WO2021131299A1 - 有機修飾金属酸化物ナノ粒子、その製造方法、euvフォトレジスト材料およびエッチングマスクの製造方法 - Google Patents
有機修飾金属酸化物ナノ粒子、その製造方法、euvフォトレジスト材料およびエッチングマスクの製造方法 Download PDFInfo
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- WO2021131299A1 WO2021131299A1 PCT/JP2020/040226 JP2020040226W WO2021131299A1 WO 2021131299 A1 WO2021131299 A1 WO 2021131299A1 JP 2020040226 W JP2020040226 W JP 2020040226W WO 2021131299 A1 WO2021131299 A1 WO 2021131299A1
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- metal oxide
- organically modified
- modifying group
- oxide nanoparticles
- modified metal
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- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 65
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 65
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000005530 etching Methods 0.000 title claims description 18
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 14
- 239000003446 ligand Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- -1 carboxylic acid carboxylate Chemical class 0.000 claims abstract description 29
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 150000001449 anionic compounds Chemical class 0.000 claims abstract description 9
- 229910001412 inorganic anion Inorganic materials 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical group [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical group [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 24
- 239000000843 powder Substances 0.000 description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 7
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 238000002296 dynamic light scattering Methods 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N Valeric acid Natural products CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UABDRQGIRJTVHT-UHFFFAOYSA-N butan-1-ol butan-1-olate zirconium(4+) Chemical compound [Zr+4].CCCCO.CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] UABDRQGIRJTVHT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 150000004696 coordination complex Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000010981 drying operation Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
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- C01G25/00—Compounds of zirconium
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- 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
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
Definitions
- the present invention relates to organically modified metal oxide nanoparticles that can be used in photoresist materials used in semiconductor manufacturing processes and the like, methods for producing the same, methods for producing EUV photoresist materials and etching masks.
- the present application claims priority based on Japanese Patent Application No. 2019-233067 filed in Japan on December 24, 2019, the contents of which are incorporated herein by reference.
- a method has been proposed in which nanoparticles of metal oxides such as zirconium and hafnium organically modified with an unsaturated carboxylic acid such as methacrylic acid are used as a negative resist material (Patent Documents 1 and 2). Since the nanoparticles of the metal oxide have the metal oxide as the core, the resist material containing the nanoparticles of the metal oxide has higher resistance to etching than the organic resist material, and further, methacrylic acid. It is characterized by high sensitivity to UV light due to its high reactivity. Further, since the structure of the nanoparticles of the metal oxide is highly symmetric, the nanoparticles of the metal oxide may remain as insoluble matter on the wafer when the resist material containing the nanoparticles of the metal oxide is developed. Low sex.
- metal oxides such as zirconium and hafnium organically modified with an unsaturated carboxylic acid such as methacrylic acid
- Patent Documents 3 to 5 a method of using a complex (monomer or salt) of a metal such as zirconium or hafnium and an organic substance represented by a carboxylic acid such as methacrylic acid as a resist material has also been proposed (Patent Documents 3 to 5). Since this resist material has a small size of the organic complex itself, it is suitable for thinning as compared with a resist material containing a nanoparticle core. However, this resist material has a higher proportion of organic substances in the formed film than the resist material having nanoparticles as the core. Therefore, this resist material has low resistance to etching. Further, since the structure of the organic complex is low in symmetry, there is a high possibility that the organic complex remains as an insoluble matter on the wafer when the resist material containing the organic complex is developed.
- organically modified metal oxide nanoparticles with the core diameter controlled to be as small as possible is important for the development of resist materials that form fine line patterns.
- organically modified metal oxide nanoparticles having a small core diameter are produced by mixing a metal alkoxide such as zirconium and an organic substance such as methacrylic acid in a non-aqueous solvent in an extremely low humidity environment.
- alkoxide is not cheap, and it is necessary to introduce and maintain expensive equipment such as a glove box in order to realize an extremely low humidity environment. Therefore, the organically modified metal oxide nanoparticles having a small core diameter have a problem in manufacturing cost.
- Unsaturated carboxylic acids such as methacrylic acid are easy to polymerize, so although they have high sensitivity, they are not always suitable because the stability after film formation is reduced when considering the entire process.
- unsaturated carboxylic acid is used as a ligand, volume shrinkage and local particle agglutination are likely to occur due to decarboxylation, polymerization, etc., resulting in variations in line width, resulting in a decrease in resolution.
- the resolution of the nanoparticles is maintained while maintaining the solubility of the nanoparticles in the resist solution. If the sensitivity can be adjusted, it will be possible to study more diverse resist material adjustment methods.
- the present invention has been made in view of such circumstances, and is an organically modified metal oxide nanoparticles that can be produced by a simple method and can increase the resolution and sensitivity of a resist material, a method for producing the same, and an EUV photoresist. It is an object of the present invention to provide a method for manufacturing a material and an etching mask.
- the reactivity that is, the sensitivity of the organically modified metal oxide nanoparticles composed of the metal oxide contained in the resist material and the ligand such as carboxylic acid was formed.
- the resolution of the resist pattern varies greatly depending on the type of ligand such as carboxylic acid that coordinates with the constituent elements of the nanoparticle core, the constituent elements and size, and the molecular weight.
- the first modifying group the present inventors have a saturated carboxylic acid having a high affinity (solubility) for a resist solution or a solvent for a developing solution, and as a second modifying group, a coordination having a smaller size (molecular weight) than the first modifying group.
- modifying groups such as children (for example, inorganic anions)
- individual organics are more densely formed during film formation while avoiding ligand polymerization during heat drying.
- modifying groups such as children (for example, inorganic anions)
- individual organics are more densely formed during film formation while avoiding ligand polymerization during heat drying.
- By forming a film filled with modified metal oxide nanoparticles it is possible to suppress variations caused by volume shrinkage and particle aggregation during EUV light irradiation, that is, structural distribution in the film, and the resolution of the resist film is improved. Found to do.
- the reactivity of the organically modified metal oxide nanoparticles during EUV light irradiation largely depends on the structure and type of the ligand.
- the present inventors have two or more types of modifying groups, and have high solubility of the nanoparticles required for the first modifying group in the resist solution and the solvent for the developing solution of the EUV non-irradiated part after EUV light irradiation.
- the composition of these ligands maintains high solubility and maintains low solubility in the solvent for the developing solution of the EUV irradiation part after EUV light irradiation while maintaining the interparticle distance closer with the second modifying group. It has been found that high sensitivity of the resist film to EUV light, in other words, low solubility of the EUV-irradiated portion in the developing solution after EUV light irradiation can be exhibited by appropriately controlling.
- the organically modified metal oxide nanoparticles of the present invention are a core having a plurality of metals and a plurality of oxygens bonded to the plurality of metals, and a saturated carboxylic acid carboxylate ligand coordinated to the core.
- a first modifying group and a second modifying group that is a core-coordinated inorganic anion that is smaller in size than the first modifying group and / or a saturated carboxylic acid carboxylate ligand that is smaller in molecular weight than the first modifying group.
- the EUV photoresist material of the present invention contains the organically modified metal oxide nanoparticles of the present invention and a solvent.
- the method for producing organically modified metal oxide nanoparticles of the present invention includes a reaction step of reacting a metal oxynitrate and / or a metal oxyacetate with a saturated carboxylic acid in a hydrophilic liquid.
- the method for producing an etching mask of the present invention includes a film forming step of applying the UV photoresist material of the present invention on a layer to be etched and drying it to obtain a resist film, and an exposure of irradiating the resist film with EUV in a predetermined pattern. It has a step and a developing step of removing a portion not irradiated with EUV in the exposure step to form an etching opening.
- the method for producing organically modified metal oxide nanoparticles, and the EUV photoresist material of the present invention a resist material that can be produced by a simple method and has high resolution and sensitivity can be obtained. Further, according to the method for manufacturing an etching mask of the present invention, the mask can be thinned.
- FIG. 1 is an SEM image of the silicon wafer obtained in Example 1.
- FIG. 2 is an SEM image of the silicon wafer obtained in Comparative Example 1.
- FIG. 3 is a schematic view showing changes in the state of the organically modified metal oxide nanoparticles during film formation, heat drying, and EUV exposure of Example 1.
- FIG. 4 is a schematic view showing changes in the state of the organically modified metal oxide nanoparticles during film formation, heat drying, and EUV exposure of Comparative Example 1.
- the organically modified metal oxide nanoparticles according to the embodiment of the present invention include a core, a first modifying group, and a second modifying group.
- the core has a plurality of metals and a plurality of oxygens bonded to the plurality of metals.
- the core contains metal oxides.
- the core can contain clusters of structures in which multiple metals are crosslinked with multiple oxygens.
- the core is preferably composed of clusters.
- Metal oxide crystals and metal oxide clusters are common in that they are a combination of metal and oxygen, but metal oxide crystals are constant in that individual particles are arranged in a three-dimensionally regular manner by themselves.
- the crystal structure is formed with the size of (for example, 3 nm to 4 nm), while the metal oxide cluster is a molecule in which each particle has a metal complex structure and the individual particles themselves do not have a crystal structure. different.
- the plurality of metals may be composed of the same type or different types.
- the first modifying group is a saturated carboxylic acid carboxylate ligand coordinated to the core.
- the second modifying group is an inorganic anion that coordinates to the core and is smaller in size than the first modifying group and / or a saturated carboxylic acid carboxylate ligand that has a lower molecular weight than the first modifying group.
- the organically modified metal oxide nanoparticles are easily soluble in propylene glycol 1-monomethyl ether 2-acetylate (PGMEA), which is a solvent for a general-purpose resist solution, and the reaction of the organically modified metal oxide nanoparticles when irradiated with EUV light.
- the first modifying group is preferably a saturated carboxylic acid carboxylate ligand having 3 or more carbon atoms, and more preferably an isobutyric acid carboxylate ligand.
- the metal is preferably one or more selected from Zr (zirconium), Hf (hafnium), and Ti (titanium), and more preferably Zr.
- the second modifying group is preferably a nitrate ion and / or a carboxylate acetate ligand.
- the first modifying group is not limited to the isobutyric acid carboxylate ligand, but other saturated carboxylic acid carboxylate coordinations such as butyric acid carboxylate ligand, valeric acid carboxylate ligand, and caproic acid carboxylate ligand. It may be a child.
- the second modifying group is an inorganic anion having a size smaller than that of the first modifying group
- the second modifying group is not limited to nitrate ion, but other inorganic anions such as chloride ion and hydroxide ion. It may be an ion.
- the second modifying group is a saturated carboxylic acid carboxylate ligand having a molecular weight smaller than that of the first modifying group
- the second modifying group is not limited to the acetate carboxylate ligand, but the formate carboxylate ligand, It may be another saturated carboxylic acid carboxylate ligand such as a propionic acid carboxylate ligand.
- the organically modified metal oxide nanoparticles of the present embodiment are represented by the general formula M 6 O 4 (OH) 4 X n Y 12-n , and preferably have a structure in which the metal is crosslinked with oxygen in the core.
- M is a metal, which is one or more selected from Zr, Hf, and Ti
- X is a first modifying group
- Y is a second modifying group
- it represents the ratio of X and Y, and it is preferable that Z defined by X / (X + Y) ⁇ 100 satisfies the relationship of 5 mL% ⁇ Z ⁇ 95 mL%.
- the size of the isobutyric acid carboxylate ligand, which is an example of the first modifying group, is about 0.53 nm
- the size of the nitrate ion, which is an example of the second modifying group is about 0.33 nm.
- the size of each of the first modifying group and the second modifying group can be obtained from the distance between the atoms at both ends by preparing the molecule with, for example, 3D molecular model drawing software. By comparing the above values, it can be confirmed that the size of the inorganic anion which is the second modifying group is smaller than the size of the carboxylic acid carboxylate ligand which is the first modifying group.
- the EUV photoresist material according to the embodiment of the present invention contains the organically modified metal oxide nanoparticles of the present embodiment and a solvent.
- the solvent include butyl acetate, PGMEA, methanol, ethanol, propanol and the like.
- the EUV photoresist material of the present embodiment may further contain a dispersant such as a carboxylic acid, a stabilizer, a photoresponsive agent such as a photoacid generator, and the like.
- the method for producing organically modified metal oxide nanoparticles includes a reaction step of reacting a metal oxynitrate and / or a metal oxyacetate with a saturated carboxylic acid in a hydrophilic liquid.
- the saturated carboxylic acid is preferably isobutyric acid.
- other saturated carboxylic acids such as butyric acid, valeric acid and caproic acid may be used.
- the hydrophilic liquid include water, methanol, ethanol, propanol, acetone and the like.
- the organically modified metal oxide nanoparticles of the present embodiment can be obtained by a simple method.
- the organically modified metal oxide nanoparticles preferably satisfy the relationship of 50 mL% ⁇ Z ⁇ 90 mL. Further, it is preferable that the metal oxynitrate is zirconium oxynitrate.
- the organically modified metal oxide nanoparticles of the present embodiment can be obtained by a simple method.
- the organically modified metal oxide nanoparticles preferably satisfy the relationship of 50 mL% ⁇ Z ⁇ 90 mL. Further, it is preferable that the metal oxyacetate is zirconium oxyacetate.
- the method for manufacturing an etching mask according to the embodiment of the present invention includes a film forming step, an exposure step, and a developing step.
- the EUV photoresist material of the present embodiment is applied onto the layer to be etched and dried to obtain a resist film.
- the type of the layer to be etched is not particularly limited. Examples of the layer to be etched include a silicon layer, a silicon oxide layer, and a silicon nitride layer.
- the resist film is irradiated with EUV light in a predetermined pattern.
- the portion not irradiated with EUV light in the exposure step is removed to form an etching opening.
- the resist film is immersed in a developing solution such as butyl acetate, and the portion not irradiated with EUV light is dissolved in the developing solution and removed.
- the line width of the etching mask can be reduced to, for example, 20 nm or less. Therefore, the mask can be thinned, and the layer to be etched can be finely etched.
- Example 1 An aqueous solution of zirconium oxynitrate was prepared by dissolving 1.2 g of zirconium oxynitrate in 3 mL of a 5 M aqueous nitric acid solution. 1 mL of isobutyric acid was added to 2 mL of this zirconium oxynitrate aqueous solution, and the mixture was stirred for 5 minutes and then allowed to stand at room temperature for 5 days. The obtained product was separated and recovered, and vacuum dried at room temperature for 1 day to obtain a white powder.
- this white powder was dissolved in 5.0 g of PGMEA.
- the undissolved white powder was removed using centrifugation and a filter with a pore size of 0.2 ⁇ m.
- the volume-based average particle size of this white powder was about 2 nm. .. From this result, it was confirmed that the obtained white powder was organically modified metal oxide nanoparticles in which isobutyric acid and nitric acid were coordinated with respect to the core composed of zirconium and oxygen.
- the core is not a metal oxide crystal, but zirconium is oxygen. It was confirmed that it was a bridged cluster.
- the ratio of the residue (ZrO 2) after the analysis was 48%.
- the white powder is, ZrO 2 conversion content a 46%, a cluster Zr 6 O of zirconium crosslinked with oxygen structure 4 ( It was confirmed that OH) 4 (C 4 H 7 O 2 ) 7.9 (NO 3 ) 4.1.
- This EUV exposure solution A was dropped onto a silicon wafer and rotated at 1500 rpm for 60 seconds to form a film, and then heated at 80 ° C. for 60 seconds to obtain a resist film A.
- the film thickness of the resist film A was measured with a spectroscopic ellipsometer (manufactured by Horiba Joban Yvon, apparatus name "UVISEL”) and found to be about 20 nm.
- FIG. 1 shows an SEM image of the developed silicon wafer after EUV exposure at an irradiation amount of 70 mJ / cm 2.
- the line width of the insolubilized resist film A (light-colored portion), which is an etching mask remaining on the silicon wafer (dark-colored portion), is 19 nm, which is a resist as compared with Comparative Example 1 described later.
- the line width of the film A was narrow, the variation in the line width was small, and the formation of nano-patterning with high resolution was confirmed.
- this white powder was dissolved in 3.0 g of PGMEA.
- the undissolved white powder was removed using centrifugation and a filter with a pore size of 0.45 ⁇ m.
- the volume-based average particle size of this white powder was about 2 nm. From this result, it was confirmed that the obtained white powder was organically modified metal oxide nanoparticles in which methacrylic acid was coordinated with respect to the core composed of zirconium and oxygen.
- PGMEA was further added to this solution and diluted double to obtain EUV exposure solution B.
- the EUV exposure solution B was dropped onto the silicon wafer and rotated at 1500 rpm for 60 seconds to form a film, and then heated at 80 ° C. for 60 seconds to obtain a resist film B. When the film thickness of the resist film B was measured with a spectroscopic ellipsometer, it was about 20 nm.
- FIG. 2 shows an SEM image of the developed silicon wafer after EUV exposure at an irradiation amount of 46 mJ / cm 2.
- the line width of the insolubilized resist film B (light-colored portion), which is an etching mask remaining on the silicon wafer (dark-colored portion), was 21 nm, and a large variation was observed in the line width. ..
- FIG. 3 is a schematic view showing changes in the state of the organically modified metal oxide nanoparticles during film formation, heat drying, and EUV exposure of Example 1.
- organically modified metal oxide nanoparticles in which isobutyric acid as the first modifying group and nitric acid as the second modifying group were coordinated with respect to the core composed of zirconium and oxygen were obtained.
- isobutyric acid which is a saturated carboxylic acid
- nitric acid which is an inorganic anion
- the polymerization of the ligand is unlikely to occur during heating and drying for removing the solvent contained in the resist solution after the film formation, and during the subsequent EUV exposure, particle aggregation or the like when the ligand is decomposed occurs. It is presumed that the particle filling structure in the membrane is less disturbed due to this. Therefore, it is considered that a nano pattern having high resolution was formed.
- isobutyric acid which is the first modifying group, is highly soluble in the resist solution of the organically modified metal oxide nanoparticles in the EUV exposure solution A and highly soluble in butyl acetate in the EUV non-irradiated portion after EUV exposure. Contribute to sex.
- nitrate which is a second modifying group, contributes to maintaining a dense particle-filled structure of nanoparticles by keeping the interparticle distance between adjacent organically modified metal oxide nanoparticles small, and in addition, EUV after EUV exposure. It is presumed that it contributes to the low solubility of the irradiated part in butyl acetate.
- FIG. 4 is a schematic view showing changes in the state of the organically modified metal oxide nanoparticles during film formation, heat drying, and EUV exposure of Comparative Example 1.
- Comparative Example 1 it is considered that organically modified metal oxide nanoparticles in which methacrylic acid was coordinated with respect to the core composed of zirconium and oxygen were obtained.
- methacrylic acid which is an unsaturated carboxylic acid, is coordinated to the core. Therefore, when the resist film B is formed, the organically modified metal oxide nanoparticles are compared with Example 1. It is sparsely filled.
- volume shrinkage and particle agglomeration proceeded due to polymerization of methacrylic acid during heat drying after film formation and decomposition during EUV exposure, resulting in variations in the particle packing structure in the film.
- a nano pattern having a low resolution was formed.
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Abstract
Description
本願は、2019年12月24日に、日本に出願された特願2019-233067号に基づき優先権を主張し、その内容をここに援用する。
また、一方で、成膜後にはレジスト液に含まれていた溶媒除去のために加熱乾燥操作を必要とする。メタクリル酸等の不飽和カルボン酸は重合しやすいため、感度は高いものの全体のプロセスを考えた場合、成膜後の安定性が低下することから、必ずしも適しているとは言えない。一種類の不飽和カルボン酸のみを配位子とした場合、脱炭酸や重合などにより体積収縮、局所的な粒子凝集が起こりやすいため、線幅にばらつきを生じ、結果として解像度の低下を招く。材料自体の構造制御、より具体的には、不飽和結合を持たないカルボン酸を含む複数の配位子による修飾とその組成制御によって、レジスト液へのナノ粒子の溶解性を維持しつつ、解像度と感度の調整が達成できれば、より多角的なレジスト材料の調整方法の検討が可能となる。
また、第二修飾基が、第一修飾基よりサイズが小さい無機陰イオンである場合、当該第二修飾基は、硝酸イオンに限らず、塩化物イオン、水酸化物イオン等の他の無機陰イオンであってもよい。第二修飾基が、第一修飾基より分子量が小さい飽和カルボン酸カルボキシレート配位子である場合、当該第二修飾基は、酢酸カルボキシレート配位子に限らず、ギ酸カルボキシレート配位子、プロピオン酸カルボキシレート配位子等の他の飽和カルボン酸カルボキシレート配位子であってもよい。
5M硝酸水溶液3mLにオキシ硝酸ジルコニウム1.2gを溶解させて、オキシ硝酸ジルコニウム水溶液を調製した。このオキシ硝酸ジルコニウム水溶液2mLにイソ酪酸1mLを加えて、5分間攪拌した後、室温で5日間静置した。得られた生成物を分離回収し、室温で1日真空乾燥して白色粉末を得た。この白色粉末の元素分析(パーキンエルマー社製、装置名「全自動元素分析装置 2400II」)の結果、炭素および窒素の含有量はそれぞれ23.0wt%および3.3wt%であり、物質量比(いわゆるmol比)では、イソ酪酸:硝酸=66:34≒7.9:4.1であった。この白色粉末の熱重量分析(リガク社製、装置名「示差熱天秤 Thermo plus EVO2」)の結果、重量減少率は52%であった。さらに、この白色粉末のIR分析(日本分光社製、装置名「フーリエ変換赤外分光光度計 FT/IR-4600」)の結果、イソ酪酸のカルボキシ基由来の吸収ピーク(1530cm-1および1430cm-1)が確認できた。
グローブボックス内で、85%ジルコニウムブトキシド1-ブタノール溶液1.40gにメタクリル酸1.02gを加えて攪拌し、約3週間静置してZr6O4(OH)4(MAA)12の単結晶を得た。この単結晶を減圧濾過により回収し、室温で1日真空乾燥し、粉砕して白色粉末を得た。この白色粉末の元素分析の結果、炭素含有量は36wt%であった。この白色粉末の熱重量分析の結果、重量減少率は57%であった。
Claims (10)
- 複数個の金属と、前記複数個の金属に結合した複数の酸素とを備えるコアと、
前記コアに配位している飽和カルボン酸カルボキシレート配位子である第一修飾基と、
前記コアに配位し、前記第一修飾基よりサイズが小さい無機陰イオンおよび/または前記第一修飾基より分子量が小さい飽和カルボン酸カルボキシレート配位子である第二修飾基と、
を有する有機修飾金属酸化物ナノ粒子。 - 前記第一修飾基が、炭素数3以上の飽和カルボン酸カルボキシレート配位子であり、
前記第二修飾基が、硝酸イオンおよび/または酢酸カルボキシレート配位子である、請求項1に記載の有機修飾金属酸化物ナノ粒子。 - 一般式M6O4(OH)4XnY12-nで表され、金属が酸素で架橋された構造をコアに持つ、請求項1または2に記載の有機修飾金属酸化物ナノ粒子。
(ただし、Mは前記金属であって、Zr、Hf、およびTiから選択される一種以上であり、Xは前記第一修飾基で、Yは前記第二修飾基で、1≦n≦11である。) - 前記金属がZrである、請求項1から3のいずれか1項に記載の有機修飾金属酸化物ナノ粒子。
- 請求項1から4のいずれか1項に記載の有機修飾金属酸化物ナノ粒子と、溶媒とを含有するEUVフォトレジスト材料。
- オキシ硝酸金属および/またはオキシ酢酸金属と飽和カルボン酸を、親水性液体中で反応させる反応工程を有する、有機修飾金属酸化物ナノ粒子の製造方法。
- 前記飽和カルボン酸が、イソ酪酸であり、
前記反応工程は、オキシ硝酸金属および/またはオキシ酢酸金属とイソ酪酸とを、親水性液体中で反応させる、請求項6に記載の有機修飾金属酸化物ナノ粒子の製造方法。 - 前記反応工程が大気雰囲気下で行われる、請求項7に記載の有機修飾金属酸化物ナノ粒子の製造方法。
- 前記オキシ硝酸金属がオキシ硝酸ジルコニウムであり、前記オキシ酢酸金属がオキシ酢酸ジルコニウムである、請求項6または7に記載の有機修飾金属酸化物ナノ粒子の製造方法。
- 被エッチング層上に請求項5に記載のEUVフォトレジスト材料を塗布し、乾燥させてレジスト膜を得る成膜工程と、
前記レジスト膜に所定のパターンでEUV光を照射する露光工程と、
前記露光工程でEUV光を照射していない部分を除去してエッチング開口部を形成する現像工程と、
を有するエッチングマスクの製造方法。
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