting of silicon compound B represented by the following general formula [2] and trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride (hereinafter referred to as “acid B”). May be obtained by reacting.
- R 2 c (H) d Si— represents (CH 3 ) 3 Si—, (CH 3 ) 2 (H) Si—, (C 4 H 9 ) (CH 3 ) 2 Si— , (C 6 H 13 ) (CH 3 ) 2 Si—, (C 8 H 17 ) (CH 3 ) 2 Si—, or (C 10 H 21 ) (CH 3 ) 2 Si—, and Y
- the chemical solution for forming a protective film of the present invention is obtained by adding the silicon compound B excessively to the acid B, and the silicon compound B that is not consumed in the reaction is converted to the protective film using the acid A generated by the reaction as a catalyst. May be formed. That is, the surplus of the silicon compound B that has not been consumed in the reaction may contribute to the formation of the protective film as the silicon compound A.
- the silicon compound B is preferably 0.2 to 100000 mol times, preferably 0.5 to 50000 mol times, and more preferably 1 to 10000 mol times with respect to the acid B. .
- the acid A accepts electrons from the silicon compound A to promote a reaction between the silicon compound A and a silanol group which is a reaction site on the surface of the silicon wafer, and the silicon compound A is converted into Si of the silicon wafer through a siloxane bond. Acts as a catalyst to chemically bond with elements.
- the acid A is considered to act like the mechanism of the upper stage of the following figure. In the figure, acid A is expressed as “L”.
- the protective film can be formed in a short time. When the amount of water in the chemical solution increases, the silicon compound A is hydrolyzed and the reactivity is easily lowered, and as a result, the protective film is hardly formed.
- the total amount of moisture in the starting material is 5000 ppm by mass or less based on the total amount of the starting material.
- the water content exceeds 5000 mass ppm, it is difficult to form the protective film in a short time.
- the smaller the total amount of water the more preferable, particularly 1000 ppm by mass or less, and even more preferable 500 ppm by mass or less.
- medical solution will fall easily when there are many amounts of water, the one where water content is small is preferable, 200 mass ppm or less, Furthermore, 100 mass ppm or less is preferable.
- 0.1 mass ppm or more may be sufficient as the moisture content in the raw material of the said chemical
- the Bronsted acid acts like the lower mechanism in the figure below, and the silanol group which is a reaction site on the substrate surface partially reacts to form the silicon compound A. It is considered that the silicon element is chemically bonded to the Si element of the silicon wafer through the siloxane bond, but the Bronsted acid in the chemical solution reacts with the silicon compound A to reduce the silicon compound A or the reactivity of the silicon compound A. Therefore, there is a tendency that sufficient water repellency cannot be expressed on the substrate surface.
- the number of particles larger than 0.5 ⁇ m in the particle measurement by the light scattering type submerged particle detector in the liquid phase in the chemical solution is 100 or less per 1 mL of the chemical solution. If the number of particles larger than 0.5 ⁇ m exceeds 100 per 1 mL of the chemical solution, pattern damage due to the particles may be induced, which causes a decrease in device yield and reliability. Further, it is preferable that the number of particles larger than 0.5 ⁇ m is 100 or less per mL of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced. The number of particles larger than 0.5 ⁇ m may be 1 or more per 1 mL of the chemical solution.
- the particle measurement in the liquid phase in the chemical solution in the present invention is performed by using a commercially available measuring device in the light scattering liquid particle measurement method using a laser as a light source.
- PSL polystyrene latex
- the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe and Cu in the chemical solution is 100 mass ppb or less with respect to the total amount of the chemical solution.
- the metal impurities of each element described above are all those that exist in the chemical solution in the form of metal fine particles, ions, colloids, complexes, oxides and nitrides, whether dissolved or undissolved. If the metal impurity content is more than 100 mass ppb with respect to the total amount of the chemical solution, the junction leakage current of the device may increase, which causes a decrease in device yield and reliability, which is not preferable.
- the metal impurity content is 100 mass ppb or less with respect to the total amount of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced.
- 0.01 mass ppb or more of each said metal impurity content may be sufficient with respect to this chemical
- the chemical solution for forming a protective film of the present invention is used by substituting the chemical solution for the cleaning solution in the step of cleaning the wafer on which the uneven pattern is formed. Further, the replaced chemical liquid may be replaced with another cleaning liquid.
- the protective solution is formed on at least the concave surface of the concavo-convex pattern while the cleaning liquid is replaced with the chemical solution for forming the protective film and the chemical solution is held on at least the concave surface of the concavo-convex pattern.
- the protective film of the present invention does not necessarily have to be formed continuously, and does not necessarily have to be formed uniformly. However, since it can impart better water repellency, it can be applied continuously and uniformly. More preferably, it is formed.
- the water-repellent protective film of the wafer refers to a film that reduces the wettability of the wafer surface by being formed on the wafer surface, that is, a film that imparts water repellency.
- the water repellency means that the surface energy of the article surface is reduced and the interaction (for example, hydrogen bond, intermolecular force) between water or other liquid and the article surface is reduced. It is.
- the effect of reducing the interaction with water is great, but it has the effect of reducing the interaction with a mixed liquid of water and a liquid other than water or a liquid other than water. By reducing the interaction, the contact angle of the liquid with the article surface can be increased.
- the protective film when the cleaning liquid is removed from the recess, that is, when dried, the protective film is formed on at least the recess surface of the recess / protrusion pattern, so that the capillary force on the recess surface is reduced and the pattern collapses. Is less likely to occur.
- the protective film can be removed by at least one treatment selected from light irradiation of the wafer surface, heating of the wafer, exposure of the wafer to ozone, and irradiation of the wafer surface with plasma.
- the protective film formed by the chemical solution for forming a protective film of the present invention is excellent in water repellency, it reduces the capillary force on the surface of the concavo-convex pattern of the wafer, and thus exhibits an effect of preventing pattern collapse.
- the cleaning step in the method for producing a wafer having a fine uneven pattern on the surface can be improved without lowering the throughput. Therefore, the method for producing a wafer having a fine concavo-convex pattern on the surface, which is carried out using the chemical solution for forming a protective film of the present invention, has high productivity.
- the chemical solution for forming a protective film according to the present invention can cope with a concavo-convex pattern having an aspect ratio of, for example, 7 or more which is expected to become higher in the future, and can reduce the cost of production of higher-density semiconductor devices.
- the conventional apparatus can be applied without significant change, and as a result, can be applied to the manufacture of various semiconductor devices.
- FIG. 1 is a schematic plan view of a wafer 1 whose surface is a surface having a fine concavo-convex pattern 2.
- FIG. 2 shows a part of the a-a ′ cross section in FIG. 1. The schematic diagram of the state in which the recessed part 4 hold
- a suitable cleaning method for a wafer having a fine concavo-convex pattern on the surface and at least a part of the concavo-convex pattern containing silicon element, using the chemical solution for forming a protective film of the present invention (Step 1) A step of making the wafer surface a surface having a fine concavo-convex pattern, then subjecting the surface to an aqueous cleaning solution, and holding the aqueous cleaning solution on at least the concave surface of the concavo-convex pattern; (Step 2) A step of replacing the aqueous cleaning liquid held on at least the concave surface of the concavo-convex pattern with a cleaning liquid A different from the aqueous cleaning liquid, (Step 3) Replacing the cleaning liquid A with a protective film-forming chemical solution, and holding the chemical solution on at least the concave surface of the concave-convex pattern; (Step 4) A step of removing liquid from the surface of the concavo-convex pattern by drying, (
- the chemical solution held on at least the concave surface of the concavo-convex pattern was replaced with a cleaning liquid B different from the chemical solution. Later, the process may be shifted to a step of removing the liquid from the surface of the concavo-convex pattern by drying (step 4).
- an aqueous cleaning liquid composed of an aqueous solution is held on at least the concave surface of the concave / convex pattern, and then the process may be shifted to a step of removing the liquid from the concave / convex pattern surface by drying (step 4).
- the protective film forming chemical can be replaced with an aqueous cleaning liquid
- the replacement with the cleaning liquid B may be omitted.
- the cleaning method of the wafer is not particularly limited as long as the chemical solution or the cleaning solution can be held on at least the concave surface of the concave / convex pattern of the wafer.
- a wafer cleaning method represented by spin cleaning in which a wafer is cleaned one by one by supplying liquid to the vicinity of the rotation center while rotating the wafer while holding the wafer substantially horizontal, or a plurality of cleaning methods in the cleaning tank.
- a batch system in which a single wafer is immersed and washed.
- the form of the chemical solution or cleaning liquid when supplying the chemical solution or cleaning liquid to at least the concave surface of the concave / convex pattern of the wafer is not particularly limited as long as it becomes liquid when held on the concave surface, for example, , Liquid, vapor, etc.
- the silicon compound A in the chemical solution is preferably a compound represented by the following general formula [1].
- R 1 s each independently contain a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms and a fluoroalkyl chain having 1 to 8 carbon atoms.
- X is at least one group selected from valent organic groups, X is each independently a monovalent organic group in which the element bonded to the Si element is nitrogen, a is an integer of 1 to 3, b Is an integer from 0 to 2, and the sum of a and b is 1 to 3.
- the monovalent organic group in which the element bonded to the Si element as X is nitrogen includes not only hydrogen, carbon, nitrogen, and oxygen elements but also silicon, sulfur, halogen elements, and the like. May be.
- X which is a reactive site, reacts quickly with silanol groups, which are reaction sites on the surface of the concave / convex pattern of the silicon wafer, and the silicon compound A reacts with the Si element of the silicon wafer via a siloxane bond.
- the wafer surface can be covered with the hydrophobic R 1 group, so that the capillary force on the concave surface of the wafer can be reduced in a short time.
- the number of X of the silicon compound A represented by 4-ab in the general formula [1] is 1 because the protective film can be formed uniformly.
- the protective film is formed on the surface of the concavo-convex pattern, at least one group selected from is more preferable because the wettability of the surface can be further reduced, that is, excellent water repellency can be imparted to the surface. Further, it is more preferable that m and n are 1 to 8 because a protective film can be formed on the surface of the concavo-convex pattern in a short time.
- Examples of the silicon compound A represented by the general formula [1] include CH 3 Si (NH 2 ) 3 , C 2 H 5 Si (NH 2 ) 3 , C 3 H 7 Si (NH 2 ) 3 , C 4 H 9 Si (NH 2 ) 3 , C 5 H 11 Si (NH 2 ) 3 , C 6 H 13 Si (NH 2 ) 3 , C 7 H 15 Si (NH 2 ) 3 , C 8 H 17 Si (NH 2 ) 3 , C 9 H 19 Si (NH 2 ) 3 , C 10 H 21 Si (NH 2 ) 3 , C 11 H 23 Si (NH 2 ) 3 , C 12 H 25 Si (NH 2 ) 3 , C 13 H 27 Si (NH 2) 3 , C 14 H 29 Si (NH 2) 3, C 15 H 31 Si (NH 2) 3, C 16 H 33 Si (NH 2) 3, C 17 H 35 Si (NH 2 ) 3 , C 18 H 37 Si (NH 2 ) 3 , (CH 3 ) 2 Si (NH 2 ) 2 , C 2 H 5 Si (
- X of the silicon compound A of the formula [1] is —N (CH 3 ) 2 , —NH 2 , —N (C 2 H 5 ) 2 , —N (CH 3 ) C (O) CH 3 , —N (CH 3 ) C (O) CF 3 , —NHC (O) —NH—Si (CH 3 ) 3 , imidazole ring, —N ⁇ C ⁇ O, —NH—C (O) —Si (CH 3 ) 3 , —N (H) 2-i (Si (H) j R 4 3-j ) i (R 4 is the number of carbon atoms in which some or all of the hydrogen elements may be replaced by fluorine elements.
- the concentration of the acid A is preferably 0.01 to 50% by mass with respect to 100% by mass of the total amount of the silicon compound A. If the addition amount is small, the effect of the acid is lowered, which is not preferable. Even if the amount is excessively large, the effect of the acid as a catalyst is not improved. is there. Therefore, the concentration of the acid A is particularly preferably 0.05 to 25% by mass with respect to 100% by mass of the total amount of the silicon compound A.
- the silicon compound A and the acid A may be diluted with a solvent.
- the total amount of silicon compound A and acid A added is 0.01 to 100% by mass with respect to 100% by mass of the total amount of the chemical solution, it is easy to form a protective film uniformly on at least the concave surface of the concave / convex pattern. Therefore, it is preferable. If it is less than 0.01% by mass, the protective effect of the uneven pattern tends to be insufficient. In addition, if the total amount of silicon compound A and acid A added is large, the cost increases.
- the silicon compound A and the acid A may come into contact with a protic solvent such as water or alcohol, or the silicon compound A and the acid A may react as a by-product, which is generated when the sum is large.
- a protic solvent such as water or alcohol
- the silicon compound A and the acid A may react as a by-product, which is generated when the sum is large.
- the amount of solid matter to be increased also increases. In many cases, the solid matter can be dissolved in the chemical solution, but the risk of remaining on the wafer as particles after drying increases, so that the chemical solution becomes difficult to handle. From such a viewpoint, the total is more preferably 0.05 to 50% by mass, and more preferably 0.1 to 30% by mass. Further, if the total amount of silicon compound A and acid A added is large, the storage stability of the chemical solution is easily increased. For this reason, 0.5 to 30% by mass, more preferably 1 to 30% by mass is preferable.
- Examples of the solvent that may be used for dilution in the chemical solution include hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxide solvents, alcohols, polyhydric alcohol derivatives, and nitrogen element-containing solvents.
- An organic solvent such as a solvent is preferably used.
- hydrocarbons, esters, ethers, halogen element-containing solvents, sulfoxide solvents, polyhydric alcohol derivatives having no OH group can be used to form a protective film on the surface of the concavo-convex pattern in a short time. Since it can form, it is more preferable.
- hydrocarbons examples include toluene, benzene, xylene, hexane, heptane, and octane.
- esters examples include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetoacetate, and the ether.
- Examples of the class include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like, and examples of the halogen element-containing solvent include perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, Perfluorocarbons such as hexafluorobenzene, hydrofluores such as 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeolora H (manufactured by Nippon Zeon) Carbon, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asahi Clin AE-3000 (manufact
- Examples of the sulfoxide solvents include dimethyl sulfoxide and the like.
- Examples of those having no group include diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl Ether, diethylene glycol monomethyl ether acetate And diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, and ethylene glycol dimethyl ether.
- nonflammable organic solvent it is preferable to use a nonflammable organic solvent because the chemical solution for forming the protective film becomes nonflammable or the flash point becomes high, thereby reducing the risk of the chemical solution.
- Many halogen element-containing solvents are nonflammable, and the nonflammable halogen element-containing solvent can be suitably used as a nonflammable organic solvent.
- the total amount of moisture in the starting material of the protective film forming chemical is preferably 5000 ppm by mass or less with respect to the total amount of the material.
- the total amount of moisture exceeds 5000 mass ppm, the effects of the silicon compound A and acid A represented by the general formula [1] are reduced, and it is difficult to form the protective film in a short time.
- the total amount of the water content is preferably as small as possible, particularly 1000 ppm by mass or less, and more preferably 500 ppm by mass or less. Therefore, it is preferable that the silicon compound A and acid A contained in the chemical solution and the solvent that may be contained in the chemical solution do not contain much water.
- the number of particles larger than 0.5 ⁇ m in the particle measurement by the light scattering type submerged particle detector in the liquid phase in the chemical solution is 100 or less per 1 mL of the chemical solution. If the number of particles larger than 0.5 ⁇ m exceeds 100 per 1 mL of the chemical solution, pattern damage due to the particles may be induced, which causes a decrease in device yield and reliability. Further, it is preferable that the number of particles larger than 0.5 ⁇ m is 100 or less per mL of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced.
- the number of particles larger than 0.5 ⁇ m in the chemical solution per 1 mL of the chemical solution is preferably as small as possible, particularly 10 or less, and more preferably 2 or less.
- the number of particles larger than 0.5 ⁇ m may be 1 or more per 1 mL of the chemical solution.
- the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe and Cu in the chemical solution is 100 mass ppb or less with respect to the total amount of the chemical solution. If the metal impurity content is more than 100 mass ppb with respect to the total amount of the chemical solution, the junction leakage current of the device may be increased, which causes a decrease in device yield and reliability. Moreover, it is preferable that the metal impurity content is 100 mass ppb or less with respect to the total amount of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced.
- the content of the metal impurities is preferably as small as possible, and particularly preferably 1 mass ppb or less, and further preferably 0.1 mass ppb or less. Moreover, 0.01 mass ppb or more of each said metal impurity content may be sufficient with respect to this chemical
- the silicon compound A before mixing, the acid A, and the mixed solution after mixing It is preferable to purify at least one of them.
- the protective film-forming chemical solution contains a solvent
- the silicon compound A and the acid A before mixing may be in a solution state containing a solvent.
- the purification is performed before the silicon before mixing.
- the target may be at least one of compound A or a solution thereof, acid A or a solution thereof, and a mixed solution after mixing.
- the purification includes removal of moisture by adsorbents such as molecular sieves and distillation, removal of metal impurities of each element of Na, Mg, K, Ca, Mn, Fe and Cu by ion exchange resin or distillation, and filter. This is performed using at least one removing means among removing contaminants such as particles by filtration. In consideration of the reactivity of the chemical solution for forming the protective film and the cleanliness of the wafer, it is preferable to remove moisture, remove metal impurities, and remove contaminants, and the removal order is not limited.
- the acid A contained in the protective film-forming chemical solution of the present invention may be obtained by a reaction.
- it may be obtained by reacting the silicon compound B represented by the following general formula [2] with the acid B.
- R 2 c (H) d Si— represents (CH 3 ) 3 Si—, (CH 3 ) 2 (H) Si—, (C 4 H 9 ) (CH 3 ) 2 Si— , (C 6 H 13 ) (CH 3 ) 2 Si—, (C 8 H 17 ) (CH 3 ) 2 Si—, or (C 10 H 21 ) (CH 3 ) 2 Si—
- Y Each independently represents a monovalent organic group in which the element bonded to the Si element is nitrogen.
- medical solution prepared by making it react with the said silicon compound B and using the at least 1 chosen from the trifluoroacetic anhydride and the trifluoromethanesulfonic anhydride for the acid B, or the said silicon compound A And a chemical prepared using acid A as a starting material are more preferable because of their excellent stability.
- the silicon compound B is excessively added to the acid B, and the surplus of the silicon compound B not consumed in the reaction contributes to the formation of the protective film as the silicon compound A. It may be a thing.
- the silicon compound B is preferably 0.2 to 100000 mol times, preferably 0.5 to 50000 mol times, and more preferably 1 to 10000 mol times with respect to the acid B. .
- the monovalent organic group in which the element bonded to the Si element as Y of the silicon compound B of the general formula [2] is nitrogen includes not only hydrogen, carbon, nitrogen, and oxygen elements but also silicon, sulfur, halogen elements, and the like May be included.
- Y of the silicon compound B of the formula [2] represents —N (CH 3 ) 2 , —NH 2 , —N (C 2 H 5 ) 2 , —N (CH 3 ) C (O) CH 3 , —N (CH 3 ) C (O) CF 3 , —NHC (O) —NH—Si (CH 3 ) 3 , imidazole ring, —NH—C (O) —Si (CH 3 ) 3 , —NH— Si (CH 3 ) 3 , —NH—Si (H) (CH 3 ) 2 , —NH—Si (CH 3 ) 2 (C 4 H 9 ), —NH—Si (CH 3 ) 2 (C 6 H 13 ), —NH—Si (CH 3 ) 2 (C 8 H 17 ), and —NH—Si (CH 3 ) 2 (C 10 H 21 ) are preferred.
- trifluoromethanesulfonic anhydride when hexamethyldisilazane is mixed as the silicon compound B and trifluoromethanesulfonic anhydride is mixed as the acid B, the trifluoromethanesulfonic anhydride immediately reacts to obtain trimethylsilyl trifluoromethanesulfonate as the acid A. .
- the trifluoromethanesulfonic anhydride reacts immediately to obtain dimethylsilyl trifluoromethanesulfonate as the acid A. It is done.
- the total amount of water in the starting material of the protective film forming chemical is preferably 5000 ppm by mass or less based on the total amount of the material.
- the amount of water in the raw material is preferably as small as possible, particularly preferably 1000 ppm by mass or less, and more preferably 500 ppm by mass or less.
- medical solution will fall easily when there are many amounts of water, the one where water content is small is preferable, 200 mass ppm or less, Furthermore, 100 mass ppm or less is preferable.
- the total amount of water in the raw material may be 0.1 mass ppm or more.
- the number of particles larger than 0.5 ⁇ m in the particle measurement by the light scattering liquid particle detector in the liquid phase in the protective film forming chemical solution is The number is preferably 100 or less per 1 mL of the chemical solution. If the number of particles larger than 0.5 ⁇ m exceeds 100 per 1 mL of the chemical solution, pattern damage due to the particles may be induced, which causes a decrease in device yield and reliability. Further, it is preferable that the number of particles larger than 0.5 ⁇ m is 100 or less per mL of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced.
- the number of particles larger than 0.5 ⁇ m in the chemical solution per 1 mL of the chemical solution is preferably as small as possible, particularly 10 or less, and more preferably 2 or less.
- the number of particles larger than 0.5 ⁇ m may be 1 or more per 1 mL of the chemical solution.
- the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the protective film forming chemical solution is the total amount of the chemical solution. It is preferable that each is 100 mass ppb or less. If the metal impurity content is more than 100 mass ppb with respect to the total amount of the chemical solution, the junction leakage current of the device may be increased, which causes a decrease in device yield and reliability, which is not preferable. . Moreover, it is preferable that the metal impurity content is 100 mass ppb or less with respect to the total amount of the chemical solution because washing with a solvent or water after forming the protective film can be omitted or reduced.
- the content of the metal impurities is preferably as small as possible, and particularly preferably 1 mass ppb or less, and further preferably 0.1 mass ppb or less. Moreover, 0.01 mass ppb or more of each said metal impurity content may be sufficient with respect to this chemical
- the silicon compound B before mixing may be in a solution state containing a solvent.
- the purification is performed before mixing.
- the target may be at least one of silicon compound B or a solution thereof, acid B or a solution thereof, and a mixed solution after mixing.
- the target solution may be at least one of the solution and the mixed solution after mixing.
- the purification includes removal of moisture by adsorbents such as molecular sieves and distillation, removal of metal impurities of each element of Na, Mg, K, Ca, Mn, Fe and Cu by ion exchange resin or distillation, and filter. This is performed using at least one removing means among removing contaminants such as particles by filtration. In consideration of the activity and cleanliness of the chemical solution for forming the protective film, it is preferable to remove moisture, remove metal impurities, and remove contaminants, and the removal order is not limited.
- the protective film-forming chemical solution of the present invention includes, in addition to the silicon compound A, acid A, and solvent represented by the general formula [1], other additives and the like as long as the object of the present invention is not impaired. It may contain.
- the additive include oxidizing agents such as hydrogen peroxide and ozone, and surfactants.
- oxidizing agents such as hydrogen peroxide and ozone
- surfactants when there is a material that cannot form a protective film with the silicon compound A in a part of the uneven pattern of the wafer, a material that can form a protective film may be added to the material. Further, other acids may be added for purposes other than the catalyst.
- the chemical solution for forming a protective film of the present invention can be stored in a state where the raw materials are divided into two or more and mixed before use.
- silicon compound A and acid A when silicon compound A and acid A are used as a part of the raw material of the protective film forming chemical solution, silicon compound A and acid A can be stored separately and mixed before use.
- the silicon compound B and the acid B when using the silicon compound B and the acid B, the silicon compound B and the acid B can be stored separately and mixed before use.
- the silicon compound and the acid before mixing may be in a solution state.
- the above silicon compound and acid can be stored in the same solution and mixed with another raw material before use.
- the protective film-forming chemical solution of the present invention includes, for example, hydrofluoroether, hydrochlorofluorocarbon, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether.
- the wafer surface is a surface having a fine concavo-convex pattern
- the resist is exposed through a resist mask, and the exposed resist is not exposed.
- a resist having a desired concavo-convex pattern is produced by etching away the resist.
- corrugated pattern can be obtained also by pressing the mold which has a pattern to a resist.
- the wafer is etched. At this time, the concave portion of the resist pattern is selectively etched. Finally, when the resist is removed, a wafer having a fine uneven pattern is obtained.
- a wafer having a fine concavo-convex pattern on the surface and at least a part of the concavo-convex pattern containing silicon element a wafer containing a film containing silicon element such as silicon, silicon oxide, or silicon nitride, or When the concavo-convex pattern is formed, those in which at least a part of the surface of the concavo-convex pattern contains a silicon element such as silicon, silicon oxide, or silicon nitride are included.
- a wafer composed of a plurality of components including at least one selected from silicon, silicon oxide, and silicon nitride is also protected on at least one surface selected from silicon, silicon oxide, and silicon nitride.
- a film can be formed.
- the wafer composed of the plurality of components at least one selected from silicon, silicon oxide, and silicon nitride is formed on the wafer surface, or when a concavo-convex pattern is formed, at least one of the concavo-convex pattern is formed.
- a part whose part is at least one selected from silicon, silicon oxide, and silicon nitride is also included.
- FIG. 1 is a schematic plan view of a wafer 1 whose surface is a surface having a fine concavo-convex pattern 2, and FIG. 2 shows a part of an a-a ′ section in FIG. 1. As shown in FIG. 1
- the width 5 of the concave portion is indicated by the interval between the convex portion 3 and the convex portion 3
- the aspect ratio of the convex portion is expressed by dividing the height 6 of the convex portion by the width 7 of the convex portion. Is done. Pattern collapse in the cleaning process tends to occur when the width of the recess is 70 nm or less, particularly 45 nm or less, and the aspect ratio is 4 or more, particularly 6 or more.
- Step 1 after making the wafer surface a surface having a fine concavo-convex pattern, an aqueous cleaning solution is applied to the surface, and the aqueous cleaning solution is applied to at least the concave surface of the concavo-convex pattern. Hold. Then, as described in the above (Step 2), the aqueous cleaning liquid held on at least the concave surface of the concavo-convex pattern is replaced with a cleaning liquid A different from the aqueous cleaning liquid.
- the cleaning liquid A include at least one of a chemical solution for forming a protective film specified in the present invention, water, an organic solvent, or a mixture thereof, or an acid, an alkali, a surfactant, and an oxidizing agent. Are mixed. Further, when a liquid other than the chemical liquid is used as the cleaning liquid A, it is preferable to replace the cleaning liquid A with the protective film-forming chemical liquid in a state where the cleaning liquid A is held on at least the concave surface of the concavo-convex pattern.
- organic solvent examples include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, and polyhydric alcohol derivatives. And nitrogen element-containing solvents.
- hydrocarbons examples include toluene, benzene, xylene, hexane, heptane, and octane.
- esters examples include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetoacetate, and the ether.
- Examples of such classes include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like, and examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, and the like.
- halogen element-containing solvent examples include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, Hydrofluorocarbons such as 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeolora H (manufactured by Nippon Zeon), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl Hydrofluoroethers such as perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asahi Clin AE-3000 (manufactured by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, and Novec 7600 (all
- Chlorocarbon hydrochlorocarbon such as chloroform
- chlorofluorocarbon such as dichlorodifluoromethane, 1,1-dichloro-2,2,3, , 3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3
- Hydrochlorofluorocarbons such as 1,3-trifluoropropene, perfluoroethers, perfluoropolyethers, etc.
- Examples of the sulfoxide solvents include dimethyl sulfoxide, and examples of alcohols include methanol, ethanol, Examples of the polyhydric alcohol derivatives include diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl, and the like.
- Chill ether propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, etc.
- solvents include formamide, N, N- dimethylformamide, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, diethylamine, triethylamine, pyridine and the like.
- acids that may be mixed in the cleaning liquid A include inorganic acids and organic acids.
- inorganic acids include hydrofluoric acid, buffered hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, etc.
- organic acids include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid , Acetic acid, trifluoroacetic acid, pentafluoropropionic acid and the like.
- alkali that may be mixed in the cleaning liquid A include ammonia and choline.
- the oxidizing agent that may be mixed with the cleaning liquid A include ozone and hydrogen peroxide.
- the cleaning liquid A is an organic solvent because the chemical liquid for forming a protective film can be provided to the recess without being brought into contact with water.
- the organic solvent contains a water-soluble organic solvent (a solubility of 5 parts by mass or more with respect to 100 parts by mass of water) because the cleaning liquid A can be easily replaced from the aqueous cleaning liquid.
- the cleaning liquid A contains an acid aqueous solution because the protective film can be formed in a short time.
- a plurality of cleaning liquids may be used as the cleaning liquid A.
- a cleaning solution containing an acid aqueous solution or an alkaline aqueous solution and the organic solvent (preferably containing a water-soluble organic solvent) are used as the cleaning solution A, and the cleaning is performed in the order of the cleaning solution containing the acid aqueous solution or the alkaline aqueous solution ⁇ the organic solvent.
- an aqueous cleaning solution may be further added, and cleaning may be performed in the order of a cleaning solution containing an aqueous acid solution or an aqueous alkaline solution ⁇ an aqueous cleaning solution ⁇ the organic solvent.
- FIG. 3 shows a schematic view of the state in which the recess 4 holds the protective film forming chemical 8 in the cleaning process.
- the wafer shown in the schematic diagram of FIG. 3 shows a part of the a-a ′ cross section of FIG. 1.
- the protective film forming chemical is supplied to the wafer 1 on which the concave / convex pattern 2 is formed.
- the chemical solution is held in the recess 4 as shown in FIG. 3, and a protective film is formed on the surface of the recess 4 to make the surface water repellent.
- the temperature at which a homogeneous protective film is easily formed is preferably 10 ° C. or higher and lower than the boiling point of the chemical solution, and more preferably 15 ° C. or higher and lower than 10 ° C. lower than the boiling point of the chemical solution.
- the temperature of the chemical solution is preferably maintained at the temperature even when held on at least the concave surface of the concave / convex pattern.
- cleaning liquids may be held at a temperature of 10 ° C. or higher and lower than the boiling point of the cleaning liquid.
- the cleaning liquid A contains an acid aqueous solution, particularly preferably a solution containing an acid aqueous solution and an organic solvent having a boiling point of 100 ° C. or higher
- the protective film can be shortened for a short time if the temperature of the cleaning liquid is raised near the boiling point of the cleaning liquid It is preferable because it is easy to form.
- the step of removing the liquid from the surface of the concavo-convex pattern by drying may be performed.
- the cleaning liquid B include an aqueous cleaning liquid composed of an aqueous solution, an organic solvent, or the aqueous cleaning liquid and the organic solvent. A mixture of at least one of acid, alkali, and surfactant, or silicon compound A and acid A contained in the chemical solution for forming a protective film, and the acid A at a lower concentration than the chemical solution. And so on.
- Examples of the organic solvent that is one of the preferred examples of the cleaning liquid B include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, and derivatives of polyhydric alcohols. And nitrogen element-containing solvents.
- hydrocarbons examples include toluene, benzene, xylene, hexane, heptane, and octane.
- esters examples include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetoacetate, and the ether.
- Examples of such classes include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like, and examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, and the like.
- halogen element-containing solvent examples include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, Hydrofluorocarbons such as 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeolora H (manufactured by Nippon Zeon), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl Hydrofluoroethers such as perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asahi Clin AE-3000 (manufactured by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec 7300, and Novec 7600 (all
- Chlorocarbon hydrochlorocarbon such as chloroform
- chlorofluorocarbon such as dichlorodifluoromethane, 1,1-dichloro-2,2,3, , 3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3
- Hydrochlorofluorocarbons such as 1,3-trifluoropropene, perfluoroethers, perfluoropolyethers, etc.
- Examples of the sulfoxide solvents include dimethyl sulfoxide, and examples of alcohols include methanol, ethanol, Examples of the polyhydric alcohol derivatives include diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl, and the like.
- Chill ether propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, etc.
- solvents include formamide, N, N- dimethylformamide, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, diethylamine, triethylamine, pyridine and the like.
- an aqueous cleaning liquid composed of an aqueous solution is held on at least the concave surface of the concave / convex pattern, and then the process may be shifted to a step of removing the liquid from the concave / convex pattern surface by drying (step 4).
- a plurality of cleaning liquids may be used as the cleaning liquid B.
- an organic solvent preferably containing a water-soluble organic solvent
- an aqueous cleaning solution can be used.
- the aqueous cleaning liquid examples include water or water mainly containing water mixed with at least one organic solvent, acid or alkali in water (for example, the water content is 50% by mass or more). It is done.
- the contact angle ⁇ with the liquid on at least the concave surface of the concave / convex pattern made water repellent by the chemical solution increases, and the capillary force P on the concave surface decreases, and further after drying. This is preferable because dirt on the wafer surface is less likely to remain.
- FIG. 4 shows a schematic diagram when the aqueous cleaning liquid is held in the recess 4 made water repellent by the protective film forming chemical.
- the wafer in the schematic diagram of FIG. 4 shows a part of the a-a ′ cross section of FIG.
- the surface of the concavo-convex pattern is water repellent by forming a protective film 10 with the chemical solution.
- the protective film 10 is held on the wafer surface even when the aqueous cleaning liquid 9 is removed from the uneven pattern surface.
- the contact angle is 70 to 110 ° on the assumption that water is held on the surface. It is preferable because it does not easily fall over. Further, the closer the contact angle is to 90 °, the smaller the capillary force on the surface of the concave portion, and the pattern collapse is less likely to occur, so 75 to 105 ° is more preferable.
- the capillary force is preferably 1.1 MN / m 2 or less. A capillary force of 1.1 MN / m 2 or less is preferable because pattern collapse hardly occurs. Further, when the capillary force is reduced, pattern collapse is less likely to occur.
- the capillary force is more preferably 0.8 MN / m 2 or less. Furthermore, it is ideal to adjust the contact angle with the cleaning liquid to around 90 ° so that the capillary force is as close as possible to 0.0 MN / m 2 .
- a step of removing the liquid from the surface of the concavo-convex pattern by drying is performed.
- the liquid held on the uneven pattern surface is removed by drying.
- the drying is preferably performed by a known drying method such as spin drying, IPA (2-propanol) vapor drying, Marangoni drying, heat drying, hot air drying, or vacuum drying.
- the liquid held on the surface may be the chemical liquid, the cleaning liquid B, the aqueous cleaning liquid, and a mixture thereof.
- the liquid mixture containing the chemical liquid may be a liquid in the middle of replacing the chemical liquid with the cleaning liquid B, or may be a liquid mixture obtained by previously mixing the chemical liquid with a cleaning liquid different from the chemical liquid.
- the uneven pattern surface is held with at least one selected from the cleaning liquid B, the aqueous cleaning liquid, and a mixture thereof, and then dried. Also good.
- a step of removing the protective film 10 is performed.
- the method is not particularly limited as long as it can cut the bond, for example, irradiating the wafer surface with light, heating the wafer, exposing the wafer to ozone, irradiating the wafer surface with plasma, For example, corona discharge on the wafer surface may be mentioned.
- the protective film 10 When the protective film 10 is removed by light irradiation, it is effective to cut the C—C bond and C—F bond in the protective film 10, and for this purpose, their binding energy is 83 kcal / mol. It is preferable to irradiate ultraviolet rays including wavelengths shorter than 340 nm and 240 nm, which are energy corresponding to 116 kcal / mol.
- a metal halide lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an excimer lamp, a carbon arc, or the like is used.
- the ultraviolet irradiation intensity is a metal halide lamp, for example, measurement with an illuminometer (irradiance intensity meter UM-10 manufactured by Konica Minolta Sensing, light receiving unit UM-360 [peak sensitivity wavelength: 365 nm, measurement wavelength range: 310 to 400 nm]) 100 mW / cm 2 or more is preferable in value, 200 mW / cm 2 or more is particularly preferable.
- the irradiation intensity is less than 100 mW / cm 2 , it takes a long time to remove the protective film 10.
- a low-pressure mercury lamp is preferable because ultraviolet rays having a shorter wavelength are irradiated, and thus the protective film 10 can be removed in a short time even if the irradiation intensity is low.
- ozone is generated at the same time as the constituent components of the protective film 10 are decomposed by ultraviolet rays, and the constituent components of the protective film 10 are oxidized and volatilized by the ozone.
- this light source a low-pressure mercury lamp or an excimer lamp is used. Further, the wafer may be heated while irradiating light.
- the wafer When heating the wafer, the wafer is heated at 400 to 700 ° C., preferably 500 to 700 ° C.
- the heating time is preferably 0.5 to 60 minutes, preferably 1 to 30 minutes.
- ozone exposure, plasma irradiation, corona discharge, etc. may be used in combination. Further, light irradiation may be performed while heating the wafer.
- ozone generated by ultraviolet irradiation with a low-pressure mercury lamp or the like or low-temperature discharge with a high voltage is provided on the wafer surface.
- the wafer may be irradiated with light while being exposed to ozone, or may be heated.
- the protective film on the wafer surface can be efficiently removed by combining light irradiation treatment, heat treatment, ozone exposure treatment, plasma irradiation treatment, corona discharge treatment, and the like. it can.
- the chemical solution of the present invention may be a one-component type in which the silicon compound A and the acid A are mixed from the beginning, or used as a two-component type of a solution containing the silicon compound A and a solution containing the acid A. When mixing, you may mix. Moreover, it is good also as a 2 liquid type of the liquid containing the said silicon compound B, and the liquid containing the said acid B.
- the contact angle of the droplet and the capillary force on the concave surface which can be considered as equivalent to the pattern collapse, have a correlation.
- Capillary force may be derived from the evaluation of the contact angle of ten droplets.
- water which is a typical aqueous cleaning solution, was used as the cleaning solution.
- the contact angle of water droplets is evaluated by dropping several microliters of water droplets on the surface of the sample (base material) as described in JIS R 3257 “Testing method for wettability of substrate glass surface”. It is made by measuring. However, in the case of a wafer having a pattern, the contact angle becomes very large. This is because a Wenzel effect and a Cassie effect occur, and the contact angle is affected by the surface shape (roughness) of the substrate, and the apparent contact angle of water droplets increases.
- the chemical solution is applied to a wafer having a smooth surface, a protective film is formed on the wafer surface, and the protective film is formed on the surface of the wafer 1 on which the fine uneven pattern 2 is formed.
- a wafer having a smooth surface a silicon wafer having a surface having a thermal oxide film layer, a silicon nitride layer or a silicon layer and having a smooth surface is used.
- evaluation method of wafer provided with chemical solution for forming protective film The following evaluations (1) to (4) were performed as methods for evaluating a wafer provided with a chemical solution for forming a protective film.
- ⁇ the surface tension
- ⁇ the contact angle
- S the pattern dimension.
- a line-and-space pattern wafer having a line width (recess width) corresponding to the pattern dimension of 45 nm was assumed.
- the pattern tends to collapse when the cleaning liquid is water when the gas-liquid interface passes through the wafer, and the pattern does not easily collapse when 2-propanol is used.
- the capillary force is 0.98 MN / m 2 when the cleaning liquid is 2-propanol (surface tension: 22 mN / m, contact angle with silicon oxide: 1 °).
- the capillary force is 3.2 MN / m 2 in water (surface tension: 72 mN / m, contact angle with silicon oxide: 2.5 °) having the largest surface tension among liquids excluding mercury.
- Capillary force is preferably 1.1 MN / m 2 or less, particularly preferably 0.8Mn / m 2 or less.
- X L , X R , Y B , and Y T indicate measurement ranges of the X coordinate and the Y coordinate, respectively.
- S 0 is an area when the measurement surface is ideally flat, and has a value of (X R ⁇ X L ) ⁇ (Y B ⁇ Y T ).
- F (X, Y) represents the height at the measurement point (X, Y), and Z 0 represents the average height in the measurement plane.
- Example 1 (1) Preparation of chemical solution for forming protective film Hexamethyldisilazane [(H 3 C) 3 Si—NH—Si (CH 3 ) 3 ] as silicon compound A; 1 g, trimethylsilyl trifluoroacetate [(CH 3 ) 3 Si—OC (O) CF 3 ]; 0.1 g and propylene glycol monomethyl ether acetate (PGMEA); 98.9 g as an organic solvent were mixed to obtain a chemical solution for forming a protective film.
- PMEA propylene glycol monomethyl ether acetate
- ion exchange resin Natural Pole's Ion Clean SL
- filtered Natural Integris Optimizer
- the metal impurity content in the chemical solution after purification was measured by an inductively coupled plasma mass spectrometer (Yokogawa Analytical Systems, Agilent 7500cs type), Na, Mg, K,
- the number of particles larger than 0.5 ⁇ m in the particle measurement by the light scattering liquid particle detector in the liquid phase was measured by a light scattering liquid particle measuring device (manufactured by Rion Co., Ltd., KS-42AF type)
- the number of particles larger than 0.5 ⁇ m was 2 per 1 mL of the drug solution.
- the total amount of water in the starting material of the chemical solution was 5000 ppm by mass or less with respect to the total amount of the raw material, and the same purification was performed.
- the initial contact angle before the surface treatment was less than 10 °.
- the contact angle after the surface treatment was 84 °, which showed the effect of imparting water repellency.
- the capillary force when water was held was calculated using the formula described in the above “Evaluation of Capillary Force”, the capillary force was 0.3 MN / m 2 and the capillary force was small.
- the contact angle after UV irradiation was less than 10 °, and the protective film could be removed.
- the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
- the chemical solution used in this example had no change in appearance even after storage at 45 ° C. for 1 week, the contact angle after the surface treatment was 84 °, and no performance degradation was observed.
- Example 2 to 56 The silicon compound A used in Example 1, the concentration of the silicon compound A, the acid A, the organic solvent, the conditions such as the treatment procedure after the surface treatment of the protective film forming chemical solution are appropriately changed, and the wafer surface treatment is performed. Furthermore, the evaluation was performed. The results are shown in Tables 1 and 2.
- (CH 3 ) 3 Si—OS (O 2 ) CF 3 ” means trimethylsilyl trifluoromethanesulfonate.
- PGMEA propylene glycol monomethyl ether acetate
- HFE-7100 hydrofluoroether (3M HFE-7100)
- CTFP means 1-chloro-3,3,3-trifluoropropene
- DCTFP means cis-1,2-dichloro-3,3,3-trifluoropropene
- Example 56 0.05 g each of trimethylsilyl trifluoroacetate and trimethylsilyl trifluoromethanesulfonate was used as acid A.
- Examples 17 to 20 after immersing the silicon wafer in the protective film forming chemical solution in “(3) Surface treatment with the protective film forming chemical solution on the surface of the silicon wafer” described above, the silicon wafer was immersed in pure water for 1 minute. The silicon wafer was taken out from the pure water and air was blown to remove the pure water on the surface.
- Examples 21 to 24 after immersing the silicon wafer in the protective film forming chemical solution in the above “(3) Surface treatment with the protective film forming chemical solution on the silicon wafer surface”, the silicon wafer was immersed in iPA for 1 minute, and finally, The silicon wafer was taken out from the iPA and air was blown to remove the surface iPA.
- Examples 29 to 30 after immersing a silicon wafer in a chemical solution for forming a protective film in “(3) surface treatment with a chemical solution for forming a protective film on the surface of the silicon wafer”, air was blown to form a protective film on the surface. The medical solution was removed. Subsequently, it was immersed in pure water for 1 minute. Finally, the silicon wafer was taken out from the pure water and air was blown to remove the pure water on the surface.
- Examples 31 to 32 after the silicon wafer was immersed in the protective film forming chemical solution in “(3) Surface treatment with the protective film forming chemical solution on the silicon wafer surface”, air was blown to form the protective film on the surface. The medical solution was removed. Subsequently, it was immersed in iPA for 1 minute. Finally, the silicon wafer was taken out from iPA and air was blown to remove iPA on the surface.
- Examples 33 to 34 after immersing the silicon wafer in the chemical solution for forming the protective film in “(3) Surface treatment with the chemical solution for forming the protective film on the surface of the silicon wafer”, air was blown to form the protective film on the surface.
- the medical solution was removed. Next, it was immersed in iPA for 1 minute, and immersed in pure water for 1 minute. Finally, the silicon wafer was taken out from the pure water, and air was blown to remove the pure water on the surface.
- Example 51 in the above “(2) Cleaning of silicon wafer”, a smooth silicon wafer with a thermal oxide film (Si wafer having a thermal oxide film layer having a thickness of 1 ⁇ m on the surface) was changed to a 1 mass% hydrofluoric acid aqueous solution. It was immersed for 2 minutes at room temperature and then immersed in pure water for 1 minute. Further, it was immersed in a 0.3 mass% hydrochloric acid aqueous solution at 98 ° C. for 1 minute, then immersed in pure water at room temperature for 1 minute, and then immersed in 2-propanol (iPA) for 1 minute.
- the same treatment as described above was performed using a smooth silicon nitride-coated silicon wafer (Si wafer having a 0.3 ⁇ m thick silicon nitride layer on the surface).
- Example 53 and Example 55 1% by mass of the silicon wafer with a smooth silicon nitride film (Si wafer having a silicon nitride layer with a thickness of 0.3 ⁇ m on the surface) was obtained in the above “(2) Cleaning of silicon wafer”.
- Si wafer having a silicon nitride layer with a thickness of 0.3 ⁇ m on the surface was obtained in the above “(2) Cleaning of silicon wafer”.
- a hydrofluoric acid aqueous solution at room temperature for 2 minutes and then immersed in pure water for 1 minute.
- a mixed solution of 0.6 mass% hydrochloric acid aqueous solution and ethylene glycol in a mass ratio of 50:50 at 98 ° C. for 1 minute and then immersed in pure water at room temperature for 1 minute 2-propanol (iPA) For 1 minute.
- iPA 2-propanol
- Example 57 Hexamethyldisilazane [(H 3 C) 3 Si—NH—Si (CH 3 ) 3 ] as the silicon compound B; 1 g, trifluoroacetic anhydride [ ⁇ CF 3 C (O) ⁇ 2 O] as the acid B; 0.1 g and 98.9 g of PGMEA as an organic solvent were mixed and reacted to give a protective film forming chemical solution containing trimethylsilyl trifluoroacetate as acid A, hexamethyldisilazane as silicon compound A, and PGMEA as organic solvent. It was the same as Example 1 except that it was obtained.
- Hexamethyldisilazane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A.
- the evaluation result showed that the contact angle after the surface treatment was 82 °, indicating the effect of imparting water repellency. Further, the capillary force when water was held was 0.4 MN / m 2 , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
- Example 58 to 71 The conditions of the silicon compound B, acid B, organic solvent, and the like used in Example 57 were changed as appropriate, and the wafer was subjected to a surface treatment and further evaluated. The results are shown in Table 3.
- C 4 H 9 Si (CH 3 ) 2 —NH—Si (CH 3 ) 2 C 4 H 9 ” means 1,3-dibutyltetramethyldisilazane
- C 8 H 17 “Si (CH 3 ) 2 —NH—Si (CH 3 ) 2 C 8 H 17 ” means 1,3-dioctyltetramethyldisilazane.
- ⁇ CF 3 S (O 2 ) ⁇ 2 O means trifluoromethanesulfonic anhydride.
- Examples 58 to 59 when trifluoroacetic anhydride used as acid B is mixed with hexamethyldisilazane which is silicon compound B, it immediately reacts and changes to trimethylsilyl trifluoroacetate.
- the examples have the same meaning as when trimethylsilyl trifluoroacetate is used as acid A.
- Examples 60 to 62 when trifluoromethanesulfonic anhydride used as acid B is mixed with hexamethyldisilazane which is silicon compound B, it immediately reacts and changes to trimethylsilyl trifluoromethanesulfonate.
- This example has the same meaning as when trimethylsilyl trifluoromethanesulfonate is used as acid A.
- Examples 63 to 65 when trifluoroacetic anhydride used as acid B is mixed with tetramethyldisilazane which is silicon compound B, it immediately reacts and changes to dimethylsilyl trifluoroacetate.
- This example has the same meaning as when dimethylsilyl trifluoroacetate is used as acid A.
- trifluoromethanesulfonic anhydride used as the acid B reacts immediately with tetramethyldisilazane which is the silicon compound B, and changes to dimethylsilyltrifluoromethanesulfonate.
- the examples have the same meaning as when dimethylsilyl trifluoromethanesulfonate is used as the acid A.
- Example 68 when trifluoroacetic anhydride used as acid B is mixed with 1,3-dibutyltetramethyldisilazane which is silicon compound B, it reacts immediately to form butyldimethylsilyl trifluoroacetate. Since this varies, this example has the same meaning as when butyldimethylsilyl trifluoroacetate is used as acid A.
- Example 69 when trifluoromethanesulfonic anhydride used as acid B was mixed with 1,3-dibutyltetramethyldisilazane, which is silicon compound B, it reacted immediately to give butyldimethylsilyl trifluoromethanesulfonate. Therefore, this example has the same meaning as that when butyldimethylsilyl trifluoromethanesulfonate is used as the acid A.
- Example 70 when trifluoroacetic anhydride used as acid B was mixed with silicon compound B 1,3-dioctyltetramethyldisilazane, it immediately reacted to form octyldimethylsilyl trifluoroacetate.
- This example has the same meaning as when octyldimethylsilyl trifluoroacetate is used as acid A.
- Example 71 when trifluoromethanesulfonic anhydride used as acid B was mixed with 1,3-dioctyltetramethyldisilazane which is silicon compound B, it reacted immediately and octyldimethylsilyl trifluoromethanesulfonate. Therefore, this example has the same meaning as the case where octyldimethylsilyl trifluoromethanesulfonate is used as the acid A.
- Example 72 As silicon compound B, hexamethyldisilazane [(H 3 C) 3 Si—NH—Si (CH 3 ) 3 ]; 1 g, as acid B, trifluoroacetic acid [CF 3 C (O) —OH]; 0.1 g And 98.9 g of PGMEA as an organic solvent are mixed and reacted as shown in the following formula to form a protective film containing trimethylsilyl trifluoroacetate as acid A, hexamethyldisilazane as silicon compound A, and PGMEA as organic solvent The procedure was the same as Example 1 except that the chemical solution was obtained.
- Hexamethyldisilazane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A.
- the evaluation results showed that the contact angle after the surface treatment was 84 °, indicating the effect of imparting water repellency. Further, the capillary force when water was held was 0.3 MN / m 2 , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
- Example 73 to 103 The conditions of the silicon compound B, the concentration of the silicon compound B used in Example 72, the acid B, the organic solvent, and the like were appropriately changed, and the wafer was subjected to surface treatment and further evaluated. The results are shown in Table 4.
- CF 3 C (O) —OH means trifluoroacetic acid
- CF 3 S (O 2 ) —OH means trifluoromethanesulfonic acid
- Example 78 a chemical solution for forming a protective film containing dimethylsilyl trifluoroacetate as acid A and tetramethyldisilazane as silicon compound A was obtained by the reaction of the following formula.
- Tetramethyldisilazane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A.
- Example 86 a chemical solution for forming a protective film containing trimethylsilyl trifluoroacetate as acid A and trimethylsilyldimethylamine as silicon compound A was obtained by the reaction of the following formula.
- Trimethylsilyldimethylamine contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining the acid A, and the component functions as silicon compound A.
- Example 88 a chemical solution for forming a protective film containing trimethylsilyl trifluoroacetate as acid A and trimethylsilyldiethylamine as silicon compound A was obtained by the reaction of the following formula.
- Trimethylsilyldiethylamine contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining the acid A, and the component functions as silicon compound A.
- Example 90 a chemical solution for forming a protective film containing butyldimethylsilyl trifluoroacetate as acid A and butyldimethyl (dimethylamino) silane as silicon compound A was obtained by the reaction of the following formula.
- Butyldimethyl (dimethylamino) silane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A.
- Example 92 a chemical solution for forming a protective film containing octyldimethylsilyl trifluoroacetate as acid A and octyldimethyl (dimethylamino) silane as silicon compound A was obtained by the reaction of the following formula.
- Octyldimethyl (dimethylamino) silane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A.
- Example 97 in the above “(2) Cleaning of silicon wafer”, a smooth silicon wafer with a thermal oxide film (Si wafer having a 1 ⁇ m thick thermal oxide film layer on the surface) was changed to a 1 mass% hydrofluoric acid aqueous solution. It was immersed for 2 minutes at room temperature and then immersed in pure water for 1 minute. Further, it was immersed in a 0.3 mass% hydrochloric acid aqueous solution at 98 ° C. for 1 minute, then immersed in pure water at room temperature for 1 minute, and then immersed in 2-propanol (iPA) for 1 minute.
- iPA 2-propanol
- Example 98 and 100 the same treatment as described above was performed using a smooth silicon nitride-coated silicon wafer (Si wafer having a silicon nitride layer having a thickness of 0.3 ⁇ m on the surface).
- Example 102 the same treatment as described above was performed using a smooth silicon wafer with a polysilicon film (Si wafer having a polysilicon layer with a thickness of 0.3 ⁇ m on the surface).
- Example 99 and Example 101 1% by mass of the silicon wafer with a smooth silicon nitride film (Si wafer having a silicon nitride layer with a thickness of 0.3 ⁇ m on the surface) was obtained in the above “(2) Cleaning of silicon wafer”.
- a hydrofluoric acid aqueous solution at room temperature for 2 minutes and then immersed in pure water for 1 minute.
- 2-propanol (iPA) For 1 minute.
- Example 103 the same treatment as described above was performed using a smooth silicon wafer with a polysilicon film (Si wafer having a polysilicon layer with a thickness of 0.3 ⁇ m on the surface).
- Example 104 1 g of hexamethyldisilazane [(H 3 C) 3 Si—NH—Si (CH 3 ) 3 ]; 1 g of trifluoroacetic acid [CF 3 C (O) OH] as acid B; PGMEA as an organic solvent; 98 g
- a chemical solution for forming a protective film was obtained by mixing.
- the contact angle after the surface treatment was 84 °, which showed the effect of imparting water repellency.
- the capillary force when water was held was 0.3 MN / m 2 , and the capillary force was small.
- the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
- Example 105 In Example 1, in the above “(2) Cleaning of silicon wafer”, a smooth silicon wafer with a thermal oxide film (Si wafer having a thermal oxide film layer having a thickness of 1 ⁇ m on the surface) was changed to a 1 mass% hydrofluoric acid aqueous solution. It was immersed for 2 minutes at room temperature and then immersed in pure water for 1 minute. Further, in the above “(3) Surface treatment with a chemical solution for forming a protective film on the silicon wafer surface”, a silicon wafer wetted with water is placed on a spin coater and rotated on the wafer surface while rotating at a speed of 1000 rpm.
- Example 2 was the same as Example 2 except that the starting material used had a total amount of moisture of 5500 ppm by mass with respect to the total amount of the starting material.
- the contact angle after the surface treatment was 70 °, which showed the effect of imparting water repellency.
- the capillary force when water was held was 1.1 MN / m 2 , and the capillary force was small.
- the contact angle after UV irradiation was less than 10 °, and the protective film could be removed.
- the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
- Comparative Example 1 The same procedure as in Example 1 was performed except that the silicon wafer was not supplied with the chemical solution for forming the protective film. That is, in this comparative example, a wafer having a surface state that is not water-repellent was evaluated. As shown in Table 5, the contact angle of the wafer was as low as 3 °, and the capillary force when water was held was as large as 3.2 MN / m 2 .
- Comparative Example 2 Hexamethyldisilazane; 1.0 g, PGMEA; 99.0 g were mixed to obtain a protective film-forming chemical solution, which was the same as Example 1. That is, in this comparative example, a chemical solution for forming a protective film containing no acid was used. As shown in Table 5, the contact angle after the surface treatment was as low as 28 °, and the capillary force when water was retained was as large as 2.8 MN / m 2 .
- Example 2 The acid A used in Example 1 was changed, and the wafer was surface-treated and further evaluated. The results are shown in Table 5.
- CH 3 S (O 2 ) —OH means methanesulfonic acid
- CH 3 COOH means acetic acid
- H 2 SO 4 means sulfuric acid (water content is 2 mass).
- H 3 PO 4 means phosphoric acid (water content is 15 mass%)
- HCl means hydrochloric acid (water content is 65 mass%)
- HNO means nitric acid (water content is 31 mass%).
- Example 1 acid A was used, and in Comparative Examples 3 to 8, acids other than acid A were used. Otherwise, the surface treatment was performed under the same conditions. It was confirmed that only Example 1 using trimethylsilyl trifluoroacetate which is acid A can impart excellent water repellency to the wafer surface. On the other hand, it was confirmed that Comparative Examples 3 to 8 could not give sufficient water repellency to the silicon wafer.
- the chemical solution capable of imparting sufficient water repellency to the surface of the silicon wafer means that the silanol group, which is a reaction site on the surface of the silicon wafer, and the silicon compound A are reacted rapidly to convert the silicon compound A to silicon via a siloxane bond. It is suggested that trimethylsilyl trifluoroacetate, which is acid A, significantly increases the reaction rate of the chemical because it is a chemical that can be chemically bonded to the Si element of the wafer.
- silicon compound A having a relatively bulky hydrocarbon group was used as R 1 of the general formula [1]. Since such silicon compound A reacts with silanol groups, which are reaction sites on the surface of the silicon wafer, and the Si element of the silicon wafer can be covered with bulky hydrocarbon groups via siloxane bonds, it is efficient.
- the wafer surface can be made water repellent. Naturally, the silicon surface A having such a relatively bulky hydrocarbon group and the acid A that can remarkably increase the reaction rate of the chemical solution are combined to repel the wafer surface more efficiently. Can do.
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Abstract
Description
(γ:表面張力、θ:接触角、S:パターン寸法)
特許文献1には、γを小さくしてパターン倒れを抑制する手法として気液界面がパターンを通過する前に洗浄液を水から2-プロパノールへ置換する技術が開示されている。しかし、この手法では、パターン倒れ防止に有効である一方、γが小さい2-プロパノール等の溶媒は通常の接触角も小さくなり、その結果、cosθが大きくなる傾向にある。そのため、対応できるパターンのアスペクト比が5以下である等、限界があると言われている。 P = 2 × γ × cos θ / S
(Γ: surface tension, θ: contact angle, S: pattern dimension)
(工程1)ウェハ表面を微細な凹凸パターンを有する面とした後、水系洗浄液を当該面に供し、凹凸パターンの少なくとも凹部表面に水系洗浄液を保持する工程、
(工程2)凹凸パターンの少なくとも凹部表面に保持された水系洗浄液を該水系洗浄液とは異なる洗浄液Aで置換する工程、
(工程3)前記洗浄液Aを保護膜形成用薬液で置換し、該薬液を凹凸パターンの少なくとも凹部表面に保持する工程、
(工程4)乾燥により凹凸パターン表面から液体を除去する工程、
(工程5)保護膜を除去する工程
を有する。 A suitable cleaning method for a wafer having a fine concavo-convex pattern on the surface and at least a part of the concavo-convex pattern containing silicon element, using the chemical solution for forming a protective film of the present invention,
(Step 1) A step of making the wafer surface a surface having a fine concavo-convex pattern, then subjecting the surface to an aqueous cleaning solution, and holding the aqueous cleaning solution on at least the concave surface of the concavo-convex pattern;
(Step 2) A step of replacing the aqueous cleaning liquid held on at least the concave surface of the concavo-convex pattern with a cleaning liquid A different from the aqueous cleaning liquid,
(Step 3) Replacing the cleaning liquid A with a protective film-forming chemical solution, and holding the chemical solution on at least the concave surface of the concave-convex pattern;
(Step 4) A step of removing liquid from the surface of the concavo-convex pattern by drying,
(Step 5) A step of removing the protective film is included.
P=2×γ×cosθ/S
(γ:表面張力、θ:接触角、S:パターン寸法)
から明らかなようにパターン倒れは、洗浄液のウェハ表面への接触角、すなわち液滴の接触角と、洗浄液の表面張力に大きく依存する。凹凸パターン2の凹部4に保持された洗浄液の場合、液滴の接触角と、パターン倒れと等価なものとして考えてよい該凹部表面の毛細管力とは相関性があるので、前記式と保護膜10の液滴の接触角の評価から毛細管力を導き出してもよい。なお、実施例において、前記洗浄液として、水系洗浄液の代表的なものである水を用いた。 Making the surface of the wafer a surface having a fine concavo-convex pattern and replacing the cleaning liquid held on at least the concave surface of the concavo-convex pattern with other cleaning liquids have already been established through various studies in other literature. Therefore, in the present invention, the evaluation of the chemical solution for forming a protective film was mainly performed. In addition, the formula P = 2 × γ × cos θ / S described in the background of the invention
(Γ: surface tension, θ: contact angle, S: pattern dimension)
As can be seen from the above, the pattern collapse greatly depends on the contact angle of the cleaning liquid to the wafer surface, that is, the contact angle of the droplets and the surface tension of the cleaning liquid. In the case of the cleaning liquid held in the
保護膜形成用薬液が供されたウェハの評価方法として、以下の(1)~(4)の評価を行った。 [Evaluation method of wafer provided with chemical solution for forming protective film]
The following evaluations (1) to (4) were performed as methods for evaluating a wafer provided with a chemical solution for forming a protective film.
保護膜が形成されたウェハ表面上に純水約2μlを置き、水滴とウェハ表面とのなす角(接触角)を接触角計(協和界面科学製:CA-X型)で測定した。 (1) Contact angle evaluation of the protective film formed on the wafer surface About 2 μl of pure water is placed on the surface of the wafer on which the protective film is formed, and the angle (contact angle) formed between the water droplet and the wafer surface is measured by a contact angle meter (Kyowa). It was measured by Interface Science: CA-X type.
下式を用いてPを算出し、毛細管力(Pの絶対値)を求めた。 (2) Evaluation of capillary force P was calculated using the following equation, and the capillary force (absolute value of P) was determined.
ここで、γは表面張力、θは接触角、Sはパターン寸法を示す。
本実施例では、パターン形状の一例として、パターン寸法に相当する線幅(凹部の幅)が45nmのラインアンドスペース形状のパターンのウェハを想定した。なお、線幅:45nmのパターンでは、気液界面がウェハを通過するときの洗浄液が水の場合はパターンが倒れやすく、2-プロパノールの場合はパターンが倒れ難い傾向がある。パターン寸法:45nm、ウェハ表面:酸化ケイ素の場合、洗浄液が、2-プロパノール(表面張力:22mN/m、酸化ケイ素との接触角:1°)では毛細管力は0.98MN/m2となる。一方、水銀を除く液体の中で表面張力が最も大きい水(表面張力:72mN/m、酸化ケイ素との接触角:2.5°)では毛細管力は3.2MN/m2となる。該毛細管力は1.1MN/m2以下が好ましく、0.8MN/m2以下が特に好ましい。 P = 2 × γ × cos θ / S
Here, γ is the surface tension, θ is the contact angle, and S is the pattern dimension.
In this example, as an example of the pattern shape, a line-and-space pattern wafer having a line width (recess width) corresponding to the pattern dimension of 45 nm was assumed. In the pattern with a line width of 45 nm, the pattern tends to collapse when the cleaning liquid is water when the gas-liquid interface passes through the wafer, and the pattern does not easily collapse when 2-propanol is used. When the pattern size is 45 nm and the wafer surface is silicon oxide, the capillary force is 0.98 MN / m 2 when the cleaning liquid is 2-propanol (surface tension: 22 mN / m, contact angle with silicon oxide: 1 °). On the other hand, the capillary force is 3.2 MN / m 2 in water (surface tension: 72 mN / m, contact angle with silicon oxide: 2.5 °) having the largest surface tension among liquids excluding mercury. Capillary force is preferably 1.1 MN / m 2 or less, particularly preferably 0.8Mn / m 2 or less.
以下の条件でメタルハライドランプのUV光をサンプルに2時間照射した。照射後に水滴の接触角が30°以下となったものを合格(表中で○と表記)とした。
・ランプ:アイグラフィックス製M015-L312
(強度:1.5kW)
・照度:下記条件における測定値が128mW/cm2
・測定装置:紫外線強度計
(コニカミノルタセンシング製、UM-10)
・受光部:UM-360
(受光波長:310~400nm、ピーク波長:365nm)
・測定モード:放射照度測定 (3) Removability of protective film The sample was irradiated with UV light from a metal halide lamp for 2 hours under the following conditions. A sample having a water droplet contact angle of 30 ° or less after irradiation was regarded as acceptable (denoted as “◯” in the table).
・ Lamp: Eye Graphics M0155-L312
(Strength: 1.5 kW)
Illuminance: The measured value under the following conditions is 128 mW / cm 2
・ Measurement device: UV intensity meter (Konica Minolta Sensing, UM-10)
・ Light receiving part: UM-360
(Receiving wavelength: 310 to 400 nm, peak wavelength: 365 nm)
・ Measurement mode: Irradiance measurement
原子間力電子顕微鏡(セイコー電子製:SPI3700、2.5μm四方スキャン)によって表面観察し、中心線平均面粗さ:Ra(nm)を求めた。なお、Raは、JIS B 0601で定義されている中心線平均粗さを測定面に対し適用して三次元に拡張したものであり、「基準面から指定面までの偏差の絶対値を平均した値」として次式で算出した。保護膜を除去した後のウェハのRa値が1nm以下であれば、洗浄によってウェハ表面が浸食されていない、および、前記保護膜の残渣がウェハ表面にないとし、合格(表中で○と表記)とした。 (4) Evaluation of surface smoothness of wafer after removal of protective film Surface observation is performed with an atomic force electron microscope (Seiko Electronics: SPI3700, 2.5 μm square scan) to obtain centerline average surface roughness: Ra (nm). It was. Note that Ra is a three-dimensional extension of the center line average roughness defined in JIS B 0601 to the measurement surface. “The absolute value of the deviation from the reference surface to the specified surface is averaged. The value was calculated by the following formula. If the Ra value of the wafer after removal of the protective film is 1 nm or less, the wafer surface is not eroded by cleaning, and the residue of the protective film is not present on the wafer surface. ).
(1)保護膜形成用薬液の調製
ケイ素化合物Aとしてヘキサメチルジシラザン〔(H3C)3Si-NH-Si(CH3)3〕;1g、酸Aとしてトリメチルシリルトリフルオロアセテート〔(CH3)3Si-OC(O)CF3〕;0.1gと有機溶媒としてプロピレングリコールモノメチルエーテルアセテート(PGMEA);98.9gを混合し、保護膜形成用薬液を得た。なお、前記薬液の出発原料中の水分の総量が、該原料の総量に対し5000質量ppm以下であることを確認した。モレキュラーシーブ4A(ユニオン昭和製)により該薬液から水分を除去し、次いで、イオン交換樹脂(日本ポール製イオンクリーンSL)により該薬液から金属不純物を除去し、次いで、フィルターろ過(日本インテグリス製オプチマイザー)により該薬液からパーティクルを除去し精製を行った。精製後の該薬液中の水分量をカールフィッシャー式水分計(京都電子製、ADP-511型)により測定を行ったところ、精製後の該薬液中の水分量は、該薬液総量に対し6質量ppmであった。また、精製後の該薬液中の金属不純物含有量を誘導結合プラズマ質量分析装置(横河アナリティカルシステムズ製、Agilent 7500cs型)により測定したところ、精製後の該薬液中のNa、Mg、K、Ca、Mn、Fe及びCuの各元素の金属不純物含有量は、該薬液総量に対しそれぞれ、Na=2質量ppb、Mg=0.04質量ppb、K=0.2質量ppb、Ca=1質量ppb、Mn=0.005質量ppb、Fe=0.08質量ppb、Cu=0.06質量ppbであった。また、液相での光散乱式液中粒子検出器によるパーティクル測定における0.5μmより大きい粒子の数を光散乱式液中粒子測定装置(リオン社製、KS-42AF型)により測定したところ、0.5μmより大きい粒子の数は該薬液1mL当たり2個であった。なお、本実施例以降の実施例においても、薬液の出発原料中の水分の総量が、該原料の総量に対し5000質量ppm以下であることを確認し、同様の精製を行い、水分量が薬液総量に対し5000質量ppm以下であり、Na、Mg、K、Ca、Mn、Fe及びCuの各元素の金属不純物含有量は、該薬液総量に対しそれぞれ100質量ppb以下であり、0.5μmより大きい粒子の数は該薬液1mL当たり100個以下であることを確認した薬液を用いた。 [Example 1]
(1) Preparation of chemical solution for forming protective film Hexamethyldisilazane [(H 3 C) 3 Si—NH—Si (CH 3 ) 3 ] as silicon compound A; 1 g, trimethylsilyl trifluoroacetate [(CH 3 ) 3 Si—OC (O) CF 3 ]; 0.1 g and propylene glycol monomethyl ether acetate (PGMEA); 98.9 g as an organic solvent were mixed to obtain a chemical solution for forming a protective film. In addition, it confirmed that the total amount of the water | moisture content in the starting raw material of the said chemical | medical solution was 5000 mass ppm or less with respect to the total amount of this raw material. Moisture is removed from the chemical solution using molecular sieve 4A (made by Union Showa), then metal impurities are removed from the chemical solution using ion exchange resin (Nippon Pole's Ion Clean SL), and then filtered (Nippon Integris Optimizer) ) To remove particles from the chemical solution for purification. When the water content in the chemical solution after purification was measured with a Karl Fischer moisture meter (ADP-511, manufactured by Kyoto Electronics Co., Ltd.), the water content in the chemical solution after purification was 6 mass relative to the total amount of the chemical solution. ppm. Further, when the metal impurity content in the chemical solution after purification was measured by an inductively coupled plasma mass spectrometer (Yokogawa Analytical Systems, Agilent 7500cs type), Na, Mg, K, The metal impurity content of each element of Ca, Mn, Fe, and Cu is Na = 2 mass ppb, Mg = 0.04 mass ppb, K = 0.2 mass ppb, Ca = 1 mass with respect to the total amount of the chemical solution, respectively. It was ppb, Mn = 0.005 mass ppb, Fe = 0.08 mass ppb, Cu = 0.06 mass ppb. Further, when the number of particles larger than 0.5 μm in the particle measurement by the light scattering liquid particle detector in the liquid phase was measured by a light scattering liquid particle measuring device (manufactured by Rion Co., Ltd., KS-42AF type), The number of particles larger than 0.5 μm was 2 per 1 mL of the drug solution. In the examples after this example, it was confirmed that the total amount of water in the starting material of the chemical solution was 5000 ppm by mass or less with respect to the total amount of the raw material, and the same purification was performed. It is 5000 mass ppm or less with respect to the total amount, and the metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe and Cu is 100 mass ppb or less with respect to the total amount of the chemical solution, from 0.5 μm A chemical solution that was confirmed to have 100 or less large particles per mL of the chemical solution was used.
平滑な熱酸化膜付きシリコンウェハ(表面に厚さ1μmの熱酸化膜層を有するSiウェハ)を室温で1質量%のフッ酸水溶液に2分浸漬し、次いで純水に1分、2-プロパノール(iPA)に1分浸漬した。 (2) Cleaning of silicon wafer A silicon wafer with a smooth thermal oxide film (Si wafer having a 1 μm thick thermal oxide film layer on the surface) is immersed in a 1% by mass hydrofluoric acid aqueous solution for 2 minutes at room temperature, and then pure water For 1 minute and then immersed in 2-propanol (iPA) for 1 minute.
シリコンウェハを、上記「(1)保護膜形成用薬液の調製」で調製した保護膜形成用薬液に20℃で10分浸漬させた。その後、シリコンウェハをiPAに1分浸漬し、次いで、水系洗浄液としての純水に1分浸漬した。最後に、シリコンウェハを純水から取出し、エアーを吹き付けて、表面の純水を除去した。 (3) Surface treatment of silicon wafer surface with chemical solution for forming protective film A silicon wafer was immersed in the chemical solution for forming a protective film prepared in “(1) Preparation of chemical solution for forming protective film” at 20 ° C. for 10 minutes. . Thereafter, the silicon wafer was immersed in iPA for 1 minute, and then immersed in pure water as an aqueous cleaning solution for 1 minute. Finally, the silicon wafer was taken out from the pure water and air was blown to remove the pure water on the surface.
実施例1で用いたケイ素化合物A、ケイ素化合物Aの濃度、酸A、有機溶媒、保護膜形成用薬液の表面処理後の処理手順などの条件を適宜変更して、ウェハの表面処理を行い、さらにその評価を行った。結果を表1~表2に示す。 [Examples 2 to 56]
The silicon compound A used in Example 1, the concentration of the silicon compound A, the acid A, the organic solvent, the conditions such as the treatment procedure after the surface treatment of the protective film forming chemical solution are appropriately changed, and the wafer surface treatment is performed. Furthermore, the evaluation was performed. The results are shown in Tables 1 and 2.
ケイ素化合物Bとして、ヘキサメチルジシラザン〔(H3C)3Si-NH-Si(CH3)3〕;1g、酸Bとして無水トリフルオロ酢酸〔{CF3C(O)}2O〕;0.1gと有機溶媒としてPGMEA;98.9gを混合し、反応させることにより、酸Aとしてトリメチルシリルトリフルオロアセテート、ケイ素化合物Aとしてヘキサメチルジシラザン、有機溶媒としてPGMEAを含む保護膜形成用薬液を得た以外は実施例1と同じとした。本実施例の薬液に含まれるヘキサメチルジシラザンは、前記の酸Aを得るための反応で消費されなかったケイ素化合物Bであり、該成分はケイ素化合物Aとして機能するものである。評価結果は表3に示すとおり、表面処理後の接触角は82°となり、撥水性付与効果を示した。また、水が保持されたときの毛細管力は0.4MN/m2となり、毛細管力は小さかった。また、UV照射後の接触角は10°未満であり保護膜は除去できた。さらに、UV照射後のウェハのRa値は0.5nm未満であり、洗浄時にウェハは浸食されず、さらにUV照射後に保護膜の残渣は残らないことが確認できた。 [Example 57]
Hexamethyldisilazane [(H 3 C) 3 Si—NH—Si (CH 3 ) 3 ] as the silicon compound B; 1 g, trifluoroacetic anhydride [{CF 3 C (O)} 2 O] as the acid B; 0.1 g and 98.9 g of PGMEA as an organic solvent were mixed and reacted to give a protective film forming chemical solution containing trimethylsilyl trifluoroacetate as acid A, hexamethyldisilazane as silicon compound A, and PGMEA as organic solvent. It was the same as Example 1 except that it was obtained. Hexamethyldisilazane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A. As shown in Table 3, the evaluation result showed that the contact angle after the surface treatment was 82 °, indicating the effect of imparting water repellency. Further, the capillary force when water was held was 0.4 MN / m 2 , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
実施例57で用いたケイ素化合物B、酸B、有機溶媒などの条件を適宜変更して、ウェハの表面処理を行い、さらにその評価を行った。結果を表3に示す。 [Examples 58 to 71]
The conditions of the silicon compound B, acid B, organic solvent, and the like used in Example 57 were changed as appropriate, and the wafer was subjected to a surface treatment and further evaluated. The results are shown in Table 3.
ケイ素化合物Bとして、ヘキサメチルジシラザン〔(H3C)3Si-NH-Si(CH3)3〕;1g、酸Bとしてトリフルオロ酢酸〔CF3C(O)-OH〕;0.1gと有機溶媒としてPGMEA;98.9gを混合し、下式のように反応させることにより、酸Aとしてトリメチルシリルトリフルオロアセテート、ケイ素化合物Aとしてヘキサメチルジシラザン、有機溶媒としてPGMEAを含む保護膜形成用薬液を得た以外は実施例1と同じとした。本実施例の薬液に含まれるヘキサメチルジシラザンは、前記の酸Aを得るための反応で消費されなかったケイ素化合物Bであり、該成分はケイ素化合物Aとして機能するものである。評価結果は表4に示すとおり、表面処理後の接触角は84°となり、撥水性付与効果を示した。また、水が保持されたときの毛細管力は0.3MN/m2となり、毛細管力は小さかった。また、UV照射後の接触角は10°未満であり保護膜は除去できた。さらに、UV照射後のウェハのRa値は0.5nm未満であり、洗浄時にウェハは浸食されず、さらにUV照射後に保護膜の残渣は残らないことが確認できた。
As silicon compound B, hexamethyldisilazane [(H 3 C) 3 Si—NH—Si (CH 3 ) 3 ]; 1 g, as acid B, trifluoroacetic acid [CF 3 C (O) —OH]; 0.1 g And 98.9 g of PGMEA as an organic solvent are mixed and reacted as shown in the following formula to form a protective film containing trimethylsilyl trifluoroacetate as acid A, hexamethyldisilazane as silicon compound A, and PGMEA as organic solvent The procedure was the same as Example 1 except that the chemical solution was obtained. Hexamethyldisilazane contained in the chemical solution of this example is silicon compound B that was not consumed in the reaction for obtaining acid A, and the component functions as silicon compound A. As shown in Table 4, the evaluation results showed that the contact angle after the surface treatment was 84 °, indicating the effect of imparting water repellency. Further, the capillary force when water was held was 0.3 MN / m 2 , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
実施例72で用いたケイ素化合物B、ケイ素化合物Bの濃度、酸B、有機溶媒などの条件を適宜変更して、ウェハの表面処理を行い、さらにその評価を行った。結果を表4に示す。 [Examples 73 to 103]
The conditions of the silicon compound B, the concentration of the silicon compound B used in Example 72, the acid B, the organic solvent, and the like were appropriately changed, and the wafer was subjected to surface treatment and further evaluated. The results are shown in Table 4.
ヘキサメチルジシラザン〔(H3C)3Si-NH-Si(CH3)3〕;1g、酸Bとしてトリフルオロ酢酸〔CF3C(O)OH〕;1gと有機溶媒としてPGMEA;98gを混合して保護膜形成用薬液を得た以外は実施例1と同じとした。評価結果は、表面処理後の接触角は84°となり、撥水性付与効果を示した。また、水が保持されたときの毛細管力は0.3MN/m2となり、毛細管力は小さかった。また、UV照射後の接触角は10°未満であり保護膜は除去できた。さらに、UV照射後のウェハのRa値は0.5nm未満であり、洗浄時にウェハは浸食されず、さらにUV照射後に保護膜の残渣は残らないことが確認できた。 [Example 104]
1 g of hexamethyldisilazane [(H 3 C) 3 Si—NH—Si (CH 3 ) 3 ]; 1 g of trifluoroacetic acid [CF 3 C (O) OH] as acid B; PGMEA as an organic solvent; 98 g The same procedure as in Example 1 was conducted except that a chemical solution for forming a protective film was obtained by mixing. As a result of the evaluation, the contact angle after the surface treatment was 84 °, which showed the effect of imparting water repellency. Further, the capillary force when water was held was 0.3 MN / m 2 , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
実施例1において、上記「(2)シリコンウェハの洗浄」で、平滑な熱酸化膜付きシリコンウェハ(表面に厚さ1μmの熱酸化膜層を有するSiウェハ)を1質量%のフッ酸水溶液に室温で2分浸漬し、純水に1分浸漬した。さらに、上記「(3)シリコンウェハ表面への保護膜形成用薬液による表面処理」で、水に濡れたシリコンウェハをスピンコーターに設置し、1000rpmの速度で回転させながら、該ウェハ表面に2-プロパノール(iPA)を1分、次いで保護膜形成用薬液を10分、次いでiPAを1分、次いで純水を1分給液し、最後に何も給液しないまま1分間回転を継続し、表面の純水を除去した。得られたウェハの評価結果は、表面処理後の接触角は82°となり、撥水性付与効果を示した。また、水が保持されたときの毛細管力は0.4MN/m2となり、毛細管力は小さかった。また、UV照射後の接触角は10°未満であり保護膜は除去できた。さらに、UV照射後のウェハのRa値は0.5nm未満であり、洗浄時にウェハは浸食されず、さらにUV照射後に保護膜の残渣は残らないことが確認できた。 [Example 105]
In Example 1, in the above “(2) Cleaning of silicon wafer”, a smooth silicon wafer with a thermal oxide film (Si wafer having a thermal oxide film layer having a thickness of 1 μm on the surface) was changed to a 1 mass% hydrofluoric acid aqueous solution. It was immersed for 2 minutes at room temperature and then immersed in pure water for 1 minute. Further, in the above “(3) Surface treatment with a chemical solution for forming a protective film on the silicon wafer surface”, a silicon wafer wetted with water is placed on a spin coater and rotated on the wafer surface while rotating at a speed of 1000 rpm. Propanol (iPA) for 1 minute, then protective film-forming chemical solution for 10 minutes, then iPA for 1 minute, then pure water for 1 minute, and finally rotating for 1 minute without supplying anything, Of pure water was removed. As a result of evaluation of the obtained wafer, the contact angle after the surface treatment was 82 °, which showed the effect of imparting water repellency. Further, the capillary force when water was held was 0.4 MN / m 2 , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
出発原料中の水分の総量が、該原料の総量に対し5500質量ppmである原料を用いた以外は実施例2と同じとした。評価結果は、表面処理後の接触角は70°となり、撥水性付与効果を示した。また、水が保持されたときの毛細管力は1.1MN/m2となり、毛細管力は小さかった。また、UV照射後の接触角は10°未満であり保護膜は除去できた。さらに、UV照射後のウェハのRa値は0.5nm未満であり、洗浄時にウェハは浸食されず、さらにUV照射後に保護膜の残渣は残らないことが確認できた。 [Example 106]
Example 2 was the same as Example 2 except that the starting material used had a total amount of moisture of 5500 ppm by mass with respect to the total amount of the starting material. As a result of the evaluation, the contact angle after the surface treatment was 70 °, which showed the effect of imparting water repellency. Further, the capillary force when water was held was 1.1 MN / m 2 , and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.
シリコンウェハに保護膜形成用薬液を供さなかった以外は、実施例1と同じとした。すなわち、本比較例では、撥水化されていない表面状態のウェハを評価した。評価結果は表5に示すとおり、ウェハの接触角は3°と低く、水が保持されたときの毛細管力は3.2MN/m2と大きかった。 Comparative Example 1
The same procedure as in Example 1 was performed except that the silicon wafer was not supplied with the chemical solution for forming the protective film. That is, in this comparative example, a wafer having a surface state that is not water-repellent was evaluated. As shown in Table 5, the contact angle of the wafer was as low as 3 °, and the capillary force when water was held was as large as 3.2 MN / m 2 .
ヘキサメチルジシラザン;1.0g、PGMEA;99.0gを混合し保護膜形成用薬液を得た以外は実施例1と同じとした。すなわち、本比較例では、酸を含まない保護膜形成用薬液を用いた。評価結果は表5に示すとおり、表面処理後の接触角は28°と低く、水が保持されたときの毛細管力は2.8MN/m2と大きかった。 Comparative Example 2
Hexamethyldisilazane; 1.0 g, PGMEA; 99.0 g were mixed to obtain a protective film-forming chemical solution, which was the same as Example 1. That is, in this comparative example, a chemical solution for forming a protective film containing no acid was used. As shown in Table 5, the contact angle after the surface treatment was as low as 28 °, and the capillary force when water was retained was as large as 2.8 MN / m 2 .
実施例1で用いた酸Aを変更して、ウェハの表面処理を行い、さらにその評価を行った。結果を表5に示す。 [Comparative Examples 3 to 8]
The acid A used in Example 1 was changed, and the wafer was surface-treated and further evaluated. The results are shown in Table 5.
実施例1で用いたケイ素化合物A、有機溶媒を適宜変更し、さらに酸A以外の酸としてトリメチルクロロシラン〔(CH3)3SiCl〕を用いて、ウェハの表面処理を行い、さらにその評価を行った。結果を表6に示す。本参考例で用いた薬液は、調合時に、白濁した外観となり、析出成分が見られたが、該薬液を精製し表面処理すると、接触角が78~84°であり、ほとんど変化がなく、本発明の実施例の薬液と同等の効果が得られた。 [Reference Examples 1 to 4]
The silicon compound A and the organic solvent used in Example 1 were appropriately changed, and the wafer was surface-treated using trimethylchlorosilane [(CH 3 ) 3 SiCl] as an acid other than the acid A, and further evaluated. It was. The results are shown in Table 6. The chemical solution used in this reference example had a cloudy appearance at the time of preparation, and precipitated components were observed. However, when the chemical solution was purified and surface-treated, the contact angle was 78 to 84 °, and there was almost no change. The same effects as those of the chemical solutions of the inventive examples were obtained.
2 ウェハ表面の微細な凹凸パターン
3 パターンの凸部
4 パターンの凹部
5 凹部の幅
6 凸部の高さ
7 凸部の幅
8 凹部4に保持された保護膜形成用薬液
9 凹部4に保持された水系洗浄液
10 保護膜 DESCRIPTION OF
Claims (14)
- 表面に微細な凹凸パターンを有し該凹凸パターンの少なくとも一部がシリコン元素を含むウェハの洗浄時に、該凹凸パターンの少なくとも凹部表面に撥水性保護膜を形成するための薬液であり、下記一般式[1]で表されるケイ素化合物Aと酸Aとを含み、該酸Aはトリメチルシリルトリフルオロアセテート、トリメチルシリルトリフルオロメタンスルホネート、ジメチルシリルトリフルオロアセテート、ジメチルシリルトリフルオロメタンスルホネート、ブチルジメチルシリルトリフルオロアセテート、ブチルジメチルシリルトリフルオロメタンスルホネート、オクチルジメチルシリルトリフルオロアセテート、及び、オクチルジメチルシリルトリフルオロメタンスルホネートからなる群から選ばれる少なくとも1つであることを特徴とする、保護膜形成用薬液。
- 前記薬液の出発原料中の水分の総量が、該原料の総量に対し5000質量ppm以下であることを特徴とする、請求項1に記載の保護膜形成用薬液。 2. The chemical solution for forming a protective film according to claim 1, wherein the total amount of moisture in the starting material of the chemical solution is 5000 ppm by mass or less based on the total amount of the raw material.
- 前記薬液中の液相での光散乱式液中粒子検出器によるパーティクル測定における0.5μmより大きい粒子の数が、該薬液1mL当たり100個以下であることを特徴とする、請求項1または請求項2に記載の保護膜形成用薬液。 The number of particles larger than 0.5 μm in particle measurement by a light scattering type submerged particle detector in the liquid phase of the chemical solution is 100 or less per 1 mL of the chemical solution. Item 3. A protective film-forming chemical solution according to Item 2.
- 前記薬液中のNa、Mg、K、Ca、Mn、Fe及びCuの各元素の金属不純物含有量が、該薬液総量に対し各100質量ppb以下であることを特徴とする、請求項1乃至請求項3のいずれかに記載の保護膜形成用薬液。 The metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the chemical solution is 100 mass ppb or less with respect to the total amount of the chemical solution. Item 4. A protective film-forming chemical solution according to any one of Items 3 to 4.
- 請求項1乃至請求項4のいずれかに記載の保護膜形成用薬液の調製方法であって、当該保護膜形成用薬液の原料である混合前のケイ素化合物A及び酸A、並びに、混合後の混合液のうち少なくとも1つを精製することを特徴とする、前記調製方法。 A method for preparing a protective film-forming chemical solution according to any one of claims 1 to 4, wherein the silicon compound A and acid A before mixing, which are raw materials of the protective film-forming chemical solution, and after mixing The said preparation method characterized by refine | purifying at least 1 among liquid mixtures.
- 請求項1乃至請求項4のいずれかに記載の保護膜形成用薬液を用いる、表面に微細な凹凸パターンを有するウェハ表面の洗浄方法であり、該方法は、洗浄液をウェハ表面から取り除いた後に該ウェハ表面から保護膜を除去する工程を有することを特徴とする、前記洗浄方法。 A method for cleaning a wafer surface having a fine uneven pattern on the surface, using the chemical solution for forming a protective film according to any one of claims 1 to 4, wherein the method is performed after removing the cleaning solution from the wafer surface. The cleaning method according to claim 1, further comprising a step of removing the protective film from the wafer surface.
- 前記ウェハ表面から保護膜を除去する工程が、ウェハ表面を光照射すること、ウェハを加熱すること、ウェハをオゾン曝露すること、及び、ウェハ表面にプラズマ照射することから選ばれる少なくとも1つの処理であることを特徴とする、請求項6に記載の前記洗浄方法。 The step of removing the protective film from the wafer surface is at least one treatment selected from light irradiation of the wafer surface, heating of the wafer, exposure of the wafer to ozone, and irradiation of the wafer surface with plasma. The cleaning method according to claim 6, wherein the cleaning method is provided.
- 表面に微細な凹凸パターンを有し該凹凸パターンの少なくとも一部がシリコン元素を含むウェハの洗浄時に、該凹凸パターンの少なくとも凹部表面に撥水性保護膜を形成するための薬液であり、下記一般式[1]で表されるケイ素化合物Aと酸Aとを含み、該酸Aはトリメチルシリルトリフルオロアセテート、トリメチルシリルトリフルオロメタンスルホネート、ジメチルシリルトリフルオロアセテート、ジメチルシリルトリフルオロメタンスルホネート、ブチルジメチルシリルトリフルオロアセテート、ブチルジメチルシリルトリフルオロメタンスルホネート、ヘキシルジメチルシリルトリフルオロアセテート、ヘキシルジメチルシリルトリフルオロメタンスルホネート、オクチルジメチルシリルトリフルオロアセテート、オクチルジメチルシリルトリフルオロメタンスルホネート、デシルジメチルシリルトリフルオロアセテート、及び、デシルジメチルシリルトリフルオロメタンスルホネートからなる群から選ばれる少なくとも1つであることを特徴とする、保護膜形成用薬液。
- 前記薬液の出発原料中の水分の総量が、該原料の総量に対し5000質量ppm以下であることを特徴とする、請求項8に記載の保護膜形成用薬液。 The chemical solution for forming a protective film according to claim 8, wherein the total amount of water in the starting material of the chemical solution is 5000 mass ppm or less with respect to the total amount of the raw material.
- 前記薬液中の液相での光散乱式液中粒子検出器によるパーティクル測定における0.5μmより大きい粒子の数が、該薬液1mL当たり100個以下であることを特徴とする、請求項8または請求項9に記載の保護膜形成用薬液。 9. The number of particles larger than 0.5 μm in particle measurement by a light scattering type submerged particle detector in the liquid phase of the chemical solution is 100 or less per 1 mL of the chemical solution. Item 10. A protective film forming chemical solution according to Item 9.
- 前記薬液中のNa、Mg、K、Ca、Mn、Fe及びCuの各元素の金属不純物含有量が、該薬液総量に対し各100質量ppb以下であることを特徴とする、請求項8乃至請求項10のいずれかに記載の保護膜形成用薬液。 The metal impurity content of each element of Na, Mg, K, Ca, Mn, Fe, and Cu in the chemical solution is 100 mass ppb or less with respect to the total amount of the chemical solution. Item 11. The protective film-forming chemical solution according to any one of Items 10.
- 請求項8乃至請求項11のいずれかに記載の保護膜形成用薬液の調製方法であって、当該保護膜形成用薬液の原料である混合前のケイ素化合物A及び酸A、並びに、混合後の混合液のうち少なくとも1つを精製することを特徴とする、前記調製方法。 A method for preparing a protective film-forming chemical solution according to any one of claims 8 to 11, wherein the silicon compound A and acid A before mixing, which are raw materials of the protective film-forming chemical solution, and after mixing The said preparation method characterized by refine | purifying at least 1 among liquid mixtures.
- 請求項8乃至請求項11のいずれかに記載の保護膜形成用薬液を用いる、表面に微細な凹凸パターンを有するウェハ表面の洗浄方法であり、該方法は、洗浄液をウェハ表面から取り除いた後に該ウェハ表面から保護膜を除去する工程を有することを特徴とする、前記洗浄方法。 A method for cleaning a wafer surface having a fine uneven pattern on the surface, which uses the protective film forming chemical solution according to any one of claims 8 to 11, wherein the method is performed after removing the cleaning solution from the wafer surface. The cleaning method according to claim 1, further comprising a step of removing the protective film from the wafer surface.
- 前記ウェハ表面から保護膜を除去する工程が、ウェハ表面を光照射すること、ウェハを加熱すること、ウェハをオゾン曝露すること、及び、ウェハ表面にプラズマ照射することから選ばれる少なくとも1つの処理であることを特徴とする、請求項13に記載の前記洗浄方法。 The step of removing the protective film from the wafer surface is at least one treatment selected from light irradiation of the wafer surface, heating of the wafer, exposure of the wafer to ozone, and irradiation of the wafer surface with plasma. The cleaning method according to claim 13, wherein there is a cleaning method.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2012519357A JP5821844B2 (en) | 2010-06-07 | 2011-06-03 | Chemical solution for protective film formation |
SG2012084679A SG185632A1 (en) | 2010-06-07 | 2011-06-03 | Liquid chemical for foaming protecting film |
CN201180028305.8A CN102934207B (en) | 2010-06-07 | 2011-06-03 | Diaphragm formation chemical solution |
KR1020127034083A KR101363441B1 (en) | 2010-06-07 | 2011-06-03 | Chemical solution for formation of protective film, process for preparing thereof and process for cleaning using the same |
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KR (1) | KR101363441B1 (en) |
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JP2015214664A (en) * | 2014-05-13 | 2015-12-03 | 信越化学工業株式会社 | Fluorine-containing coating agent and article treated with the same |
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Also Published As
Publication number | Publication date |
---|---|
KR101363441B1 (en) | 2014-02-21 |
KR20130020908A (en) | 2013-03-04 |
CN102934207A (en) | 2013-02-13 |
TWI425002B (en) | 2014-02-01 |
TW201206949A (en) | 2012-02-16 |
JP2016036038A (en) | 2016-03-17 |
JP5821844B2 (en) | 2015-11-24 |
JP6032338B2 (en) | 2016-11-24 |
JPWO2011155407A1 (en) | 2013-08-01 |
CN102934207B (en) | 2016-04-06 |
SG185632A1 (en) | 2012-12-28 |
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