WO2012114864A1 - シラン化合物及びそれを用いた単分子層又は多分子層形成用組成物 - Google Patents
シラン化合物及びそれを用いた単分子層又は多分子層形成用組成物 Download PDFInfo
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- WO2012114864A1 WO2012114864A1 PCT/JP2012/052713 JP2012052713W WO2012114864A1 WO 2012114864 A1 WO2012114864 A1 WO 2012114864A1 JP 2012052713 W JP2012052713 W JP 2012052713W WO 2012114864 A1 WO2012114864 A1 WO 2012114864A1
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- silane compound
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- -1 Silane compound Chemical class 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title abstract description 13
- 239000002356 single layer Substances 0.000 title abstract 3
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 125000001424 substituent group Chemical group 0.000 claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000005647 linker group Chemical group 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 5
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- 229920002120 photoresistant polymer Polymers 0.000 claims description 45
- 239000004065 semiconductor Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005462 imide group Chemical group 0.000 claims description 2
- CYMRPDYINXWJFU-UHFFFAOYSA-N 2-carbamoylbenzoic acid Chemical group NC(=O)C1=CC=CC=C1C(O)=O CYMRPDYINXWJFU-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 42
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
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- 239000010703 silicon Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
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- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 238000010894 electron beam technology Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
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- WBUSESIMOZDSHU-UHFFFAOYSA-N 3-(4,5-dihydroimidazol-1-yl)propyl-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCN=C1 WBUSESIMOZDSHU-UHFFFAOYSA-N 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- VMJFYMAHEGJHFH-UHFFFAOYSA-M triphenylsulfanium;bromide Chemical compound [Br-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VMJFYMAHEGJHFH-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/165—Monolayers, e.g. Langmuir-Blodgett
Definitions
- the present invention relates to a composition for coating a substrate surface to form a monomolecular layer or a multimolecular layer in a resist lower layer.
- the present invention relates to a composition for forming a monomolecular layer or a multimolecular layer on a stepped (uneven) surface.
- An ion implantation step in manufacturing a semiconductor element such as a field effect transistor may employ a step of introducing impurity ions imparting n-type or p-type conductivity into a semiconductor substrate using a photoresist pattern as a mask.
- the semiconductor substrate has a stepped or uneven surface by forming a gate electrode and a gate wiring using a semiconductor material or a metal material such as polycrystalline silicon, aluminum, or titanium nitride.
- the thickly formed portion is not completely removed and tends to remain.
- the bottom shape of the resist pattern tends to be a skirt shape and a residue is generated.
- a method of treating the surface of a silicon wafer, which is a typical example of a semiconductor substrate, with HMDS (hexamethylene disilazane) to make the surface hydrophobic (water repellent) has been conventionally known.
- the surface of the silicon wafer exhibits hydrophilicity when a natural oxide film is formed. This is because a photoresist film formed by applying a photoresist solution to the hydrophilic surface and pre-baking has poor adhesion to a silicon wafer.
- the hydrophobicity and hydrophilicity of the substrate surface can be evaluated by the contact angle of water.
- the contact angle is largely changed before and after the light irradiation, the liquid repellent performance is obtained before the light irradiation, and the substituent has a hydrophilic performance by dissociation of the group having the liquid repellent performance when irradiated with light.
- a photodegradable coupling agent is described which results in.
- Patent Document 2 describes a compound that forms an organic thin film capable of selectively converting surface physical properties by light irradiation in order to make the pattern formation process simple and highly reliable.
- the present invention can form a desired photoresist pattern that does not have a bottom shape or a shape in which adjacent patterns are connected at the bottom, even on a substrate surface having a step.
- the present invention provides a novel composition for use in the surface treatment of a substrate on which a pattern is to be formed to form a monomolecular layer or a multimolecular layer on the substrate. Furthermore, this invention provides the novel silane compound used for the said composition.
- the first aspect of the present invention is the following formula (1A) or the following formula (1B): [In the formula, each R 1 independently represents a methyl group or an ethyl group, each X independently represents a linking group having 1 to 10 carbon atoms, and Z represents a phthalic group which may have at least one substituent.
- Ar represents a phenyl group or a naphthyl group independently, and the linking group represented by X contains at least one oxygen atom or sulfur atom in the main chain;
- the phenyl group may have at least one substituent.
- It is a silane compound represented by these.
- the phthalimide group is represented by the following formula (2)
- the maleimide group is represented by the following formula (3)
- the succinimide group is represented by the following formula (4).
- the nitrogen atom of the group represented by the formula (2), formula (3) or formula (4) is bonded to the oxygen atom of the formula (1A).
- examples of the substituent include a methyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a hydroxy group, a methoxy group, a fluoro group, and a chloro group.
- the substitution position of these substituents with respect to the phenyl group is not particularly limited, and may have two or more or two or more of the substituents. Even when the phthalimide group, the maleimide group, or the succinimide group has a substituent, the substituent can be selected from the above examples.
- the second aspect of the present invention is a composition for forming a monomolecular layer or a multimolecular layer containing the silane compound and an organic solvent.
- the composition for forming a monomolecular layer or a multimolecular layer is further represented by the following formula (5): [Wherein, R 2 independently represents a methyl group or an ethyl group, and Y represents an alkyl group having 1 to 5 carbon atoms or a phenyl group which may have at least one substituent. ]
- the silane compound represented by these can be included.
- examples of the substituent include an amino group, an imidazolyl group, a pyridyl group, a mercapto group, and a sulfo group.
- At least one of its hydrogen atoms may be substituted with an alkyl group such as a methyl group.
- an alkyl group such as a methyl group.
- examples of the substituent include a methyl group.
- a third aspect of the present invention includes a step of forming a monomolecular layer or a multimolecular layer on a semiconductor substrate using the composition according to the second aspect of the present invention, a photoresist film on the monomolecular layer or the multimolecular layer.
- a method of forming a photoresist pattern comprising: a step of exposing a semiconductor substrate covered with the monomolecular layer or polymolecular layer and the photoresist film; and a step of developing the photoresist film after the exposure. It is.
- a substrate having a step formed on the surface can be used as the semiconductor substrate.
- the step is caused by, for example, the gate electrode and the gate wiring of the semiconductor element.
- the composition according to the present invention can form a monomolecular layer or a multimolecular layer on the surface of the substrate, particularly on the surface of the substrate on which a step is formed.
- This monomolecular layer or polymolecular layer can adjust the bottom shape of the photoresist pattern formed thereon, for example, it can be prevented from becoming a skirt shape, and adjacent patterns are connected at the bottom. It is possible to prevent the shape from being changed.
- FIG. 1 is a photograph of an image obtained by observing a cross section of a photoresist pattern formed as a comparative example with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the composition according to the present invention includes a silane compound represented by the above formula (1A) or (1B). Since the silane compound has a structure represented by these formulas, an acid is generated by exposure, so that the acid can be diffused into the upper resist film and the bottom shape of the formed resist pattern can be changed.
- examples of the linking group having 1 to 10 carbon atoms represented by X include an alkylene group, a phenylene group, and a cyclohexylene group. When the linking group is an alkylene group having 3 or more carbon atoms, the main chain may be branched.
- the composition according to the present invention includes a silane compound represented by the formula (5) in addition to the silane compound represented by the formula (1A) or (1B), thereby forming a single molecule on the substrate. It is possible to control the hydrophobicity of the surface of the layer or the multilayer.
- the silane compound represented by Formula (5) only 1 type may be used and it may be used in combination of 2 or more type.
- the ratio of the silane compound represented by the formula (5) to the sum of the silane compound represented by the formula (1A) or the formula (1B) and the silane compound represented by the formula (5) is, for example, 1 mass. % To 99% by mass, preferably 5% to 95% by mass.
- the composition according to the present invention can contain water and an organic acid in addition to the silane compound.
- an organic acid By containing water and an organic acid, the storage stability of the composition according to the present invention is enhanced, and the silane compound is formed when the composition is applied on a substrate and baked to form a monomolecular layer or a multimolecular layer.
- the condensation reaction can be promoted.
- the organic acid include carboxylic acids such as acetic acid, maleic acid, oxalic acid, citric acid, malic acid, and succinic acid.
- the composition according to the present invention can contain a surfactant.
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether.
- polyoxyethylene alkyl aryl ethers polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc.
- Sorbitan fatty acid esters polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop (registered trademark) EF301, EF303, EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.
- the compounding quantity of these surfactant is 0.2 mass% or less normally in all the components of the composition based on this invention, Preferably it is 0.1 mass% or less.
- One kind selected from these surfactants may be added, or two or more kinds may be added in combination.
- composition according to the present invention can be prepared by dissolving each of the above components in an appropriate organic solvent, and is used in a uniform solution state.
- organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene Glycolpropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate 2-hydroxy-3- Methyl
- the ratio of the solid content excluding the organic solvent from the composition according to the present invention is, for example, 0.001% by mass to 10% by mass, preferably 0.1% by mass. Thru
- the silicon wafer On a semiconductor substrate (for example, a silicon wafer on which a gate electrode is formed, the silicon wafer may be covered with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film), a suitable spinner, coater, or the like.
- the composition according to the present invention is applied by a simple application method, and then baked using a heating means such as a hot plate. Baking conditions are appropriately selected from baking temperatures of 80 ° C. to 180 ° C. and baking times of 0.3 minutes to 10 minutes.
- a silicon nitride substrate, a quartz substrate, a glass substrate (including non-alkali glass, low alkali glass, and crystallized glass), or a glass substrate on which an ITO film is formed may be used.
- the layer formed using the composition according to the present invention is extremely thin, and it is difficult to measure its thickness. Furthermore, it is difficult to specify whether the layer is a monomolecular layer or a polymolecular layer.
- a photoresist film is formed on the monomolecular layer or the multimolecular layer formed on the semiconductor substrate through the above process.
- the formation of the photoresist film can be performed by a general method, that is, by applying a photoresist solution and baking.
- the photoresist solution is not particularly limited as long as it is sensitive to exposure light.
- a negative photoresist that lowers the alkali dissolution rate by crosslinking with an acid in a positive photoresist comprising a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, a polymer containing a hydroxyl group, an aminoplast crosslinking agent, and a photoacid generator.
- Photoresist chemically amplified photoresist consisting of a binder having a group that decomposes by acid to increase alkali dissolution rate and photoacid generator, low molecular weight compound and alkali that decomposes by acid to increase alkali dissolution rate of photoresist
- a chemically amplified photoresist comprising a soluble binder and a photoacid generator, a binder having a group that decomposes with an acid to increase the alkali dissolution rate, and a low molecular compound that decomposes with an acid to increase the alkali dissolution rate of the photoresist;
- a resist sensitive to an electron beam or EUV (extreme ultraviolet) may be used.
- photoresist pattern When forming a photoresist pattern, exposure is performed through a photomask (reticle) for forming a predetermined pattern.
- a photomask for forming a predetermined pattern.
- a KrF excimer laser, an ArF excimer laser, EUV, or an electron beam can be used.
- post-exposure heating Post ExposureEBake
- the conditions for the post-exposure heating are appropriately selected from heating temperatures of 80 ° C. to 150 ° C. and heating times of 0.3 minutes to 60 minutes.
- the semiconductor substrate on which the photoresist film is formed is exposed through a photomask and then developed with an alkaline developer.
- alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine, and propylamine.
- alkali metal hydroxides such as potassium hydroxide and sodium hydroxide
- quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline
- ethanolamine ethanolamine
- propylamine propylamine
- An alkaline aqueous solution such as an aqueous amine solution such as ethylenediamine can be used as an example.
- a surfactant or the like can be added to these developers.
- the development conditions are appropriately selected from a development temperature of 5 ° C. to 50 ° C. and a development time of 10 seconds to 300 seconds.
- the resist underlayer film formed from the resist underlayer film forming composition of the present invention is easily developed at room temperature using a 2.38 mass% tetramethylammonium hydroxide aqueous solution that is widely used for developing photoresists. be able to.
- Example 1 A solution was prepared using a silane compound, water, acetic acid and PGME (propylene glycol monomethyl ether) shown in Table 1 below. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.03 micrometer, and prepared the composition for monomolecular layer or multimolecular layer formation.
- PhTMS represents phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
- ImTES represents N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole (manufactured by Gelest). Represents.
- Example 1 The composition prepared in Example 1 was applied onto a silicon wafer using a spin coater and baked on a hot plate at 100 ° C. for 1 minute. Then, it is immersed for 1 minute in OK73 thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) consisting of 70% by mass of propylene glycol monomethyl ether and 30% by mass of propylene glycol monomethyl ether acetate, spin-dried and then dried at 100 ° C. for 30 seconds. A monomolecular layer or a multimolecular layer was formed on a silicon wafer.
- OK73 thinner manufactured by Tokyo Ohka Kogyo Co., Ltd.
- a commercially available photoresist solution (trade name: V146G, manufactured by JSR Corporation) was applied with a spinner at a rotation speed of 1050 rpm, and heated on a hot plate at 110 ° C. for 1 minute to form a photoresist film ( A film thickness of 0.360 ⁇ m) was formed.
- a Nikon Corporation NSR-S205C, KrF scanner (wavelength 248 nm, NA: 0.75, ANNULAR), the photoresist pattern line width and the width between the lines are set to 0.16 ⁇ m after development. Exposure was performed through the mask. Thereafter, the film was heated after exposure for 1 minute at 110 ° C. on a hot plate. After cooling, development was performed using a 0.26 N aqueous tetramethylammonium hydroxide solution as a developer.
- the surface of a silicon wafer was treated with hexamethyldisilazane (HMDS), and a photoresist film (film thickness 0.360 ⁇ m) was formed on the surface by the same method as described above. A pattern was formed. The result is shown in FIG.
- the shape of the obtained photoresist pattern had a shape in which the bottom portions of adjacent patterns were connected. That is, by forming a monomolecular layer or a polymolecular layer on a silicon wafer using the composition according to the present invention, the bottom shape of the photoresist pattern formed on this layer could be changed. It is considered that the bottom shape of the photoresist pattern was changed because the compound 5 contained in the composition prepared in Example 1 served as a photoacid generator, and the acid generated by exposure was transferred to the photoresist film.
- HMDS hexamethyldisilazane
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Abstract
Description
で表されるシラン化合物である。
で表されるシラン化合物を含むことができる。
前記炭素原子数1乃至5のアルキル基が置換基を有する場合、該置換基として例えばアミノ基、イミダゾリル基、ピリジル基、メルカプト基、スルホ基が挙げられる。ここで、アミノ基“-NH2”はその水素原子の少なくとも1つがアルキル基、例えばメチル基で置換されていてもよい。前記フェニル基が置換基を有する場合、該置換基としては、例えばメチル基が挙げられる。
マグネチックスターラーを備えた1000mL四口フラスコに、N-ヒドロキシフタルイミド15.77g及びテトラヒドロフラン(THF)450gを仕込み、氷浴下、2-クロロエタンスルホニルクロリド17.33gを加えた。次に、トリエチルアミン(Et3N)21.52gをテトラヒドロフラン20gで希釈した溶液を、30分かけて滴下した。この間、内温を4~7℃に保った。その後、5~10℃にて2時間攪拌した。反応終了後、反応液中に析出した塩をろ過し、ろ液を酢酸エチル1000mLで希釈した。ろ液を純水200gで2回洗浄後、濃縮乾燥し、化合物1の粗物26.14gを得た。この粗物に1,2-ジクロロエタン(DCE)60gを加え、30℃で溶解させた後、氷冷下、析出した結晶をろ過乾燥し、化合物1を13.29g得た(収率54%)。
マグネチックスターラーを備えた200mL四口フラスコに、上記合成例1で得た化合物1 7.00g、メルカプトプロピルトリエトキシシラン6.26g及び1,2-ジクロロエタン56gを仕込み、氷浴下、ピリジン0.55gを1,2-ジクロロエタン14gで希釈した溶液を、2時間かけて滴下した。その後、室温にて一晩攪拌した。反応終了後、反応液を濃縮乾燥し、化合物2の粗物を12.23g得た。この粗物をシリカゲルカラムにて精製し(展開溶媒:酢酸エチル/ヘキサン=1/1)、化合物2を5.63g得た(収率44%)。
マグネチックスターラーを備えた500mL四口フラスコに、トリエチルアミン23.04g及びエタノール(EtOH)135gを仕込み、攪拌した。次に、氷浴下、2-クロロエタンスルホニルクロリド16.87gを1,2-ジクロロエタン51gで希釈した溶液を滴下し、15℃にて1時間攪拌した。反応終了後、反応液を酢酸エチル300mLで希釈し、有機相を純水100gで2回、飽和食塩水100gで1回洗浄した。前記有機相を濃縮乾燥し、化合物3を12.50g得た(収率89%)。
マグネチックスターラーを備えた200mL四口フラスコに、上記合成例3で得た化合物3 12.50g及びジクロロメタン50gを仕込み、氷浴下、トリエチルアミン18.58gをジクロロメタン(DCM)10gで希釈した溶液を加えた。次に、メルカプトプロピルトリエトキシシラン20.79gをジクロロメタン40gで希釈した溶液を滴下した。その後、室温にて一晩攪拌した。反応終了後、反応液を濃縮乾燥し、化合物4を41.07g得た(収率99%)。
マグネチックスターラーを備えた500mL四口フラスコに、上記合成例4で得た化合物4 10.76g、トリフェニルスルホニウムブロミド6.47g、純水160g及びクロロホルム160gを仕込み、室温にて2時間攪拌した。反応終了後、クロロホルム相を抜き取り、硫酸ナトリウムで乾燥した。その硫酸ナトリウムをろ過後、ろ液を濃縮乾燥し、化合物5を9.87g得た(収率86%)。
下記表1に示す、シラン化合物、水、酢酸及びPGME(プロピレングリコールモノメチルエーテル)を用い、溶液を作製した。その後、孔径0.03μmのポリエチレン製ミクロフィルターを用いてろ過して、単分子層又は多分子層形成用組成物を調製した。表1において、“PhTMS”はフェニルトリメトキシシラン(東京化成工業(株)製)を表し、“ImTES”はN-(3-トリエトキシシリルプロピル)-4,5-ジヒドロイミダゾール(Gelest社製)を表す。
実施例1で調製した組成物を、シリコンウェハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間ベークした。その後、プロピレングリコールモノメチルエーテル70質量%及びプロピレングリコールモノメチルエーテルアセテート30質量%からなるOK73シンナー(東京応化工業(株)製)にて、1分間浸漬させ、スピンドライ後、100℃で30秒間乾燥させ、シリコンウェハー上に単分子層又は多分子層を形成した。この層の上に、市販のフォトレジスト溶液(JSR(株)製、商品名:V146G)をスピナーにより回転数1050rpmで塗布し、ホットプレート上で110℃にて1分間加熱してフォトレジスト膜(膜厚0.360μm)を形成した。次いで、(株)ニコン製NSR-S205C、KrFスキャナー(波長248nm、NA:0.75、ANNULAR)を用い、現像後にフォトレジストパターンのライン幅及びそのライン間の幅が0.16μmになるよう設定されたマスクを通して、露光を行った。その後、ホットプレート上110℃で1分間露光後加熱を行なった。冷却後、現像液として0.26規定の水酸化テトラメチルアンモニウム水溶液を用いて現像した。
Claims (6)
- 請求項1に記載のシラン化合物及び有機溶剤を含む、単分子層又は多分子層形成用組成物。
- さらに水及び有機酸を含む請求項2に記載の単分子層又は多分子層形成用組成物。
- 請求項2乃至請求項4のいずれか一項に記載の組成物を用いて半導体基板上に単分子層又は多分子層を形成する工程、前記単分子層又は多分子層上にフォトレジスト膜を形成する工程、前記単分子層又は多分子層と前記フォトレジスト膜で被覆された半導体基板を露光する工程、及び前記露光後に前記フォトレジスト膜を現像する工程を含む、フォトレジストパターンの形成方法。
- 前記半導体基板は表面に段差が形成されている、請求項5に記載のフォトレジストパターンの形成方法。
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WO2009104748A1 (ja) * | 2008-02-22 | 2009-08-27 | 株式会社ルネサステクノロジ | 被露光基板用撥水化剤組成物、レジストパターンの形成方法及び該形成方法により製造した電子デバイス、被露光基板の撥水化処理方法、被露光基板用撥水化剤セット及びそれを用いた被露光基板の撥水化処理方法 |
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