JP2020086176A - Composition for forming monomolecular layer or multimolecular layer, monomolecular layer or multimolecular layer, and laminate, and organic silicon compound - Google Patents
Composition for forming monomolecular layer or multimolecular layer, monomolecular layer or multimolecular layer, and laminate, and organic silicon compound Download PDFInfo
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- JP2020086176A JP2020086176A JP2018221626A JP2018221626A JP2020086176A JP 2020086176 A JP2020086176 A JP 2020086176A JP 2018221626 A JP2018221626 A JP 2018221626A JP 2018221626 A JP2018221626 A JP 2018221626A JP 2020086176 A JP2020086176 A JP 2020086176A
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- layer
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- forming
- carbon atoms
- multimolecular
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- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 66
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 55
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 183
- 230000001681 protective effect Effects 0.000 claims description 39
- 239000002356 single layer Substances 0.000 claims description 28
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- 238000001039 wet etching Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005380 borophosphosilicate glass Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001312 dry etching Methods 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 4
- 229920005591 polysilicon Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 9
- 230000002940 repellent Effects 0.000 abstract description 2
- 239000005871 repellent Substances 0.000 abstract description 2
- -1 2-methyl-cyclopropyl group Chemical group 0.000 description 107
- 239000010408 film Substances 0.000 description 67
- 239000000126 substance Substances 0.000 description 17
- 229920002120 photoresistant polymer Polymers 0.000 description 16
- 239000004065 semiconductor Substances 0.000 description 16
- 235000012431 wafers Nutrition 0.000 description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000010511 deprotection reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 0 CC1(*)OC(C=CCC2C*S(*)(*)*)=C2O1 Chemical compound CC1(*)OC(C=CCC2C*S(*)(*)*)=C2O1 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
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- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006439 1-n-propyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
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- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
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- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
本発明は、基板表面に塗布して、単分子層又は多分子層をレジスト下層に形成するための単分子層又は多分子層形成用組成物、及びそれを用いた単分子層又は多分子層及び積層体、並びに有機ケイ素化合物に関する。 The present invention provides a composition for forming a monomolecular layer or a multimolecular layer as a resist lower layer by coating on the surface of a substrate, and a monomolecular layer or a polymolecular layer using the same. And a laminate, and an organosilicon compound.
半導体素子製造において、半導体基板の代表例であるシリコンウェハーの加工のために、様々な表面処理が実施される。例えば、シリコンウェハー表面をＨＭＤＳ（ヘキサメチルジシラザン）で処理し、当該表面を疎水性（撥水性）にする方法が従来から知られている。シリコンウェハー表面は、自然酸化膜が形成されていると親水性を示す。その親水性の表面に、フォトレジスト溶液を塗布し、プリベークして形成されるフォトレジスト膜は、シリコンウェハーとの密着性が悪いからである。 In the manufacture of semiconductor devices, various surface treatments are performed for processing a silicon wafer, which is a typical example of a semiconductor substrate. For example, a method of treating the surface of a silicon wafer with HMDS (hexamethyldisilazane) to make the surface hydrophobic (water repellent) has been conventionally known. The surface of a silicon wafer is hydrophilic when a natural oxide film is formed. This is because the photoresist film formed by applying a photoresist solution to the hydrophilic surface and prebaking it has poor adhesion to the silicon wafer.
基板表面の疎水性及び親水性は、水の接触角によって評価することができる。特許文献１には、光照射の前後で接触角を大きく変化させ、光照射前は撥液性能を有し、光照射された際に撥液性能を有する基の解離により親水性能を有する構造を生じるという光分解性カップリング剤が記載されている。特許文献２には、パターン形成工程を簡潔且つ高信頼性とするために、光照射によって選択的に表面物性を変換することのできる有機薄膜を形成する化合物が記載されている。 The hydrophobicity and hydrophilicity of the substrate surface can be evaluated by the contact angle of water. Patent Document 1 discloses a structure in which a contact angle is largely changed before and after light irradiation, liquid repellency is provided before light irradiation, and hydrophilic property is obtained by dissociation of a group having liquid repellency when light is irradiated. Photodegradable coupling agents that result are described. Patent Document 2 describes a compound that forms an organic thin film whose surface physical properties can be selectively converted by light irradiation in order to make the pattern formation process simple and highly reliable.
本発明は、基板表面の密着性、撥液性などの特性を変更することができる、具体的には光照射により、該特性が変化する単分子層又は多分子層を形成するための新規な単分子層又は多分子層形成用組成物、及びそれを用いた単分子層又は多分子層及び積層体、並びに有機ケイ素化合物を提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention can change characteristics such as adhesion and liquid repellency of a substrate surface, and more specifically, a novel novel method for forming a monomolecular layer or a multimolecular layer whose characteristics are changed by light irradiation. An object is to provide a composition for forming a monomolecular layer or a multimolecular layer, a monomolecular layer or a multimolecular layer and a laminate using the composition, and an organosilicon compound.
本発明は第１観点として、下記一般式（１）で表される有機ケイ素化合物と、有機溶剤とを含む、単分子層又は多分子層形成用組成物、
第２観点として、さらに水及び有機酸を含む、請求項１に記載の単分子層又は多分子層形成用組成物、
第３観点として、さらに光酸発生剤を含む、請求項１又は２に記載の単分子層又は多分子層形成用組成物、
第４観点として、密着性付与剤である、請求項１〜３のいずれか一項に記載の単分子層又は多分子層形成用組成物、
第５観点として、請求項１〜４の何れか一項に記載の単分子層又は多分子層形成用組成物を用いて形成された、単分子層又は多分子層、
第６観点として、基板と、前記基板上に請求項１〜４の何れか一項に記載の単分子層又は多分子層形成用組成物を用いて形成された単分子層又は多分子層とを具備する、積層体、
第７観点として、前記単分子層又は多分子層上に形成された保護膜をさらに具備する、請求項６に記載の積層体、
第８観点として、前記保護膜が、耐ウエットエッチング保護膜である、請求項７に記載の積層体、
第９観点として、前記基板が、銀、銅、グラフェン、ガラス、シリコン、ポリシリコン、酸化シリコン（ＳｉＯ２）、窒化シリコン（ＳｉＮ）、酸窒化シリコン（ＳｉＯＮ）、ＢＰＳＧ（Ｂｏｒｏ−Ｐｈｏｓｐｈｏ Ｓｉｌｉｃａｔｅ Ｇｌａｓｓ）、チタン（Ｔｉ）、窒化チタン（ＴｉＮ）、酸窒化チタン（ＴｉＯＮ）、タンタル（Ｔａ）、窒化タンタル（ＴａＮ）、タングステン（Ｗ）、窒化タングステン（ＷＮ）、窒化ガリウム（ＧａＮ）、ヒ化ガリウム（ＧａＡｓ）、ゲルマニウム（Ｇｅ）、窒化インジウム（ＩｎＮ）、リン化インジウム（ＩｎＰ）及び窒化アルミニウム（ＡｌＮ）から選択される少なくとも１種を含む基板である、請求項６に記載の積層体、
第１０観点として、基板上に、請求項１〜４の何れか一項に記載の単分子層又は多分子層形成用組成物を塗布し、ベークして単分子層又は多分子層を形成する第１工程、
前記単分子層又は多分子層にフォトマスクを介して露光する第２工程、
を含む、パターン化された単分子層又は多分子層を有する基板の製造方法、
第１１観点として、前記第２工程の後、前記単分子層又は多分子層を酸で処理してベークすることにより、保護されたカテコール基を脱保護する第３工程を有する、請求項１０記載のパターン化された単分子層又は多分子層を有する基板の製造方法、
第１２観点として、基板上に、請求項１〜４の何れか一項に記載の単分子層又は多分子層形成用組成物を塗布し、ベークして単分子層又は多分子層を形成する第１工程と、
前記単分子層又は多分子層の上に保護膜形成用組成物を塗布し、ベークして保護膜を形成する第２工程と、
前記保護膜上にレジストパターンを形成する第３工程と、
前記レジストパターンを介して前記保護膜をドライエッチングして保護膜パターンを形成する第４工程と、
ドライエッチング後の前記保護膜パターンをウエットエッチングマスクとして、前記基板をウエットエッチングする第５工程と、
を含むパターン化された基板の製造方法、
第１３観点として、基板上に、請求項１〜４の何れか一項に記載の単分子層又は多分子層形成用組成物を塗布し、ベークして単分子層又は多分子層を形成する第１工程と、
前記単分子層又は多分子層の上に光酸発生剤を含むレジストを用いてレジスト層を形成する第２工程と、
前記レジスト層にフォトマスクを介して露光してレジストパターンを形成する第３工程と、
前記レジストパターンを除去する第４工程と、
を含むパターン化された基板の製造方法、
第１４観点として、下記一般式（１）で表される有機ケイ素化合物。
As a second aspect, the composition for forming a monolayer or a multilayer according to claim 1, further comprising water and an organic acid.
As a third aspect, the composition for forming a monomolecular layer or a multimolecular layer according to claim 1 or 2, further comprising a photoacid generator.
As a fourth aspect, a composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 3, which is an adhesion promoter.
As a fifth aspect, a monomolecular layer or a multimolecular layer formed using the composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 4,
As a sixth aspect, a substrate and a monomolecular layer or a multimolecular layer formed on the substrate using the composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 4. Including a laminated body,
As a seventh aspect, the laminate according to claim 6, further comprising a protective film formed on the monomolecular layer or the polymolecular layer.
As an eighth aspect, the laminate according to claim 7, wherein the protective film is a wet etching resistant protective film.
As a ninth aspect, the substrate is silver, copper, graphene, glass, silicon, polysilicon, silicon oxide (SiO 2 ), silicon nitride (SiN), silicon oxynitride (SiON), BPSG (Boro-Phospho Silicate Glass). , Titanium (Ti), titanium nitride (TiN), titanium oxynitride (TiON), tantalum (Ta), tantalum nitride (TaN), tungsten (W), tungsten nitride (WN), gallium nitride (GaN), gallium arsenide The laminate according to claim 6, which is a substrate containing at least one selected from (GaAs), germanium (Ge), indium nitride (InN), indium phosphide (InP), and aluminum nitride (AlN).
As a tenth aspect, the composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 4 is applied onto a substrate and baked to form a monomolecular layer or a multimolecular layer. The first step,
A second step of exposing the monolayer or polylayer through a photomask;
Comprising a patterned monolayer or multi-layered substrate,
As an eleventh aspect, after the second step, there is a third step of deprotecting the protected catechol group by treating the monolayer or polylayer with an acid and baking. A method of manufacturing a substrate having a patterned monolayer or multilayer,
As a twelfth aspect, the composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 4 is applied onto a substrate and baked to form a monomolecular layer or a multimolecular layer. The first step,
A second step of applying a protective film-forming composition onto the monomolecular layer or the polymolecular layer and baking to form a protective film;
A third step of forming a resist pattern on the protective film,
A fourth step of forming a protective film pattern by dry etching the protective film through the resist pattern;
A fifth step of wet-etching the substrate using the protective film pattern after dry etching as a wet etching mask;
A method of manufacturing a patterned substrate including
As a thirteenth aspect, the composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 4 is applied onto a substrate and baked to form a monomolecular layer or a multimolecular layer. The first step,
A second step of forming a resist layer using a resist containing a photoacid generator on the monolayer or polylayer,
A third step of forming a resist pattern by exposing the resist layer through a photomask,
A fourth step of removing the resist pattern,
A method of manufacturing a patterned substrate including
A fourteenth aspect is an organosilicon compound represented by the following general formula (1).
本発明に係る単分子層又は多分子層形成用組成物は、基板表面の密着性、撥液性などの特性を変更することができる単分子層又は多分子層を形成することができ、また、単分子層又は多分子層は、層中の化合物の保護カテコール基を脱保護することで、基板表面の密着性、撥液性などの特性をさらに変更することができ、種々の応用が可能な単分子層又は多分子層及び積層体を提供することができる。 The composition for forming a monomolecular layer or a multimolecular layer according to the present invention can form a monomolecular layer or a multimolecular layer capable of changing the properties of the substrate surface such as adhesion and liquid repellency, and By deprotecting the protective catechol group of the compound in the mono-layer or multi-layer, it is possible to further change the properties such as adhesion and liquid repellency of the substrate surface, and various applications are possible. It is possible to provide various monolayers or multilayers and laminates.
本発明に係る単分子層又は多分子層形成用組成物は、下記式（１）で表される有機ケイ素化合物と、有機溶剤とを含む。
ここで、式（１）中、Ａ１、Ａ２は、各々独立に水素原子、炭素原子数１〜６のアルキル基又は炭素原子数６〜４０のフェニル基であり、Ｒ１は単結合又は硫黄原子で連結されていてもよい炭素原子数１〜６のアルキレン基であり、Ｒ２〜Ｒ４は各々独立にハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数６〜４０のフェニル基又は炭素原子数１〜６のアルコキシ基であり、Ｒ２〜Ｒ４の少なくとも１つは炭素原子数１〜６のアルコキシ基である。 Here, in the formula (1), A 1 and A 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group having 6 to 40 carbon atoms, and R 1 is a single bond or It is an alkylene group having 1 to 6 carbon atoms which may be linked by a sulfur atom, and R 2 to R 4 are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 40 carbon atoms. It is a phenyl group or an alkoxy group having 1 to 6 carbon atoms, and at least one of R 2 to R 4 is an alkoxy group having 1 to 6 carbon atoms.
上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ
る。
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
上記炭素原子数１〜６のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、シクロプロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、シクロブチル基、１−メチル−シクロプロピル基、２−メチル−シクロプロピル基、ｎ−ペンチル基、１−メチル−ｎ−ブチル基、２−メチル−ｎ−ブチル基、３−メチル−ｎ−ブチル基、１，１−ジメチル−ｎ−プロピル基、１，２−ジメチル−ｎ−プロピル基、２，２−ジメチル−ｎ−プロピル基、１−エチル−ｎ−プロピル基、シクロペンチル基、１−メチル−シクロブチル基、２−メチル−シクロブチル基、３−メチル−シクロブチル基、１，２−ジメチル−シクロプロピル基、２，３−ジメチル−シクロプロピル基、１−エチル−シクロプロピル基、２−エチル−シクロプロピル基、ｎ−ヘキシル基、１−メチル−ｎ−ペンチル基、２−メチル−ｎ−ペンチル基、３−メチル−ｎ−ペンチル基、４−メチル−ｎ−ペンチル基、１，１−ジメチル−ｎ−ブチル基、１，２−ジメチル−ｎ−ブチル基、１，３−ジメチル−ｎ−ブチル基、２，２−ジメチル−ｎ−ブチル基、２，３−ジメチル−ｎ−ブチル基、３，３−ジメチル−ｎ−ブチル基、１−エチル−ｎ−ブチル基、２−エチル−ｎ−ブチル基、１，１，２−トリメチル−ｎ−プロピル基、１，２，２−トリメチル−ｎ−プロピル基、１−エチル−１−メチル−ｎ−プロピル基、１−エチル−２−メチル−ｎ−プロピル基、シクロヘキシル基、１−メチル−シクロペンチル基、２−メチル−シクロペンチル基、３−メチル−シクロペンチル基、１−エチル−シクロブチル基、２−エチル−シクロブチル基、３−エチル−シクロブチル基、１，２−ジメチル−シクロブチル基、１，３−ジメチル−シクロブチル基、２，２−ジメチル−シクロブチル基、２，３−ジメチル−シクロブチル基、２，４−ジメチル−シクロブチル基、３，３−ジメチル−シクロブチル基、１−ｎ−プロピル−シクロプロピル基、２−ｎ−プロピル−シクロプロピル基、１−ｉ−プロピル−シクロプロピル基、２−ｉ−プロピル−シクロプロピル基、１，２，２−トリメチル−シクロプロピル基、１，２，３−トリメチル−シクロプロピル基、２，２，３−トリメチル−シクロプロピル基、１−エチル−２−メチル−シクロプロピル基、２−エチル−１−メチル−シクロプロピル基、２−エチル−２−メチル−シクロプロピル基及び２−エチル−３−メチル−シクロプロピル基等が挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t- Butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n -Butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1 -Methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2- Ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1 -Dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group Group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2- Trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2- Dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group Group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2 3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2- Examples thereof include a methyl-cyclopropyl group and a 2-ethyl-3-methyl-cyclopropyl group.
炭素原子数６〜４０のフェニル基としては、フェニル基、ｏ−メチルフェニル基、ｍ−メチルフェニル基、ｐ−メチルフェニル基、ｏ−クロルフェニル基、ｍ−クロルフェニル基、ｐ−クロルフェニル基、ｏ−フルオロフェニル基、ｐ−フルオロフェニル基、ｏ−メトキシフェニル基、ｐ−メトキシフェニル基、ｐ−ニトロフェニル基、ｐ−シアノフェニル基、α−ナフチル基、β−ナフチル基、ｏ−ビフェニリル基、ｍ−ビフェニリル基、ｐ−ビフェニリル基、１−アントリル基、２−アントリル基、９−アントリル基、１−フェナントリル基、２−フェナントリル基、３−フェナントリル基、４−フェナントリル基及び９−フェナントリル基等が挙げられる。 Examples of the phenyl group having 6 to 40 carbon atoms include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group. , O-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group Group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group and 9-phenanthryl group Groups and the like.
上記炭素原子数１〜６のアルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｉ−ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基、ｎ−ペンチルオキシ基、１−メチル−ｎ−ブトキシ基、２−メチル−ｎ−ブトキシ基、３−メチル−ｎ−ブトキシ基、１，１−ジメチル−ｎ−プロポキシ基、１，２−ジメチル−ｎ−プロポキシ基、２，２−ジメチル−ｎ−プロポキシ基、１−エチル−ｎ−プロポキシ基、ｎ−ヘキシルオキシ基、１−メチル−ｎ−ペンチルオキシ基、２−メチル−ｎ−ペンチルオキシ基、３−メチル−ｎ−ペンチルオキシ基、４−メチル−ｎ−ペンチルオキシ基、１，１−ジメチル−ｎ−ブトキシ基、１，２−ジメチル−ｎ−ブトキシ基、１，３−ジメチル−ｎ−ブトキシ基、２，２−ジメチル−ｎ−ブトキシ基、２，３−ジメチル−ｎ−ブトキシ基、３，３−ジメチル−ｎ−ブトキシ基、１−エチル−ｎ−ブトキシ基、２−エチル−ｎ−ブトキシ基、１，１，２−トリメチル−ｎ−プロポキシ基、１，２，２−トリメチル−ｎ−プロポキシ基、１−エチル−１−メチル−ｎ−プロポキシ基、及び１−エチル−２−メチル−ｎ−プロポキシ基等が挙げられる。 Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n. -Pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n -Propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n- Butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n -Butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2- Examples thereof include a methyl-n-propoxy group.
このように本発明の単分子層又は多分子層形成用組成物に含有される有機ケイ素化合物は、保護基で保護されたカテコール基（以下、保護カテコール基ともいう）とシリル基とを有するものである。シリル基の置換位置は、保護カテコール基に対してオルト位でもメタ位でもよいが、好ましくは下記式（１−１）に示すようにメタ位である。 Thus, the organosilicon compound contained in the composition for forming a monomolecular layer or a multimolecular layer of the present invention has a catechol group protected by a protecting group (hereinafter, also referred to as a protected catechol group) and a silyl group. Is. The substitution position of the silyl group may be ortho or meta with respect to the protected catechol group, but is preferably meta as shown in the following formula (1-1).
Ｒ２〜Ｒ４の少なくとも１つがメトキシ基又はエトキシ基から選ばれることが好ましい。
かかる有機ケイ素化合物は新規である。特に、下記化合物はシラン基が基板と結合して保護カテコール基又はカテコール基が表面に並ぶような膜を容易に形成することができるものである。
At least one of R 2 to R 4 is preferably selected from a methoxy group or an ethoxy group.
Such organosilicon compounds are new. In particular, the following compounds can easily form a protective catechol group or a film in which catechol groups are arranged on the surface by bonding a silane group to a substrate.
本発明に係る単分子層又は多分子層形成用組成物は、上記有機ケイ素化合物及び有機溶媒以外に水及び有機酸を含有することができる。水及び有機酸を含むことにより、本発明に係る組成物の保存安定性を高めると共に、当該組成物を基板上に塗布し、ベークして単分子層又は多分子層を形成する際に有機ケイ素化合物の縮合反応を促進させることができる。有機酸としては、例えばギ酸、酢酸、マレイン酸、シュウ酸、クエン酸、リンゴ酸、コハク酸のようなカルボン酸化合物が挙げられる。 The composition for forming a monomolecular layer or a multimolecular layer according to the present invention may contain water and an organic acid in addition to the organic silicon compound and the organic solvent. By containing water and an organic acid, the storage stability of the composition according to the present invention is increased, and at the same time, the composition is applied onto a substrate and baked to form a monomolecular layer or a polymolecular layer. It is possible to accelerate the condensation reaction of the compound. Examples of the organic acid include carboxylic acid compounds such as formic acid, acetic acid, maleic acid, oxalic acid, citric acid, malic acid and succinic acid.
本発明に係る単分子層又は多分子層形成用組成物は界面活性剤を含有することができる。界面活性剤としては、例えばポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェノールエーテル、ポリオキシエチレンノニルフェノールエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレートなどのポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ（登録商標）ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５２（三菱マテリアル電子化成（株）（旧（株）ジェムコ）製）、メガファック（登録商標）Ｆ１７１、同Ｆ１７３、同Ｒ３０（ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１（住友スリーエム（株）製）、アサヒガード（登録商標）ＡＧ７１０、サーフロン（登録商標）Ｓ−３８２、同ＳＣ１０１、同ＳＣ１０２、同ＳＣ１０３、同ＳＣ１０４、同ＳＣ１０５、同ＳＣ１０６（旭硝子（株）製）等のフッ素系界面活性剤、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）を挙げることができる。これらの界面活性剤の配合量は、本発明に係る組成物の全成分中、通常０．２質量％以下、好ましくは０．１質量％以下である。これらの界面活性剤から選択された１種類を添加してもよいし、２種以上の組合せで添加することもできる。 The composition for forming a monomolecular layer or a multimolecular layer according to the present invention may contain a surfactant. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether. Polyoxyethylene alkylaryl ethers, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Polyoxyethylene sorbitan such as sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants such as fatty acid esters, F-Top (registered trademark) EF301, EF303, EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Gemco)), Megafac (registered trademark) F171, F173, R30 (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, and SC102. Examples thereof include fluorosurfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The blending amount of these surfactants is usually 0.2% by mass or less, preferably 0.1% by mass or less, based on all components of the composition according to the present invention. One kind selected from these surfactants may be added, or two or more kinds may be added in combination.
本発明に係る単分子層又は多分子層形成用組成物は、上記有機ケイ素化合物及び各成分を適当な有機溶剤に溶解させることによって調製でき、均一な溶液状態で用いられる。そのような有機溶剤として、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドンが挙げられる。これらの有機溶剤は単独又は２種以上の組合せで使用することができる。 The composition for forming a monomolecular layer or a multimolecular layer according to the present invention can be prepared by dissolving the above organosilicon compound and each component in an appropriate organic solvent, and is used in a uniform solution state. As such an organic solvent, for example, 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 Glycol propyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate , Methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, Examples include butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.
本発明に係る単分子層又は多分子層形成用組成物から有機溶剤を除いた（水及び有機酸を含む場合はこれらも除いた）固形分の割合は、例えば０．００１質量％乃至１０質量％、好ましくは０．１質量％乃至５質量％である。 The ratio of the solid content obtained by removing the organic solvent from the composition for forming a monomolecular layer or the multimolecular layer according to the present invention (when water and an organic acid are also removed) is, for example, 0.001% by mass to 10% by mass. %, preferably 0.1% by mass to 5% by mass.
かかる単分子層又は多分子層形成用組成物は、基板等に塗布してベークすることにより、単分子層又は多分子層を形成できる。ここで、単分子層又は多分子層とは、１分子又は１〜１０程度の多分子で形成された層をいい、通常の膜厚としては測定できない程度、例えば、０．０１ｎｍ〜１０ｎｍ又は１ｎｍ〜５ｎｍ程度の膜をいうが、場合によっては、島状に点在する場合も含む。
このような基板上に形成される単分子層又は多分子層は、表面の疎水性を制御することができ、基板の表面の耐薬品性を向上させることができ、また、基板上に形成されるレジスト膜、レジスト下層膜、又は半導体用ウエットエッチング液に対する耐性を向上させる保護膜又はレジスト下層との密着性を向上させることができる。
また、単分子層又は多分子層形成用組成物を用いて形成される単分子層又は多分子層は、保護カテコール基を有しているが、保護カテコール基は、酸処理などにより、容易に脱保護できるので、カテコール基として用いることができる。これにより、表面の疎水性や耐薬品性や密着性を変更することができる。さらに、場合によっては、所望のパターンを形成するためのフォトマスク（レチクル）を通して露光を行うことにより、所望の領域に存在する保護カテコール基のみを脱保護してカテコール基とすることができ、この場合、所望の領域と他の領域との表面の特性を変化させることができる。例えば、所望の領域又は他の領域と所望の物質との接合性、密着性を選択的に向上させることができ、所望の物質を選択的に接合することができる。
なお、所望の物資としては、銅、グラフェン、銀インクなどを挙げることができる。
また、本発明の単分子層又は多分子層形成用組成物を塗布して単分子層又は多分子層を形成する基板としては、ガラス基板、シリコン基板、ＴｉＮ基板、Ｔａ基板、ＴａＮ基板、Ｗ基板、ＧａＡｓ基板などを挙げることができる。
本発明の基板としては、銀、銅、グラフェン、ガラス、シリコン、ポリシリコン、酸化シリコン（ＳｉＯ２）、窒化シリコン（ＳｉＮ）、酸窒化シリコン（ＳｉＯＮ）、ＢＰＳＧ（Ｂｏｒｏ−Ｐｈｏｓｐｈｏ Ｓｉｌｉｃａｔｅ Ｇｌａｓｓ）、チタン（Ｔｉ）、窒化チタン（ＴｉＮ）、酸窒化チタン（ＴｉＯＮ）、タンタル（Ｔａ）、窒化タンタル（ＴａＮ）、タングステン（Ｗ）、窒化タングステン（ＷＮ）、窒化ガリウム（ＧａＮ）、ヒ化ガリウム（ＧａＡｓ）、ゲルマニウム（Ｇｅ）、窒化インジウム（ＩｎＮ）、リン化インジウム（ＩｎＰ）及び窒化アルミニウム（ＡｌＮ）から選択される少なくとも１種を含む基板を挙げることができ、例えば、シリコンウエハ、ゲルマニウムウエハ、及びヒ化ガリウム、リン化インジウム、窒化ガリウム、窒化インジウム、窒化アルミニウム等の化合物半導体ウエハが挙げられる。
表面に無機膜が形成された基板を用いる場合、当該無機膜は、例えば、ＡＬＤ（原子層堆積）法、ＣＶＤ（化学気相堆積）法、反応性スパッタ法、イオンプレーティング法、真空蒸着法、スピンコーティング法（スピンオングラス：ＳＯＧ）により形成される。前記無機膜として、例えば、ポリシリコン膜、酸化ケイ素膜、窒化珪素膜、ＢＰＳＧ（Ｂｏｒｏ−Ｐｈｏｓｐｈｏ Ｓｉｌｉｃａｔｅ Ｇｌａｓｓ）膜、窒化チタン膜、酸窒化チタン膜、窒化タングステン膜、窒化ガリウム膜、及びヒ化ガリウム膜が挙げられる。
The composition for forming a monomolecular layer or a multimolecular layer can be applied to a substrate or the like and baked to form a monomolecular layer or a multimolecular layer. Here, the monomolecular layer or the multimolecular layer refers to a layer formed of one molecule or polymolecules of about 1 to 10 and is a level that cannot be measured as a normal film thickness, for example, 0.01 nm to 10 nm or 1 nm. A film having a thickness of about 5 nm is included, but in some cases, it also includes the case of being scattered like islands.
The monolayer or multilayer formed on such a substrate can control the hydrophobicity of the surface, improve the chemical resistance of the surface of the substrate, and can be formed on the substrate. Adhesion with a resist film, a resist underlayer film, or a protective film or a resist underlayer for improving resistance to a wet etching solution for semiconductors can be improved.
Further, a monomolecular layer or a multimolecular layer formed using the composition for forming a monomolecular layer or a multimolecular layer has a protected catechol group, but the protected catechol group is easily treated by an acid treatment or the like. Since it can be deprotected, it can be used as a catechol group. Thereby, the hydrophobicity, chemical resistance and adhesiveness of the surface can be changed. Further, in some cases, by exposing through a photomask (reticle) for forming a desired pattern, only the protected catechol group existing in the desired region can be deprotected to be a catechol group. In this case, the surface characteristics of the desired area and the other area can be changed. For example, the bondability and adhesiveness between a desired region or another region and a desired substance can be selectively improved, and the desired substance can be selectively joined.
The desired materials may include copper, graphene, silver ink, and the like.
Further, as a substrate for forming the monomolecular layer or the polymolecular layer by applying the composition for forming a monomolecular layer or the polymolecular layer of the present invention, a glass substrate, a silicon substrate, a TiN substrate, a Ta substrate, a TaN substrate, W Substrates, GaAs substrates and the like can be mentioned.
The substrate of the present invention includes silver, copper, graphene, glass, silicon, polysilicon, silicon oxide (SiO 2 ), silicon nitride (SiN), silicon oxynitride (SiON), BPSG (Boro-Phospho Silicate Glass), titanium. (Ti), titanium nitride (TiN), titanium oxynitride (TiON), tantalum (Ta), tantalum nitride (TaN), tungsten (W), tungsten nitride (WN), gallium nitride (GaN), gallium arsenide (GaAs). ), germanium (Ge), indium nitride (InN), indium phosphide (InP), and aluminum nitride (AlN). Examples of the substrate include a silicon wafer, a germanium wafer, and Examples thereof include compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride and aluminum nitride.
When a substrate having an inorganic film formed on its surface is used, the inorganic film is formed by, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum deposition method. , Spin coating method (spin on glass: SOG). Examples of the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium oxynitride film, a tungsten nitride film, a gallium nitride film, and gallium arsenide film. Examples include membranes.
以下、本発明に係る単分子層又は多分子層形成用組成物の使用について説明する。半導体基板（例えば、ゲート電極 が形成されているシリコンウェハー、該シリコンウェハーは酸化珪素膜、窒化珪素膜、酸化窒化珪素膜、ＴｉＮ膜、Ｔａ膜、ＴａＮ膜、Ｗ膜又はＧａＡｓ膜で被覆されていてもよい。）の上に、スピナー、コーター等の適当な塗布方法により本発明に係る単分子層又は多分子層形成用組成物を塗布し、その後、ホットプレート等の加熱手段を用いてベークする。ベーク条件としては、ベーク温度８０℃乃至１８０℃、ベーク時間０．３分乃至１０分間の中から適宜選択される。半導体基板にかえて、窒化珪素基板、石英基板、ガラス基板（無アルカリガラス、低アルカリガラス、結晶化ガラスを含む）、ＩＴＯ膜が形成されたガラス基板を用いてもよい。 Hereinafter, use of the composition for forming a monolayer or a multilayer according to the present invention will be described. Semiconductor substrate (for example, a silicon wafer having a gate electrode formed thereon, the silicon wafer is covered with a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a TiN film, a Ta film, a TaN film, a W film or a GaAs film). The composition for forming a monomolecular layer or a multimolecular layer according to the present invention is applied to the above by a suitable coating method such as a spinner or a coater, and then baked using a heating means such as a hot plate. To do. The baking conditions are appropriately selected from a baking temperature of 80° C. to 180° C. and a baking time of 0.3 minutes to 10 minutes. Instead of the semiconductor substrate, 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.
その後、半導体基板上に残留する過剰な有機ケイ素化合物を溶剤で除去し、乾燥させることによって、単分子層又は多分子層が形成される。ここで、本発明に係る単分子層又は多分子層形成用組成物を用いて形成される単分子層又は多分子層は極めて薄い。そのため、当該層が単分子層、多分子層のいずれであるか特定することも困難である場合がある。 Then, the excess organosilicon compound remaining on the semiconductor substrate is removed with a solvent and dried to form a monomolecular layer or a multimolecular layer. Here, the monomolecular layer or the multimolecular layer formed using the composition for forming a monomolecular layer or the multimolecular layer according to the present invention is extremely thin. Therefore, it may be difficult to specify whether the layer is a monolayer or a polylayer.
上記過程を経て半導体基板上に形成された単分子層又は多分子層の上に、フォトレジスト膜を形成する。フォトレジスト膜の形成は一般的な方法、すなわち、フォトレジスト溶液の塗布及びベークによって行うことができる。 A photoresist film is formed on the monomolecular layer or the multimolecular layer formed on the semiconductor substrate through the above process. The photoresist film can be formed by a general method, that is, by coating and baking a photoresist solution.
フォトレジスト溶液としては、露光後に感光するものであれば特に限定はない。ノボラック樹脂と１，２−ナフトキノンジアジドスルホン酸エステルとからなるポジ型フォトレジスト、水酸基を含むポリマー、アミノプラスト架橋剤、光酸発生剤からなる系で酸によって架橋してアルカリ溶解速度を下げるネガ型フォトレジスト、酸により分解してアルカリ溶解速度を上昇させる基を有するバインダーと光酸発生剤からなる化学増幅型フォトレジスト、酸により分解してフォトレジストのアルカリ溶解速度を上昇させる低分子化合物とアルカリ可溶性バインダーと光酸発生剤とからなる化学増幅型フォトレジスト、酸により分解してアルカリ溶解速度を上昇させる基を有するバインダーと酸により分解してフォトレジストのアルカリ溶解速度を上昇させる低分子化合物と光酸発生剤からなる化学増幅型フォトレジストなどがある。電子線又はＥＵＶ（極端紫外線）に感応するレジストを用いてもよい。 The photoresist solution is not particularly limited as long as it is exposed to light after exposure. Positive type photoresist consisting of novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, polymer containing hydroxyl group, aminoplast cross-linking agent, negative type to reduce alkali dissolution rate by crosslinking with acid in a system consisting of photo-acid generator Photoresist, chemically amplified photoresist consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, low molecular weight compound and alkali that decomposes with acid to increase the alkali dissolution rate of photoresist A chemically amplified photoresist consisting of a soluble binder and a photo-acid generator, a binder having a group that decomposes with an acid to increase the alkali dissolution rate, and a low molecular weight compound that decomposes with an acid to increase the alkali dissolution rate of a photoresist There is a chemically amplified photoresist made of a photoacid generator. You may use the resist sensitive to an electron beam or EUV (extreme ultraviolet).
フォトレジストパターンを形成する際、露光は所定のパターンを形成するためのフォトマスク（レチクル）を通して行われる。露光には、例えば、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、ＥＵＶ、電子線を使用することができる。露光後、必要に応じて露光後加熱（Ｐｏｓｔ Ｅｘｐｏｓｕｒｅ Ｂａｋｅ）が行われる。露光後加熱の条件としては、加熱温度８０℃乃至１５０℃、加熱時間０．３分乃至６０分間の中から適宜選択される。フォトレジスト膜が形成された半導体基板に、フォトマスクを通して露光を行い、その後アルカリ性現像液により現像する。 When forming a photoresist pattern, exposure is performed through a photomask (reticle) for forming a predetermined pattern. For the exposure, for example, KrF excimer laser, ArF excimer laser, EUV, or electron beam can be used. After the exposure, post exposure heating (Post Exposure Bake) is performed if necessary. The post-exposure heating conditions are appropriately selected from a heating temperature of 80° C. to 150° C. and a heating time 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.
アルカリ性現像液としては、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリンなどの水酸化四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミンなどのアミン水溶液等のアルカリ性水溶液を例として挙げることができる。さらに、これらの現像液に界面活性剤などを加えることもできる。 As the alkaline developer, an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline, ethanolamine, propylamine As an example, an alkaline aqueous solution such as an amine aqueous solution such as ethylenediamine can be given. Further, a surfactant or the like can be added to these developers.
現像の条件としては、現像温度５℃乃至５０℃、現像時間１０秒乃至３００秒から適宜選択される。本発明の単分子層又は多分子層形成用組成物から形成される単分子層又は多分子層は、フォトレジストの現像に汎用されている２．３８質量％の水酸化テトラメチルアンモニウム水溶液を用いて、室温で容易に現像を行うことができる。 The developing conditions are appropriately selected from a developing temperature of 5° C. to 50° C. and a developing time of 10 seconds to 300 seconds. As the monomolecular layer or the multimolecular layer formed from the composition for forming a monomolecular layer or the multimolecular layer of the present invention, a 2.38 mass% tetramethylammonium hydroxide aqueous solution which is generally used for developing a photoresist is used. Therefore, the development can be easily performed at room temperature.
ここで、以上説明した例では、本発明の単分子層又は多分子層形成用組成物を用いて形成された単分子層又は多分子層の上にレジスト層を設けたが、単分子層又は多分子層の上に、従来から公知のレジスト下層膜（又は保護膜）や保護膜を設け、その上にさらにレジスト層を設けてもよい。これにより、従来から公知のレジスト下層膜（又は保護膜）と基板との密着性を向上させ、また、耐過酸化水素水などの耐薬品性のための保護膜の耐薬品性をさらに向上させるなどの効果を発揮することができる。
上記レジスト層は、自体公知の方法にてパターン化され、そのレジスト層を介してレジスト下層膜（又は保護膜）をドライエッチングすることによりレジスト下層膜（又は保護膜）がパターン化され、該レジスト下層膜（又は保護膜）がウエットエッチングマスクとなり、該基板を半導体用ウエットエッチング液にて加工することができる。
なお、ここで、保護膜とは、特開２００９−０５３７０４号公報、ＷＯ２０１５／０３００６０号公報、ＷＯ２０１８／０５２１３０号公報、特願２０１７−２４６１４２、特願２０１７−２４６１４３、特願２０１８−１２１２８２、特願２０１８−２０６８６０などに記載された保護膜形成用組成物やレジスト下層形成用組成物を用いて形成されたものをいう。
Here, in the example described above, the resist layer was provided on the monomolecular layer or the polymolecular layer formed using the composition for forming a monomolecular layer or the polymolecular layer of the present invention, but the monomolecular layer or A conventionally known resist underlayer film (or protective film) or protective film may be provided on the polymolecular layer, and a resist layer may be further provided thereon. This improves the adhesion between the conventionally known resist underlayer film (or protective film) and the substrate, and further improves the chemical resistance of the protective film for chemical resistance such as hydrogen peroxide resistance. It is possible to exert effects such as.
The resist layer is patterned by a method known per se, and the resist underlayer film (or protective film) is patterned by dry-etching the resist underlayer film (or protective film) through the resist layer. The lower layer film (or protective film) serves as a wet etching mask, and the substrate can be processed with a wet etching solution for semiconductors.
Here, the protective film means Japanese Patent Application Laid-Open No. 2009-053704, WO2015/030060, WO2018/052130, Japanese Patent Application 2017-246142, Japanese Patent Application 2017-246143, Japanese Patent Application 2018-121282, Japanese Patent Application No. A composition formed using the protective film forming composition or the resist lower layer forming composition described in 2018-206860 and the like.
また、本発明の単分子層又は多分子層形成用組成物を用いて形成された単分子層又は多分子層の中の保護カテコール基は、上述したとおり、酸処理などにより、容易に脱保護できる、カテコール基とすることができ、表面の疎水性や耐薬品性や密着性を変更することができる。
ここで、脱保護のための酸としては、ｐ−トルエンスルホン酸（ｐＴＳＡ）やトリフルオロスルホン酸などを用いることができ、これよりも強酸を用いることもできる。
脱保護は、例えば、１〜５質量％程度のｐ−トルエンスルホン酸（ｐＴＳＡ）やトリフルオロスルホン酸溶液を噴霧又は塗布した後、１５０℃以上、好ましくは、１５０〜１８０℃でベークすることにより脱保護することができる。ベーク時間は、例えば、３０秒〜３００秒であるが、６０秒程度が好ましい。
In addition, the protected catechol group in the monomolecular layer or the polymolecular layer formed by using the composition for forming a monomolecular layer or the multimolecular layer of the present invention is easily deprotected by acid treatment or the like as described above. It can be a catechol group and can change the hydrophobicity, chemical resistance and adhesion of the surface.
Here, as the acid for deprotection, p-toluenesulfonic acid (pTSA), trifluorosulfonic acid, or the like can be used, and a stronger acid than this can also be used.
Deprotection is carried out, for example, by spraying or applying a p-toluenesulfonic acid (pTSA) or trifluorosulfonic acid solution of about 1 to 5% by mass and then baking at 150° C. or higher, preferably 150 to 180° C. Can be deprotected. The baking time is, for example, 30 seconds to 300 seconds, but is preferably about 60 seconds.
また、脱保護は、上述したような光酸発生剤含有レジストから発生する酸によっても可能である。すなわち、光酸発生剤レジストを単分子層又は多分子層上に設け、光照射してパターニングする際に、光照射領域のみに発生した酸を単分子層又は多分子層に作用させて脱保護する方法である。この場合、ポジ型レジストであれば、現像後、レジストが除去された領域のみの単分子層又は多分子層の保護カテコール基がカテコール基となる。これにより、所望の領域と他の領域との表面の特性を変化させることができる。
また、このような所望の領域のみをカテコール基とする方法としては、レジストなどのマスクを設けてマスクを設けていない領域のみに酸を作用させて脱保護する方法を用いることもできる。
Further, the deprotection can be performed by using the acid generated from the photoacid generator-containing resist as described above. That is, when a photoacid generator resist is provided on a monomolecular layer or a polymolecular layer and is irradiated with light for patterning, the acid generated only in the light-irradiated region is applied to the monomolecular layer or the polymolecular layer for deprotection. Is the way to do it. In this case, in the case of a positive type resist, after development, the protected catechol group of the monomolecular layer or the multimolecular layer only in the region where the resist is removed becomes the catechol group. As a result, the surface characteristics of the desired area and the other area can be changed.
Further, as a method of making only such a desired region a catechol group, a method of providing a mask such as a resist and allowing acid to act only on a region where no mask is provided to perform deprotection can also be used.
半導体用ウエットエッチング液としては、半導体用ウエハをエッチング加工するための一般的な薬液を使用することができ、例えば酸性を示す物質、塩基性を示す物質何れも使用することができる。
酸性を示す物質としては、例えば過酸化水素、フッ酸、フッ化アンモニウム、酸性フッ化アンモニウム、フッ化水素アンモニウム、バッファードフッ酸、塩酸、硝酸、硫酸、リン酸又はこれらの混合液が挙げられる。具体例としては、ＳＣ−２（塩酸−過酸化水素溶液）が挙げられる。
塩基性を示す物質としては、アンモニア、水酸化ナトリウム、水酸化カリウム、シアン化ナトリウム、シアン化カリウム、トリエタノールアミン等の有機アミンと過酸化水素水とを混合し、ｐＨを塩基性にした、塩基性過酸化水素水を挙げることができる。具体例としては、ＳＣ−１（アンモニア−過酸化水素溶液）が挙げられる。その他、ｐＨを塩基性にすることができるもの、例えば、尿素と過酸化水素水を混合し、加熱により尿素の熱分解を引き起こすことでアンモニアを発生させ、最終的にｐＨを塩基性にするものも、ウエットエッチングの薬液として使用できる。
As the wet etching liquid for semiconductors, a general chemical liquid for etching a semiconductor wafer can be used, and for example, both a substance showing acidity and a substance showing basicity can be used.
Examples of the substance exhibiting acidity include hydrogen peroxide, hydrofluoric acid, ammonium fluoride, ammonium acid fluoride, ammonium hydrogen fluoride, buffered hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or a mixed solution thereof. .. As a specific example, SC-2 (hydrochloric acid-hydrogen peroxide solution) can be mentioned.
Examples of the basic substance include ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, triethanolamine, and the like, which are mixed with an organic hydrogen peroxide solution to make the pH basic. Hydrogen peroxide water can be mentioned. A specific example is SC-1 (ammonia-hydrogen peroxide solution). Others that can make the pH basic, for example, by mixing urea and aqueous hydrogen peroxide and heating to cause thermal decomposition of urea to generate ammonia, and finally making the pH basic Can also be used as a chemical solution for wet etching.
これらの中でも、酸性過酸化水素水又は塩基性過酸化水素水であることが好まししい。
これらの薬液は、界面活性剤等の添加剤が含まれていてもよい。
半導体用ウエットエッチング液の使用温度は２５℃乃至９０℃であることが望ましく、４０℃乃至８０℃であることがさらに望ましい。ウエットエッチング時間としては、０．５分乃至３０分であることが望ましく、１分乃至２０分であることがさらに望ましい。
Among these, acidic hydrogen peroxide water or basic hydrogen peroxide water is preferable.
These chemicals may contain additives such as surfactants.
The use temperature of the wet etching solution for semiconductors is preferably 25° C. to 90° C., more preferably 40° C. to 80° C. The wet etching time is preferably 0.5 minutes to 30 minutes, more preferably 1 minute to 20 minutes.
以上、本発明の単分子層又は多分子層形成用組成物を用いて単分子層又は多分子層を形成する方法を説明したが、特に、パターン化された単分子層又は多分子層を有する基板を製造する方法の一例をまとめると、以下のようになる。
例えば、基板上に、本発明の単分子層又は多分子層形成用組成物を塗布し、ベークして単分子層又は多分子層を形成する第１工程と、前記単分子層又は多分子層の上に保護膜形成用組成物を塗布し、ベークして保護膜を形成する第２工程と、前記保護膜上にレジストパターンを形成する第３工程と、前記レジストパターンをマスクとして前記保護膜をドライエッチングして保護膜パターンを形成する第４工程と、ドライエッチング後の前記保護膜パターンをマスクとして、前記基板をウエットエッチングする第５工程と、を含むパターン化された基板の製造方法を挙げることができる。
ここで、パターン化された単分子層又は多分子層の中の保護カテコール基は、上述したとおり、酸処理などにより、容易に脱保護できる、カテコール基としてもよく、これにより、表面の疎水性や耐薬品性や密着性を変更することができる。
The method for forming a monolayer or a polylayer using the composition for forming a monolayer or a polylayer according to the present invention has been described above. In particular, the composition has a patterned monolayer or a polylayer. The following is a summary of an example of a method for manufacturing a substrate.
For example, the first step of applying the composition for forming a monomolecular layer or a multimolecular layer of the present invention onto a substrate and baking to form the monomolecular layer or the multimolecular layer; and the monomolecular layer or the multimolecular layer. A second step of applying a protective film forming composition on the protective film and baking to form a protective film; a third step of forming a resist pattern on the protective film; and the protective film using the resist pattern as a mask. And a fifth step of wet-etching the substrate using the protective film pattern after dry etching as a mask. Can be mentioned.
Here, as described above, the protected catechol group in the patterned monolayer or polylayer may be a catechol group that can be easily deprotected by an acid treatment or the like, whereby the hydrophobicity of the surface can be improved. The chemical resistance and adhesion can be changed.
また、基板上に、本発明の単分子層又は多分子層形成用組成物を塗布し、ベークして単分子層又は多分子層を形成する第１工程と、前記単分子層又は多分子層の上に光酸発生剤を含むレジストを用いてレジスト層を形成する第２工程と、前記レジスト層をパターン露光（フォトマスクを介して露光）してレジストパターンを形成する第３工程と、前記レジストパターンを除去する第４工程と、を含むパターン化された基板の製造方法を挙げることができる。
ここで、第３工程で露光された領域には光酸発生剤から酸が生じ、下層の単分子層又は多分子層に作用するので、その領域の単分子層又は多分子層の保護カテコール基は脱保護される。よって、この脱保護されたカテコール基を有する単分子層又は多分子層をそのまま利用するように用いてもよいし、第３工程の後、この領域の単分子層又は多分子層を除去して用いてもよい。
The first step of applying the composition for forming a monomolecular layer or a multimolecular layer of the present invention onto a substrate and baking to form the monomolecular layer or the multimolecular layer, and the monomolecular layer or the multimolecular layer A second step of forming a resist layer using a resist containing a photo-acid generator, and a third step of forming a resist pattern by pattern-exposing the resist layer (exposing through a photomask); A method of manufacturing a patterned substrate including a fourth step of removing the resist pattern can be mentioned.
Here, in the region exposed in the third step, an acid is generated from the photo-acid generator and acts on the lower monolayer or multilayer, and therefore the protective catechol group of the monolayer or multilayer in that region is generated. Is deprotected. Therefore, the monolayer or polylayer having the deprotected catechol group may be used as it is, or the monolayer or polylayer in this region may be removed after the third step. You may use.
以下、本発明に係る単分子層又は多分子層形成用組成物の具体例を説明するが、これによって本発明が限定されるものではない。 Hereinafter, specific examples of the composition for forming a monolayer or a multilayer according to the present invention will be described, but the present invention is not limited thereto.
（合成例１）
フラスコにサフロール（２４．１ｇ）、トリメトキシシラン（２０．０ｇ）、トルエン２２０ｍｌを入れ、Ａｒ置換後、Ｋａｒｓｔｅｄｔ触媒０．５ｍｌを添加し、３０℃で６時間反応させた。下記式に示す反応後、カラム精製し微黄色透明液体として化合物Ｃ−１（５．７ｇ）を得た。
(Synthesis example 1)
Safrole (24.1 g), trimethoxysilane (20.0 g) and 220 ml of toluene were placed in the flask, and after substitution with Ar, 0.5 ml of Karstedt's catalyst was added and reacted at 30° C. for 6 hours. After the reaction shown by the following formula, column purification was performed to obtain a compound C-1 (5.7 g) as a slightly yellow transparent liquid.
（実施例１）
化合物１（０．１ｇ）、酢酸（０．３ｇ）、水（０．３ｇ）をプロピレングリコールモノメチルエーテル（９．３ｇ）に溶解させた後、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、実施例１の単分子層又は多分子層形成用組成物を調製した。
(Example 1)
Compound 1 (0.1 g), acetic acid (0.3 g) and water (0.3 g) were dissolved in propylene glycol monomethyl ether (9.3 g) and then filtered using a polyethylene microfilter having a pore size of 0.03 μm. Then, the composition for forming a monomolecular layer or a multimolecular layer of Example 1 was prepared.
（実施例２）
化合物１を、下記式に示す化合物Ｃ−２（Ｅｎａｍｉｎｅ製）にした他は実施例１と同様に、実施例２の単分子層又は多分子層形成用組成物を得た。
(Example 2)
A composition for forming a monomolecular layer or a multimolecular layer of Example 2 was obtained in the same manner as in Example 1 except that the compound C-2 (manufactured by Enamine) represented by the following formula was used as the compound 1.
（光酸発生剤溶液）
ｉ線用光酸発生剤である、みどり化学社製ＰＡＩ１００１（０．１ｇ）をγ―ブチロラクトン９．９ｇに溶解させ、光酸発生剤溶液を調製した。
(Photo acid generator solution)
A PAI1001 (0.1 g) manufactured by Midori Kagaku Co., which is a photoacid generator for i-rays, was dissolved in 9.9 g of γ-butyrolactone to prepare a photoacid generator solution.
（単分子層又は多分子層の形成）
実施例１〜２で調製した単分子層又は多分子層形成用組成物を、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。実施例１及び実施例２の単分子層又は多分子層形成用組成物を用いて形成した単分子層又は多分子層をそれぞれ実施例１１及び実施例１２の単分子層又は多分子層とする。
(Formation of monolayer or multilayer)
The composition for forming a monomolecular layer or a multimolecular layer prepared in Examples 1 and 2 was applied on a silicon wafer using a spin coater, and baked on a hot plate at 100°C for 1 minute. Then, it was immersed 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 for 1 minute, spin-dried and then dried at 100° C. for 30 seconds. , A monolayer or a polylayer was formed on a silicon wafer. The monomolecular layer or the multimolecular layer formed by using the composition for forming a monomolecular layer or the multimolecular layer of Example 1 and Example 2 is referred to as the monomolecular layer or the polymolecular layer of Example 11 and Example 12, respectively. ..
（パターニング評価）
実施例１１及び実施例１２の単分子層又は多分子層の上に光酸発生剤溶液をスピンコーターにより塗布し、ホットプレート上で１００℃にて１分間加熱した。次いで、ｉ線露光装置（波長３６５ｎｍ）を用い、マスクを通して、露光を行った。その後、ホットプレート上１５０℃で１分間露光後加熱を行った。その後、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秒間乾燥させた。本作業により、実施例１１及び実施例１２の単分子層又は多分子層の光照射された露光部のみが酸により変性し、カテコールを発現させた。
実施例１１及び実施例１２の単分子層又は多分子層の塗布後（初期）と、パターニング後の露光部及び未露光部のＮＭＤ−３（水酸化テトラメチルアンモニウム（TMAH）２．３８質量％含有水溶液、東京応化工業（株）製）に対する接触角を測定した。結果を下記表１に示す。
(Patterning evaluation)
The photoacid generator solution was applied onto the monomolecular layer or the polymolecular layer of Example 11 and Example 12 by a spin coater, and heated on a hot plate at 100° C. for 1 minute. Then, using an i-line exposure device (wavelength 365 nm), exposure was performed through a mask. After that, post-exposure heating was performed on a hot plate at 150° C. for 1 minute. Then, it was immersed in OK73 thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute, spin-dried, and dried at 100° C. for 30 seconds. By this operation, only the light-exposed exposed portions of the monomolecular layer or the polymolecular layer of Example 11 and Example 12 were modified with acid to express catechol.
NMD-3 (tetramethylammonium hydroxide (TMAH) 2.38% by mass) after the application of the monomolecular layer or the multimolecular layer of Example 11 and Example 12 (initial stage) and in the exposed and unexposed areas after patterning. The contact angle with the contained aqueous solution, manufactured by Tokyo Ohka Kogyo Co., Ltd. was measured. The results are shown in Table 1 below.
（密着性試験（塩基性過酸化水素水耐性））
塩基性過酸化水素水への耐性評価として、実施例１１及び実施例１２と同様にしてシリコンウェハーに単分子層又は多分子層を形成した。その後、半導体用反射防止膜ＧＦ５２（日産化学（株）製）をシリコンウェハーに塗布し、２２０℃、１分間加熱することで、膜厚８０ｎｍとなるように成膜した。次に、２８％アンモニア水、３３％過酸化水素、水をそれぞれ重量比１対１対２となるように混合し、塩基性過酸化水素水を調製した。前記の保護膜形成組成物を塗布したシリコンウェハーを５０℃に加温したこの塩基性過酸化水素水中に浸漬し、浸漬直後から保護膜が基板から剥離するまでの時間を測定した。この結果を表２に示す。なお、処理なしとは、実施例１１及び実施例１２の単分子層又は多分子層を形成しないで、半導体用反射防止膜ＧＦ５２（日産化学（株）製）をシリコンウェハーに塗布した場合である。
(Adhesion test (basic hydrogen peroxide resistance))
For evaluation of resistance to basic hydrogen peroxide solution, a monomolecular layer or a multimolecular layer was formed on a silicon wafer in the same manner as in Example 11 and Example 12. After that, a semiconductor antireflection film GF52 (manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and heated at 220° C. for 1 minute to form a film having a thickness of 80 nm. Next, 28% ammonia water, 33% hydrogen peroxide, and water were mixed in a weight ratio of 1:1 to 2 to prepare a basic hydrogen peroxide solution. The silicon wafer coated with the above-mentioned protective film forming composition was immersed in this basic hydrogen peroxide water heated to 50° C., and the time immediately after the immersion until the protective film was peeled from the substrate was measured. The results are shown in Table 2. It should be noted that “without treatment” means that the antireflection film for semiconductor GF52 (manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer without forming the monomolecular layer or the multimolecular layer in Examples 11 and 12. ..
上記の結果から実施例１１〜１２の単分子層又は多分子層を設けた後、半導体用反射防止膜ＧＦ５２（日産化学製）をシリコンウェハーに塗布した場合には、単分子層又は多分子層を塗らないときと比較して、塩基性過酸化水素水に対して塗布膜が基板から剥離しにくいことが示された。 From the above results, when the antireflection film for semiconductor GF52 (manufactured by Nissan Kagaku Co., Ltd.) was applied to a silicon wafer after providing the monomolecular layer or the polymolecular layer of Examples 11 to 12, the monomolecular layer or the polymolecular layer was applied. It was shown that the coating film was less likely to be peeled from the substrate with respect to the basic hydrogen peroxide solution, as compared with the case where was not coated.
Claims (14)
前記単分子層又は多分子層にフォトマスクを介して露光する第２工程、
を含む、パターン化された単分子層又は多分子層を有する基板の製造方法。 A first step of applying the composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 4 on a substrate, and baking to form the monomolecular layer or the multimolecular layer,
A second step of exposing the monolayer or polylayer through a photomask;
A method of manufacturing a substrate having a patterned monolayer or multilayer comprising:
前記単分子層又は多分子層の上に保護膜形成用組成物を塗布し、ベークして保護膜を形成する第２工程と、
前記保護膜上にレジストパターンを形成する第３工程と、
前記レジストパターンを介して前記保護膜をドライエッチングして保護膜パターンを形成する第４工程と、
ドライエッチング後の前記保護膜パターンをウエットエッチングマスクとして、前記基板をウエットエッチングする第５工程と、
を含むパターン化された基板の製造方法。 A first step of applying the composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 4 on a substrate, and baking to form the monomolecular layer or the multimolecular layer,
A second step of applying a protective film-forming composition onto the monomolecular layer or the polymolecular layer and baking to form a protective film;
A third step of forming a resist pattern on the protective film,
A fourth step of forming a protective film pattern by dry etching the protective film through the resist pattern;
A fifth step of wet-etching the substrate using the protective film pattern after dry etching as a wet etching mask;
A method of manufacturing a patterned substrate including:
前記単分子層又は多分子層の上に光酸発生剤を含むレジストを用いてレジスト層を形成する第２工程と、
前記レジスト層にフォトマスクを介して露光してレジストパターンを形成する第３工程と、
前記レジストパターンを除去する第４工程と、
を含むパターン化された基板の製造方法。 A first step of applying the composition for forming a monomolecular layer or a multimolecular layer according to any one of claims 1 to 4 on a substrate, and baking to form the monomolecular layer or the multimolecular layer,
A second step of forming a resist layer using a resist containing a photoacid generator on the monolayer or polylayer,
A third step of forming a resist pattern by exposing the resist layer through a photomask,
A fourth step of removing the resist pattern,
A method of manufacturing a patterned substrate including:
An organosilicon compound represented by the following general formula (1).
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