WO2015118774A1 - 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、感活性光線性又は感放射線性膜を備えたマスクブランクス、フォトマスク、パターン形成方法、電子デバイスの製造方法、及び、電子デバイス - Google Patents
感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、感活性光線性又は感放射線性膜を備えたマスクブランクス、フォトマスク、パターン形成方法、電子デバイスの製造方法、及び、電子デバイス Download PDFInfo
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- WO2015118774A1 WO2015118774A1 PCT/JP2014/082855 JP2014082855W WO2015118774A1 WO 2015118774 A1 WO2015118774 A1 WO 2015118774A1 JP 2014082855 W JP2014082855 W JP 2014082855W WO 2015118774 A1 WO2015118774 A1 WO 2015118774A1
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- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical group N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 125000004621 quinuclidinyl group Chemical group N12C(CC(CC1)CC2)* 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical group CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
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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
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- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
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- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
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- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
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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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
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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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
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- G03F1/78—Patterning of masks by imaging by charged particle beam [CPB], e.g. electron beam patterning of masks
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2059—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2059—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam
- G03F7/2063—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam for the production of exposure masks or reticles
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- G—PHYSICS
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
Definitions
- the present invention is suitable for use in ultra-microlithography processes such as the manufacture of VLSI and high-capacity microchips and other fabrication processes, and is capable of forming a highly detailed pattern using electron beams or extreme ultraviolet rays.
- the present invention relates to a production method, an electronic device, a novel compound, and a production method of the novel compound.
- the present invention particularly relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a process using a substrate having a specific undercoat film, an actinic ray-sensitive or radiation-sensitive film using the same, and an activity-sensitive film.
- the present invention relates to a mask blank provided with a light-sensitive or radiation-sensitive film, a photomask, a pattern forming method, an electronic device manufacturing method, an electronic device, a novel compound, and a novel compound manufacturing method.
- Patent Documents 1 and 2 disclose additives suitable for lithography technology.
- a so-called negative chemically amplified resist composition mainly comprising an alkali-soluble resin, a crosslinking agent, and an acid generator is effectively used (for example, Patent Document 3- 6).
- JP 2008-273844 A Japanese Patent Laid-Open No. 2000-1448 JP 2011-35173 A JP 2008-268935 A JP 2013-44808 A JP 2002-99085 A
- An object of the present invention is to provide an activity-sensitive material capable of forming an ultrafine pattern (for example, a line width of 50 nm or less) excellent in resolution, roughness characteristics, in-plane uniformity (CDU) of pattern line width and etching resistance.
- the present invention is as follows. [1] Actinic ray-sensitive or radiation-sensitive containing an alkali-soluble resin (A) having a phenolic hydroxyl group and a crosslinking agent (C) having a total of two or more hydroxymethyl groups or alkoxymethyl groups in the molecule.
- A alkali-soluble resin
- C crosslinking agent
- a resin composition wherein the crosslinking agent (C) includes the crosslinking agent (C1), has a molecular weight of 420 or more, and has 2 to 4 hydroxymethyl groups or alkoxymethyl groups in the molecule,
- the content of the crosslinking agent (C1) is 60 mol% to 100 mol% with respect to the total amount of the crosslinking agent (C), and the total concentration of hydroxymethyl groups or alkoxymethyl groups of the crosslinking agent (C) is
- the actinic ray-sensitive or radiation-sensitive resin composition is 0.30 mmol / g or more with respect to 1 g of the solid content in the actinic ray-sensitive or radiation-sensitive resin composition.
- R 1 each independently represents a hydrogen atom, an alkyl group, an aryl group, a hydroxymethyl group, alkoxymethyl group, or a group represented by -CH 2 -O-R 11, R 11 is an aryl group or an acyl Represents a group. However, in the whole molecule, 2 or more and 4 or less R 1 is a hydroxymethyl group or an alkoxymethyl group.
- R 2 represents a hydrogen atom, an alkyl group, an aryl group, or a group represented by —CO—A
- A represents an alkyl group, an alkoxy group, N (R 22 ) 2
- R 22 represents the number of carbon atoms. 4 or less alkyl groups are represented.
- R 2 independently represents a hydrogen atom, an alkyl group, an aryl group, or a group represented by —CO—A when n is 2 or more.
- Z 1 represents a hydrogen atom when n is 1, and represents a linking group or a single bond when n is 2 or more.
- n represents an integer of 1 to 4.
- X 1 and X 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxymethyl group or an alkoxymethyl group. However, at least one of the two X 1 is a hydroxymethyl group or an alkoxymethyl group.
- Y 1 represents a carbon atom, a nitrogen atom or an oxygen atom when both X 1 are a hydroxymethyl group or an alkoxymethyl group, and when one X 1 is neither a hydroxymethyl group nor an alkoxymethyl group, Y 1 1 is a nitrogen atom, and X 2 is a hydroxymethyl group or an alkoxymethyl group.
- Y 2 represents a single bond, an alkylene group or a cycloalkylene group.
- Z 2 represents an organic group.
- R 1 each independently represents a hydrogen atom, an alkyl group, an aryl group, a hydroxymethyl group, alkoxymethyl group, or a group represented by -CH 2 -O-R 11, R 11 is an aryl group or an acyl Represents a group. However, in the whole molecule, two or more R 1 are a hydroxymethyl group or an alkoxymethyl group.
- Z b represents an atomic group necessary for forming a ring together with the carbon atom in the general formula (Ib), and this ring may have a substituent.
- Each R independently represents an alkyl group or a cycloalkyl group.
- R 1c independently represents an alkyl group.
- Z c represents an atomic group necessary for forming a ring together with the carbon atom in the formula, and this ring may have a substituent.
- A represents a sulfur atom or an iodine atom
- R 1 represents a hydrogen atom or an organic group, and when a plurality of R 1 are present, R 1 may be the same or different
- R represents an (o + 1) -valent organic group, and when there are a plurality of R, R may be the same or different
- X represents a single bond or a linking group, and when a plurality of Xs are present, Xs may be the same or different
- a N contained nitrogen atom represent a basic moiety, if A N there are multiple, A N may be the same or different and
- n is an integer of 1 to 3
- o represents an integer of 1 to 10
- Y ⁇ represents an anion, R 1,
- actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], further comprising a compound that generates an acid upon irradiation with actinic rays or radiation.
- a photo produced by a method comprising exposing the actinic ray-sensitive or radiation-sensitive film included in the mask blank according to [9], and developing the exposed actinic-ray-sensitive or radiation-sensitive film. mask.
- a pattern forming method comprising: exposing the film; and developing the exposed film with a developer to form a pattern.
- a method for manufacturing an electronic device including the pattern forming method according to [11] or [12].
- actinic ray sensitivity capable of forming an ultrafine pattern (for example, a line width of 50 nm or less) excellent in resolution, roughness characteristics, in-plane uniformity (CDU) of pattern line width and etching resistance.
- the notation that does not indicate substitution and non-substitution includes not only a substituent but also a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- active light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), and the like.
- light means actinic rays or radiation.
- exposure here means not only exposure by far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in exposure. Hereinafter, embodiments of the present invention will be described in detail.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises an alkali-soluble resin having a phenolic hydroxyl group described later, a molecular weight of 420 or more, and a total of 2 to 2 hydroxymethyl groups or alkoxymethyl groups in the molecule.
- Contains four cross-linking agents hereinafter also referred to as “cross-linking agent (C1)”.
- the composition of the present invention contains the crosslinking agent (C1) in a proportion of 60 mol% to 100 mol% with respect to the total amount of the crosslinking agent (C) contained in the composition of the present invention.
- the total concentration of hydroxymethyl groups or alkoxymethyl groups possessed by C) is 0.30 mmol / g or more with respect to 1 g of the solid content in the composition of the present invention.
- the “crosslinking agent (C)” means a crosslinking agent having a total of two or more hydroxymethyl groups or alkoxymethyl groups in the molecule, and includes the crosslinking agent (C1) of the present invention.
- the composition of the present invention contains the crosslinking agent (C1) of the present invention in the above-described proportion, whereby the resolution, roughness characteristics, and pattern in an ultrafine pattern having a line width of 50 nm or less are obtained. It has been found that line width in-plane uniformity (CDU) and etch resistance are improved. The reason for this is not necessarily clear, but the cross-linking agent (C1) of the present invention having 2 to 4 cross-linking groups is blended at a specific ratio to form a uniform cross-linked film. It is presumed that the light-sensitive or radiation-sensitive film has low swellability, and resolution, roughness characteristics, CDU, and etching resistance are improved. In addition, the crosslinking agent (C1) of the present invention has a molecular weight of 420 or more, and suppression of volatilization is presumed to contribute to further improvement of CDU.
- the crosslinking agent (C1) is a compound having a molecular weight of 420 or more and a total of 2 to 4 hydroxymethyl groups or alkoxymethyl groups in the molecule.
- the number of hydroxymethyl groups or alkoxymethyl groups in the crosslinking agent (C1) is preferably two, and the hydroxymethyl group or alkoxymethyl group is an aromatic ring or a hetero atom. Bonding is preferred.
- the molecular weight of the crosslinking agent (C1) is preferably 420 to 1000, more preferably 430 to 800, and further preferably 440 to 600.
- the crosslinking agent (C1) is preferably a compound represented by the following general formula (I).
- R 1 each independently represents a hydrogen atom, an alkyl group, an aryl group, a hydroxymethyl group, alkoxymethyl group, or a group represented by -CH 2 -O-R 11, R 11 is an aryl group or an acyl Represents a group. However, in the whole molecule, 2 or more and 4 or less R 1 is a hydroxymethyl group or an alkoxymethyl group.
- R 2 represents a hydrogen atom, an alkyl group, an aryl group, or a group represented by —CO—A
- A represents an alkyl group, an alkoxy group, N (R 22 ) 2
- R 22 represents the number of carbon atoms. 4 or less alkyl groups are represented.
- R 2 independently represents a hydrogen atom, an alkyl group, an aryl group, or a group represented by —CO—A when n is 2 or more.
- Z 1 represents a hydrogen atom when n is 1, and represents a linking group or a single bond when n is 2 or more.
- n represents an integer of 1 to 4.
- R 1 of 4 or less is a hydroxymethyl group or an alkoxymethyl group.
- R 1 contained in the whole molecule two or three R 1 are preferably a hydroxymethyl group or an alkoxymethyl group, and two R 1 are a hydroxymethyl group or More preferably, it is an alkoxymethyl group. More preferably, two hydroxymethyl groups or alkoxymethyl groups represented by R 1 are substituted with different benzene rings.
- the alkyl moiety in the alkoxymethyl group is preferably an alkyl group having 6 or less carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, A neopentyl group, a hexyl group, etc. are mentioned.
- the alkyl group represented by R 1 is, for example, preferably an alkyl group having 1 to 5 carbon atoms, and the aryl group is preferably, for example, an aryl group having 6 to 18 carbon atoms.
- the aryl group represented by R 11 for example, preferably an aryl group having 6 to 18 carbon atoms
- the acyl group e.g., the alkyl moiety having a carbon number Acyl groups that are 1 to 6 alkyl groups are preferred.
- R 1 other than a hydroxymethyl group and an alkoxymethyl group is preferably an alkyl group or an aryl group.
- alkyl group represented by R 2 for example, an alkyl group having 1 to 6 carbon atoms is preferable, and as the aryl group, for example, an aryl group having 6 to 18 carbon atoms is preferable.
- the alkyl group represented by A in —CO—A as R 2 is preferably an alkyl group having 1 to 6 carbon atoms, and the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. In one embodiment of the present invention, A preferably has 6 or less carbon atoms.
- R 2 is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
- n is preferably an integer of 2 to 4, and more preferably 2.
- Z 1 represents a hydrogen atom when n is 1, and represents a linking group when n is 2 or more.
- Z 1 is preferably a divalent to tetravalent linking group, and more preferably a divalent linking group.
- the linking group represented by Z 1 is not particularly limited. For example, specific examples in the case where Z 1 is a divalent linking group include an alkylene group, an arylene group, or a group in which two or more of these are combined. These linking groups may further have a substituent.
- Z 1 is a divalent linking group
- R 3 and R 4 are the same as R 3 and R 4 in formula (I-B) to be described later. * Represents a binding site with the benzene ring which is the remainder of the general formula (I).
- the crosslinking agent (C1) is preferably a compound represented by the following general formula (IB).
- R 1 has the same meaning as R 1 in the general formula (I).
- R 3 and R 4 each independently represents a hydrogen atom or an organic group. R 3 and R 4 may combine with each other to form a ring.
- At least one of the organic groups represented by R 3 and R 4 is preferably an organic group having 2 or more carbon atoms, and more preferably both are organic groups having 2 or more carbon atoms.
- Examples of the organic group represented by R 3 and R 4 include an alkyl group, a cycloalkyl group, an aryl group, and the like, and R 3 and R 4 are bonded to each other to be described in detail below. It is preferable to form a ring.
- Examples of the ring formed by combining R 3 and R 4 with each other include, for example, an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a combination of two or more of these rings
- the polycyclic fused ring formed can be mentioned.
- These rings may have a substituent.
- substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, an acyl group, and an alkoxycarbonyl group. , A nitro group, a halogen, or a hydroxy group.
- R 3 and R 4 in the general formula (IB) are preferably bonded to form a polycyclic condensed ring including a benzene ring, and a fluorene structure is formed. Is more preferable.
- R 3 and R 4 in the general formula (IB) are preferably bonded to form a fluorene structure represented by the following general formula (Id). .
- R 7 and R 8 each independently represents a substituent.
- substituents include an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, an acyl group, an alkoxycarbonyl group, a nitro group, a halogen atom, and a hydroxy group.
- N1 and n2 each independently represents an integer of 0 to 4, preferably 0 or 1.
- the crosslinking agent (C) is preferably represented by the following general formula (Ib).
- R 1 has the same meaning as R 1 in the general formula (I).
- Z b represents an atomic group necessary for forming a ring together with the carbon atom in the formula, and this ring may have a substituent.
- the ring formed by Z b together with the carbon atom in the formula is the same as that described for the ring formed by combining R 3 and R 4 with each other in the description of the general formula (IB).
- the crosslinking agent (C) is preferably represented by the following general formula (Ic).
- R 1c independently represents an alkyl group.
- Z c represents an atomic group necessary for forming a ring together with the carbon atom in the formula, and this ring may have a substituent.
- the alkyl group represented by R is, for example, preferably an alkyl group having 1 to 6 carbon atoms
- the cycloalkyl group is, for example, a cycloalkyl group having 3 to 12 carbon atoms. preferable.
- alkyl group represented by R 1c for example, an alkyl group having 1 to 5 carbon atoms is preferable.
- the crosslinking agent (C1) is preferably represented by the following general formula (Ie), (If) or (Ig). Wherein, R 1 has the same meaning as R 1 in the general formula (I).
- crosslinking agent (C1) is preferably a compound represented by the following general formula (II).
- X 1 and X 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxymethyl group or an alkoxymethyl group. However, at least one of the two X 1 is a hydroxymethyl group or an alkoxymethyl group.
- Y 1 represents a carbon atom, a nitrogen atom or an oxygen atom when both X 1 are a hydroxymethyl group or an alkoxymethyl group.
- X 1 is neither a hydroxymethyl group nor an alkoxymethyl group
- Y 1 is a nitrogen atom
- X 2 is a hydroxymethyl group or an alkoxymethyl group.
- Y 2 represents a single bond, an alkylene group or a cycloalkylene group.
- Z 2 represents an organic group.
- Any two of X 1 , X 2 and Y 2 may be bonded to form a ring.
- the alkyl group as X 1 and X 2 is preferably an alkyl group having 1 to 30 carbon atoms. Specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, Examples include decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group.
- the alkyl group as X 1 and X 2 may have a substituent.
- the cycloalkyl group as X 1 and X 2 may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 30 carbon atoms. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a bornyl group.
- the cycloalkyl group as X 1 and X 2 may have a substituent.
- the alkyl part of the alkoxy group in the alkoxymethyl group as X 1 and X 2 may be linear or cyclic.
- As the alkoxy group in the alkoxymethyl group a methoxy group and an ethoxy group are more preferable, and a methoxy group is particularly preferable.
- the alkylene group as Y 2 preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group.
- the cycloalkylene group as Y 2 is preferably a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group.
- the organic group represented by Z 2 is preferably an organic group having a molecular weight of 100 or more and 2000 or less, particularly preferably 200 or more and 1500 or less.
- crosslinking agent (C) is shown with molecular weight (Molecular weight).
- the content of the crosslinking agent (C1) is preferably 1 to 50% by mass, more preferably 2 to 40% based on the solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. % By weight, more preferably 5 to 20% by weight, and particularly preferably 10 to 15% by weight.
- a crosslinking agent (C1) may be used independently and may be used in combination of 2 or more type. As described above, the crosslinking agent (C1) is added at a ratio such that the total concentration of hydroxymethyl groups or alkoxymethyl groups of the crosslinking agent (C1) with respect to 1 g of the solid content in the composition of the present invention is 0.30 mmol / g or more. ).
- the total concentration of hydroxymethyl groups or alkoxymethyl groups of the crosslinking agent (C) with respect to 1 g of the solid content in the composition of the present invention is 0.30 to 1.00 mmol / g. It is preferably 0.40 to 0.90 mmol / g, more preferably 0.60 to 0.80 mmol / g.
- the composition of the present invention contains the crosslinking agent (C1) in a proportion of 60 mol% to 100 mol% with respect to the total amount of the crosslinking agent (C) contained in the composition of the present invention.
- the ratio of the crosslinking agent (C1) to the crosslinking agent (C) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and 90 to 100 mol%. More preferably.
- the crosslinking agent (C) means a crosslinking agent having a total of two or more hydroxymethyl groups or alkoxymethyl groups in the molecule, and includes the crosslinking agent (C1) of the present invention.
- the content of the crosslinking agent (C) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. It is more preferably 5 to 20% by mass, particularly preferably 10 to 15% by mass.
- crosslinking agent (C) other than the crosslinking agent (C1) of the present invention examples include, for example, hydroxymethylated or alkoxymethylated phenol compounds, alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds, and alkoxymethylated ureas.
- a compound that does not correspond to the crosslinking agent (C1) of the present invention can be used as appropriate from the crosslinking agent selected from the series compounds. Specific examples include those that do not correspond to the crosslinking agent (C1) of the present invention among the crosslinking agents described in paragraphs 0070 to 0074 of JP2013-44808A.
- composition of the present invention may further contain a crosslinking agent other than the crosslinking agent (C) as long as the effects of the present invention are not impaired.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains an alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as “resin (A)”).
- the phenolic hydroxyl group in the present invention is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxy group.
- the aromatic ring of the aromatic ring group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
- the resin (A) in the exposed portion, the resin (A) will be described later, “Structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain. ”, A crosslinking reaction proceeds from the structural site between the resin (A) containing a phenolic hydroxyl group and the above-mentioned crosslinking agent (C1), and a negative pattern is formed.
- composition of this invention contains the "acid generator (B)" mentioned later, by the effect
- R 2 represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom (preferably a fluorine atom);
- B ′ represents a single bond or a divalent linking group;
- Ar ′ represents an aromatic ring;
- m represents an integer of 1 or more.
- methyl group which may have a substituent for R 2 examples include a trifluoromethyl group and a hydroxymethyl group.
- R 2 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom for developability reasons.
- Examples of the divalent linking group for B ′ include a carbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group (—S ( ⁇ O) 2 —), —O —, —NH— or a divalent linking group in combination of these is preferred.
- B ′ preferably represents a single bond, a carbonyloxy group (—C ( ⁇ O) —O—) or —C ( ⁇ O) —NH—, and a single bond or a carbonyloxy group (—C ( ⁇ O)) —O—) is more preferable, and a single bond is particularly preferable from the viewpoint of improving dry etching resistance.
- the aromatic ring of Ar ′ is a monocyclic or polycyclic aromatic ring, and may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, or a phenanthrene ring.
- M is preferably an integer of 1 to 5, and most preferably 1.
- the substitution position of —OH is the meta position even in the para position relative to the bond position with B ′ of the benzene ring (or the polymer main chain when B ′ is a single bond).
- the para position and the meta position are preferable, and the para position is more preferable.
- the aromatic ring of Ar ′ may have a substituent other than the group represented by the above —OH.
- substituents include an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, an alkoxy group, Examples include a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, and an arylcarbonyl group.
- the repeating unit having a phenolic hydroxyl group is more preferably a repeating unit represented by the following general formula (II ′) for reasons of crosslinking reactivity, developability, and dry etching resistance.
- R 12 represents a hydrogen atom or a methyl group.
- Ar represents an aromatic ring.
- R 12 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom for reasons of developability.
- Ar in the general formula (II ′) has the same meaning as Ar ′ in the general formula (II), and the preferred range is also the same.
- the repeating unit represented by the general formula (II ′) is a repeating unit derived from hydroxystyrene (that is, a repeating unit in which R 12 is a hydrogen atom and Ar is a benzene ring in the general formula (II ′)). It is preferable from the viewpoint of sensitivity.
- Resin (A) may be composed only of repeating units having a phenolic hydroxyl group as described above.
- the resin (A) may have a repeating unit as described later in addition to the repeating unit having a phenolic hydroxyl group as described above.
- the content of the repeating unit having a phenolic hydroxyl group is preferably 10 to 98 mol%, more preferably 30 to 97 mol%, based on all the repeating units of the resin (A). More preferably, it is 40 to 95 mol%.
- the resin (A) has a “structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a group having a non-acid-decomposable hydrocarbon structure”, so that a high glass transition temperature (Tg) can be obtained. This is preferable because the etching resistance is improved.
- the glass transition temperature (Tg) of the resin (A) is increased, and a very hard resist film can be formed. Resistance can be controlled. Therefore, the diffusibility of the acid in the exposed portion of actinic rays or radiation such as an electron beam or extreme ultraviolet rays is greatly suppressed, so that the resolution, pattern shape and LER in a fine pattern are further improved. Further, it is considered that the resin (A) having a non-acid-decomposable hydrocarbon structure contributes to further improvement in dry etching resistance.
- the hydrocarbon structure has a high hydrogen radical donating property, and becomes a hydrogen source during decomposition of the photoacid generator, further improving the decomposition efficiency of the photoacid generator and further increasing the acid generation efficiency. It is estimated that this contributes to better sensitivity.
- the above-mentioned specific structure that the resin (A) according to the present invention may have is derived from a phenolic hydroxyl group in which an aromatic ring such as a benzene ring and a group having a non-acid-decomposable hydrocarbon structure are present. Connected through oxygen atoms. As described above, the structure not only contributes to high dry etching resistance, but also can increase the glass transition temperature (Tg) of the resin (A), and the combination effect provides high resolution. Presumed.
- non-acid-decomposable means a property in which a decomposition reaction does not occur depending on an acid generated by a photoacid generator and an acid generated by an acid generating structure (a) described later.
- the group having a non-acid-decomposable hydrocarbon structure is preferably a group stable to acids and alkalis.
- the group stable to acid and alkali means a group that does not exhibit acid decomposability and alkali decomposability.
- the acid decomposability means the property of causing a decomposition reaction by the action of an acid generated by the photoacid generator and an acid generated by the acid generation structure (a) described later.
- Alkali decomposability means the property of causing a decomposition reaction by the action of an alkali developer, and the group exhibiting alkali decomposability is preferably used in a positive actinic ray-sensitive or radiation-sensitive resin composition.
- groups for example, groups having a lactone structure
- the group having a hydrocarbon structure is not particularly limited as long as it is a monovalent group having a hydrocarbon structure, but the total carbon number is preferably 5 to 40, more preferably 7 to 30.
- the hydrocarbon structure may have an unsaturated bond in the ring.
- the hydrocarbon structure in a group having a hydrocarbon structure means a chain, branched hydrocarbon group, a structure having a monocyclic alicyclic hydrocarbon group, or a polycyclic alicyclic hydrocarbon structure. It may be a bridge type.
- the monocyclic alicyclic hydrocarbon group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. You may have two or more groups. In the case of having a plurality of monocyclic alicyclic hydrocarbon groups, it is preferable to have 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferable to have two.
- Examples of the chain or branched hydrocarbon group include those having 1 to 20 carbon atoms (more preferably 1 to 10 carbon atoms, still more preferably 1 to 7 carbon atoms), propyl group, isopropyl group, and n-butyl.
- Examples of the polycyclic alicyclic hydrocarbon structure include bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms, and polycyclic cyclostructures having 6 to 30 carbon atoms are preferable.
- an adamantane structure and a decalin structure A norbornane structure, a norbornene structure, a cedrol structure, an isobornane structure, a bornane structure, a dicyclopentane structure, an ⁇ -pinene structure, a tricyclodecane structure, a tetracyclododecane structure, and an androstane structure.
- a part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
- hydrocarbon structure examples include an adamantane structure, a decalin structure, a norbornane structure, a norbornene structure, a cedrol structure, a structure having a plurality of cyclohexyl groups, a structure having a plurality of cycloheptyl groups, a structure having a plurality of cyclooctyl groups, and cyclodecanyl.
- a structure having a plurality of groups, a structure having a plurality of cyclododecanyl groups, and a tricyclodecane structure, and an adamantane structure is most preferable from the viewpoint of dry etching resistance (that is, the group having the non-acid-decomposable hydrocarbon structure is And most preferably a group having a non-acid-decomposable adamantane structure).
- the chemical formulas for these hydrocarbon structures are shown below.
- the hydrocarbon structure may have a substituent.
- substituents include an alkyl group (preferably 1 to 6 carbon atoms), a cycloalkyl group (preferably 3 to 10 carbon atoms), an aryl group (preferably Has 6 to 15 carbon atoms, halogen atom, hydroxyl group, alkoxy group (preferably 1 to 6 carbon atoms), carboxyl group, carbonyl group, thiocarbonyl group, alkoxycarbonyl group (preferably 2 to 7 carbon atoms), and these Examples include a group formed by combining groups (preferably having a total carbon number of 1 to 30, more preferably a total carbon number of 1 to 15).
- any one hydrogen in the structure represented by any of the above formulas (7), (23), (40), (41) and (51), or the structure of the above formula (48) A structure having two monovalent groups each having an atom as a bond is preferable.
- the structure represented by any one of the above formulas (23), (40) and (51), and any structure in the structure of the above formula (48) A structure having two monovalent groups each having one hydrogen atom as a bond is more preferable, and a structure represented by the above formula (40) is most preferable.
- the group having a hydrocarbon structure is preferably a monovalent group having any one hydrogen atom of the hydrocarbon structure as a bond.
- the structure in which the hydrogen atom of the phenolic hydroxyl group is substituted with the above-described group having a non-acid-decomposable hydrocarbon structure is preferably contained in the resin (A) as a repeating unit having this structure. Reduce the number of cross-linking points in the resin (A), such as phenolic hydroxyl groups and phenol ortho-position carbon, suppress excessive progress of the reaction in the film with the acid generated by exposure, and improve PEB stability. From the viewpoint of further improvement, the above structure is more preferably contained in the resin (A) as a repeating unit represented by the following general formula (1). According to this structure, for example, even when a resist film is left after exposure, an excessive reaction of acid generated by exposure is suppressed.
- R represents a hydrogen atom or a methyl group
- X represents a group having a non-acid-decomposable hydrocarbon group
- Ar represents an aromatic ring
- L represents a divalent linking group.
- R in the general formula (1) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.
- an aromatic carbon which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, naphthalene ring, anthracene ring, fluorene ring, phenanthrene ring, etc.
- a hydrogen ring or a heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc.
- aromatic ring heterocycles Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable.
- the aromatic ring of Ar may have a substituent other than the group represented by —OX, and examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group ( Preferably 3 to 10 carbon atoms, aryl group (preferably 6 to 15 carbon atoms), halogen atom, hydroxyl group, alkoxy group (preferably 1 to 6 carbon atoms), carboxyl group, alkoxycarbonyl group (preferably 2 carbon atoms) To 7), an alkyl group, an alkoxy group and an alkoxycarbonyl group are preferable, and an alkoxy group is more preferable.
- an alkyl group preferably having 1 to 6 carbon atoms
- a cycloalkyl group Preferably 3 to 10 carbon atoms, aryl group (preferably 6 to 15 carbon atoms), halogen atom, hydroxyl group, alkoxy group (preferably 1 to 6 carbon atoms), carboxyl group, alkoxycarbonyl group
- X represents a group having a non-acid-decomposable hydrocarbon group, and preferably represents a group having a non-acid-decomposable hydrocarbon structure. Specific examples and preferred ranges of the group having a non-acid-decomposable hydrocarbon structure represented by X are the same as those described above. X is more preferably a group represented by —Y—X 2 in the general formula (4) described later.
- Examples of the divalent linking group for L include a carbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group (—S ( ⁇ O) 2 —), —O—. , —NH— or a divalent linking group in combination of these is preferred.
- L preferably represents a single bond, a carbonyloxy group (—C ( ⁇ O) —O—) or —C ( ⁇ O) —NH—, and a single bond or a carbonyloxy group (—C ( ⁇ O) — O-) is more preferable, and a single bond is particularly preferable from the viewpoint of improving dry etching resistance.
- the repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (4).
- the resin (A) having a repeating unit represented by the general formula (4) is used, the Tg of the resin (A) increases, and a very hard resist film is formed. Therefore, acid diffusibility and dry etching resistance are improved. More reliable control.
- R 13 represents a hydrogen atom or a methyl group.
- Y represents a single bond or a divalent linking group.
- X 2 represents a non-acid-decomposable hydrocarbon group.
- R 13 in the general formula (4) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.
- Y is preferably a divalent linking group.
- Preferred groups as the divalent linking group for Y are a carbonyl group, a thiocarbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group, —COCH 2 —, —NH—.
- a divalent linking group (preferably having a total carbon number of 1 to 20, more preferably a total carbon number of 1 to 10), more preferably a carbonyl group, —COCH 2 —, a sulfonyl group, —CONH— , —CSNH—, more preferably a carbonyl group, —COCH 2 —, and particularly preferably a carbonyl group.
- X 2 represents a hydrocarbon group and is non-acid-decomposable.
- the total carbon number of the hydrocarbon group is preferably 5 to 40, and more preferably 7 to 30.
- the hydrocarbon group may have an unsaturated bond in the ring.
- Such a hydrocarbon group is a chain or branched hydrocarbon group, a group having a monocyclic alicyclic hydrocarbon group, or a polycyclic alicyclic hydrocarbon group, and has a bridged type. Also good.
- the monocyclic alicyclic hydrocarbon group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. You may have two or more groups. In the case of having a plurality of monocyclic alicyclic hydrocarbon groups, it is preferable to have 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferable to have two.
- Preferred examples of the chain or branched hydrocarbon group include those having 1 to 20 carbon atoms, more preferably those having 1 to 10 carbon atoms, and further preferably those having 1 to 7 carbon atoms.
- Specific examples of the chain and branched hydrocarbon groups include propyl, isopropyl, n-butyl, s-butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, and 2-ethylhexyl. Group, octyl group and the like.
- Examples of the polycyclic alicyclic hydrocarbon group include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and groups having a polycyclic cyclo structure having 6 to 30 carbon atoms are preferable. And adamantyl group, norbornyl group, norbornenyl group, isobornyl group, camphanyl group, dicyclopentyl group, ⁇ -pinel group, tricyclodecanyl group, tetracyclododecyl group, and androstanyl group.
- a part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
- the polycyclic alicyclic hydrocarbon groups described above X 2 preferably an adamantyl group, a decalin group, a norbornyl group, a norbornenyl group, a cedrol group, a group having a plurality of cyclohexyl groups, having plural groups cycloheptyl group, a cyclooctyl group A group having a plurality, a group having a plurality of cyclodecanyl groups, a group having a plurality of cyclododecanyl groups, and a tricyclodecanyl group, and an adamantyl group is most preferable from the viewpoint of dry etching resistance.
- the same chemical formula as the chemical formula of the hydrocarbon structure in the above-described group having a hydrocarbon structure can be mentioned, and the preferred range is also the same.
- the hydrocarbon group for X 2 include a monovalent group having any one hydrogen atom in the above-described hydrocarbon structure as a bond.
- the alicyclic hydrocarbon group may have a substituent, and examples of the substituent include the same as those described above as the substituent that the hydrocarbon structure may have.
- the substitution position of —O—Y—X 2 in the general formula (4) may be a para position, a meta position, or an ortho position with respect to the bonding position of the benzene ring to the polymer main chain, but the para position is preferred.
- the repeating unit represented by the general formula (1) is most preferably a repeating unit represented by the following general formula (4 ′).
- R 13 represents a hydrogen atom or a methyl group.
- R 13 in the general formula (4 ′) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.
- the substitution position of the adamantyl ester group in the general formula (4 ′) may be in the para position, the meta position, or the ortho position with respect to the bonding position with the polymer main chain of the benzene ring, but the para position is preferred.
- repeating unit having “a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a group having a non-acid-decomposable hydrocarbon structure” include the following.
- repeating unit represented by the general formula (4) examples include the following.
- the resin (A) is a resin containing a repeating unit having “a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a group having the above-described non-acid-decomposable hydrocarbon structure”
- the content is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, more preferably 5 to 20 mol%, based on all repeating units of the resin (A). Is more preferably 10 to 15 mol%.
- Resin (A) may have a crosslinkable group, and preferably has a repeating unit having a crosslinkable group.
- Preferred examples of the repeating unit having a crosslinkable group described above include the following repeating units (Q).
- the repeating unit (Q) has a structure containing at least one methylol group which may have a substituent.
- the “methylol group” is a group represented by the following general formula (M), and in one embodiment of the present invention, a hydroxymethyl group or an alkoxymethyl group is preferable.
- R 2 , R 3 and Z are as defined in the general formula (Q-1) described later. First, the general formula (Q-1) will be described.
- R 1 represents a hydrogen atom, a methyl group, or a halogen atom.
- R 2 and R 3 represents a hydrogen atom, an alkyl group or a cycloalkyl group.
- L represents a divalent linking group or a single bond.
- Y represents a monovalent substituent excluding a methylol group.
- Z represents a hydrogen atom or a substituent.
- m represents an integer of 0 to 4.
- n represents an integer of 1 to 5.
- m + n is 5 or less.
- the plurality of Y may be the same as or different from each other.
- the plurality of R 2 , R 3 and Z may be the same as or different from each other.
- Y, R 2, 2 or more R 3 and Z may be bonded to each other to form a ring structure.
- "Y, R 2, 2 or more R 3 and Z are bonded together to form a ring structure" is represented by the same symbol in the case of the group represented by the same symbols there are multiple It means that groups may be bonded to each other to form a ring structure, or groups represented by different symbols may be bonded to each other to form a ring.
- Methyl group represented by R 1 may have a substituent, examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, a halogen atom, a hydroxyl group such as an iodine atom, include isopropyl Can do.
- Examples of the methyl group which may have a substituent include a methyl group, a trifluoromethyl group, and a hydroxymethyl group.
- Examples of the halogen atom for R 1 include fluorine, chlorine, bromine, and iodine.
- R 1 is preferably a hydrogen atom or a methyl group.
- Examples of the alkyl group represented by R 2 and R 3 include a linear or branched alkyl group having 1 to 10 carbon atoms, and examples of the cycloalkyl group include cycloalkyl having 3 to 10 carbon atoms.
- the group can be mentioned. Specific examples include a hydrogen atom, a methyl group, a cyclohexyl group, and a t-butyl group.
- the alkyl group and cycloalkyl group here may have a substituent. Examples of the substituent include those described later as the substituent of the monovalent substituent of Y.
- Examples of the divalent linking group represented by L include a monocyclic or polycyclic aromatic ring having 6 to 18 carbon atoms, —C ( ⁇ O) —, —O—C ( ⁇ O) —, —CH 2 —. O—C ( ⁇ O) —, a thiocarbonyl group, a linear or branched alkylene group (preferably having a carbon number of 1 to 10, more preferably 1 to 6), a linear or branched alkenylene group (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms), a sulfonyl group, —O—, —NH—, —S—, Examples thereof include a cyclic lactone structure or a divalent linking group combining these (preferably having a total carbon number of 1 to 50, more preferably a total carbon number of 1 to 30, and even more preferably a total carbon
- aromatic ring in L of the general formula (Q-1) may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring.
- Aromatic heterocycles including heterocycles can be mentioned. Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable.
- the divalent linking group represented by L may have a substituent, and the substituent is the same as that described later as the substituent of the monovalent substituent represented by Y. Is mentioned.
- Examples of the monovalent substituent represented by Y include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms), alkynyl.
- a group preferably having 2 to 12 carbon atoms
- a cycloalkyl group (monocyclic or polycyclic may be preferred, preferably having 3 to 12 carbon atoms)
- an aryl group preferably having 6 to 18 carbon atoms
- a hydroxy group Alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamido groups, halogen atoms, haloalkyl groups, and sulfonic acid ester groups.
- Preferable examples include an alkyl group, a cycloalkyl group, a halogen atom, a haloalkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an ester group, and an aryl group, and more preferable examples include an alkyl group, a halogen atom, and a hydroxy group. Group and alkoxy group.
- the monovalent substituent of Y may further have a substituent.
- substituents include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group, a cycloalkyl group, an alkoxy group, and a carboxyl group. Group, an alkoxycarbonyl group, an aryl group, an alkoxyalkyl group, and a group obtained by combining these, and those having 8 or less carbon atoms are preferable.
- m is 2 or more
- a plurality of Y may be bonded to each other through a single bond or a linking group to form a ring structure.
- the linking group in this case include an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, and an alkylene group.
- the halogen atom include the same ones methyl group represented by R 1 is exemplified by optionally may substituent has.
- the haloalkyl group include an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Specific examples include a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and an undecafluorocyclohexyl group.
- Examples of the monovalent substituent represented by Z include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms), alkynyl. Group (preferably having 2 to 12 carbon atoms), cycloalkyl group (preferably having 3 to 8 carbon atoms), aryl group (which may be monocyclic or polycyclic and preferably having 6 to 18 carbon atoms), haloalkyl group Alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylsulfonyl group, arylsulfonyl group, cyano group, alkylthio group, arylthio group, alkoxyalkyl group and heterocyclic group.
- alkyl group which may be linear or branched, preferably 1 to 12 carbon atoms
- Preferable examples include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkanoyl group, an alkenyl group, a haloalkyl group, and an alkoxyalkyl group.
- the alkanoyl group is preferably an alkanoyl group having 2 to 20 carbon atoms.
- an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable.
- aryloxycarbonyl group examples include aryloxycarbonyl groups having 7 to 30 carbon atoms, such as phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2 -Butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3 Nitrophenyl oxycarbonyl group, 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl
- the alkylsulfonyloxy group is preferably an alkylsulfonyloxy group having 1 to 20 carbon atoms.
- the arylsulfonyloxy group is preferably an arylsulfonyloxy group having 6 to 30 carbon atoms.
- an alkylsulfonyl group having 1 to 20 carbon atoms is preferable.
- the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, 2 -Methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4 -Cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl
- alkylthio group examples include alkylthio groups having 1 to 30 carbon atoms, such as methylthio group, ethylthio group, propylthio group, n-butylthio group, trifluoromethylthio group, hexylthio group, t-butylthio group, 2-ethylhexylthio group. Group, cyclohexylthio group, decylthio group and dodecylthio group.
- arylthio group examples include arylthio groups having 6 to 30 carbon atoms, such as a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a tolylthio group, a methoxyphenylthio group, a naphthylthio group, a chlorophenylthio group, and trifluoromethyl.
- a phenylthio group, a cyanophenylthio group, and a nitrophenylthio group are mentioned.
- the heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom.
- the heterocyclic group include a thienyl group, a benzo [b] thienyl group, a naphtho [2,3-b] thienyl group, a thiantenyl group, a furyl group, a pyranyl group, an isobenzofuranyl group, a chromenyl group, and a xanthenyl group.
- Phenoxathiinyl group 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl Group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, ⁇ -carbolynyl group, phenanthridinyl group Le group, Cridinyl, perimidinyl, phenanthrol
- N is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and particularly preferably 2 or 3.
- m is preferably 0 or 1.
- the repeating unit (Q) represented by the general formula (Q-1) is preferably a repeating unit represented by the following general formula (2) or (3).
- R 1 , R 2 , R 3 , Y, Z, m and n are as defined in the general formula (Q-1).
- Ar represents an aromatic ring.
- W 1 and W 2 represent a divalent linking group or a single bond.
- R 1 , R 2 , R 3 , Y, Z, m and n are the same as those described in the general formula (Q-1), and the preferred ranges are also the same.
- Specific examples of the aromatic ring represented by Ar include the same examples as those in the case where L in the general formula (Q-1) is an aromatic ring, and the preferred range is also the same.
- Examples of the divalent linking group represented by W 1 and W 2 include a monocyclic or polycyclic aromatic hydrocarbon ring which may have a substituent having 6 to 18 carbon atoms, —C ( ⁇ O) — , —O—C ( ⁇ O) —, —CH 2 —O—C ( ⁇ O) —, a thiocarbonyl group, a linear or branched alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1).
- a linear or branched alkenylene group preferably having 2 to 10 carbon atoms, more preferably 2 to 6
- a cycloalkylene group preferably having 3 to 10 carbon atoms, more preferably 5 to 10 carbon atoms
- examples thereof include a sulfonyl group, —O—, —NH—, —S—, a cyclic lactone structure, or a divalent linking group obtained by combining these.
- repeating unit (Q) represented by the general formula (Q-1) is more preferably represented by the following general formula (2 ′) or (3 ′).
- R 1 , Y, Z, m and n in the general formulas (2 ′) and (3 ′) have the same meanings as the groups in the general formula (Q-1), and specific examples and preferred ranges are also the same.
- Ar in the general formula (2 ′) has the same meaning as Ar in the general formula (2), and the preferred range is also the same.
- W 3 is a divalent linking group. Examples of the divalent linking group represented by W 3 include a monocyclic or polycyclic aromatic hydrocarbon ring, —C ( ⁇ O) —, linear, which may have a substituent having 6 to 18 carbon atoms.
- branched alkylene group preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms
- cycloalkylene group preferably having 3 to 10 carbon atoms, more preferably 5 to 10 carbon atoms
- -O-, cyclic lactone examples thereof include a structure or a divalent linking group obtained by combining these.
- f is an integer of 0 to 6.
- An integer of 0 to 3 is preferable, and an integer of 1 to 3 is more preferable.
- g is 0 or 1.
- the general formula (2 ′) is particularly preferably represented by any one of the following general formulas (1-a) to (1-c).
- the repeating unit (Q) is particularly preferably a repeating unit represented by any one of the following general formulas (1-a) to (1-c) or a repeating unit represented by the above general formula (3 ′). .
- R 1 , Y and Z in the general formulas (1-a) to (1-c) have the same meanings as the groups in the general formula (Q-1), and specific examples and preferred ranges thereof are also the same.
- Y ′′ represents a hydrogen atom or a monovalent substituent.
- Examples of the monovalent substituent include the same monovalent substituents as those described above for Y. However, Y ′′ represents methylol. It may be a group.
- R 4 represents a hydrogen atom or a monovalent substituent. Specific examples of the monovalent substituent include the same as those in the case where Z in the general formula (Q-1) is a monovalent substituent.
- f represents an integer of 1 to 6.
- a preferred range is as described in the general formula (2 ′).
- m is 0 or 1
- n represents an integer of 1 to 3.
- R 4 is a hydrogen atom, an alkyl group (which may be linear or branched and preferably has 1 to 12 carbon atoms), an alkenyl group ( 2 to 12 carbon atoms are preferred), an alkynyl group (preferably 2 to 12 carbon atoms), a cycloalkyl group (preferably 3 to 8 carbon atoms), an aryl group (monocyclic or polycyclic may be used) And a haloalkyl group, an alkanoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, an alkylthio group, an arylthio group, and A heterocyclic group is mentioned.
- Preferable examples include a hydrogen atom, an alkyl group (which may be linear or branched and
- haloalkyl group alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylsulfonyl group, arylsulfonyl group, cyano group, alkylthio group, arylthio group and heterocyclic group are as follows: It is the same as Y of the said General formula (1), and its preferable range is also the same.
- the content of the repeating unit (Q) is preferably 5 to 50 mol% with respect to all repeating units contained in the resin (A) from the viewpoint of crosslinking efficiency and developability, and is preferably 5 to 40 mol%. More preferably, it is more preferably 5 to 20 mol%, and particularly preferably 5 to 15 mol%.
- Specific examples of the repeating unit (Q) include the following structures.
- A represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- R 1 represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 6 carbon atoms.
- L represents a single bond or a divalent linking group.
- Ar represents a divalent aromatic ring group.
- Y represents a single bond or a divalent linking group.
- A is preferably a hydrogen atom or a methyl group.
- the divalent linking group represented by L may have a substituent, and specific examples of the divalent linking group represented by L and the substituent that the divalent linking group may have are described above. It is the same as that in L in the general formula (1).
- L is preferably a single bond.
- Examples of the divalent linking group represented by Y include a monocyclic or polycyclic aromatic ring having 6 to 18 carbon atoms, —C ( ⁇ O) —, —O—C ( ⁇ O) —, —CH 2 —. O—C ( ⁇ O) —, a thiocarbonyl group, a linear or branched alkylene group (preferably having a carbon number of 1 to 10, more preferably 1 to 6), a linear or branched alkenylene group (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms), a sulfonyl group, —O—, —NH—, —S—, Examples thereof include a cyclic lactone structure or a divalent linking group combining these (preferably having a total carbon number of 1 to 50, more preferably a total carbon number of 1 to 30, and even more preferably a total
- Y is preferably an ethylene group or a methylenecarbonyl group.
- R 1 represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 6 carbon atoms.
- specific examples of the linear, branched or cyclic monovalent hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and structural isomers thereof.
- an alkyl group such as a cyclopentyl group and a cyclohexyl group are preferable, and a methyl group is particularly preferable. If the number of carbon atoms exceeds 6, the ability to form a crosslink may be lowered.
- repeating unit represented by the general formulas (1-1) and (1-2) include the following, but are not limited thereto.
- the resin (A) may or may not have the repeating unit represented by the general formula (1-1) or (1-2). Generally, it is 1 to 30 mol%, preferably 1 to 20 mol%, more preferably 2 to 10 mol%, still more preferably 5 to 10 mol%, based on all repeating units in (A). It is.
- Resin (A) is a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain (hereinafter referred to as “acid generating structure” from the viewpoint of improving at least one of resolution, roughness characteristics, and EL (exposure latitude). It is preferable that the repeating unit (A1) having (a) ") is included.
- the resin (A) may have a repeating unit represented by the following general formula (5) as a repeating unit (A1) having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
- a repeating unit (A1) having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
- the acid generation structure (a) of the resin (A) and the compound (B) described later are the same component.
- R 41 represents a hydrogen atom or a methyl group.
- L 41 represents a single bond or a divalent linking group.
- L 42 represents a divalent linking group.
- S represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
- R 41 is a hydrogen atom or a methyl group as described above, and more preferably a hydrogen atom.
- Examples of the divalent linking group of L 41 and L 42 include an alkylene group, a cycloalkylene group, an arylene group, —O—, —SO 2 —, —CO—, —N (R) —, —S—, -CS- and combinations of two or more thereof are mentioned, and those having a total carbon number of 20 or less are preferred.
- R represents an aryl group, an alkyl group, or cycloalkyl.
- the divalent linking group of L 42 is preferably an arylene group, an arylene group having 6 to 18 carbon atoms (more preferably 6 to 10 carbon atoms) such as a phenylene group, a tolylene group or a naphthylene group, or, for example, Preferred examples include divalent aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.
- the alkylene group of L 41 and L 42 is preferably an alkylene group having 1 to 12 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, and a dodecanylene group.
- Preferred examples of the cycloalkylene group represented by L 41 and L 42 include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group.
- the arylene group of L 41 and L 42 preferably includes those having 6 to 14 carbon atoms such as a phenylene group and a naphthylene group.
- alkylene groups, cycloalkylene groups and arylene groups may further have a substituent.
- substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group.
- the acid generating structure (a) preferably has a sulfonium salt structure or an iodonium salt structure (more preferably a sulfonium salt structure), and an ionic structure site containing a sulfonium salt or an iodonium salt (more preferably an ion containing a sulfonium salt). Is more preferred. More specifically, a group represented by the following general formula (PZI) or (PZII) is preferable as the acid generating structure (a).
- R 201 to R 203 each independently represents an organic group.
- the organic group as R 201 to R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
- Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
- Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
- Use of a ring structure in which two of R 201 to R 203 are combined to form a ring structure is preferable because it can be expected to suppress the exposure machine from being contaminated with decomposition products during exposure.
- Z ⁇ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion.
- the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.
- a non-nucleophilic anion is an anion having a remarkably low ability to cause a nucleophilic reaction, and an anion capable of suppressing degradation with time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the resin is improved, and the temporal stability of the composition is also improved.
- Examples of the organic group represented by R 201 to R 203 include an aryl group, an alkyl group, a cycloalkyl group, a cycloalkenyl group, and an indolyl group.
- the cycloalkyl group and the cycloalkenyl group at least one of the carbon atoms forming the ring may be a carbonyl carbon.
- R 201 to R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
- the aryl group in R 201 , R 202 and R 203 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the alkyl group, cycloalkyl group, and cycloalkenyl group in R 201 , R 202, and R 203 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group). Butyl group, pentyl group), cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, norbornyl group), cycloalkenyl group having 3 to 10 carbon atoms (for example, pentadienyl group, cyclohexenyl group) Can be mentioned.
- R 201 , R 202 and R 203 may further have a substituent.
- substituents include nitro groups, halogen atoms such as fluorine atoms (preferably fluorine atoms), carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkyl groups (preferably having 1 to 15 carbon atoms), alkoxy groups (preferably 1 to 15 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), an arylthio group (preferably 6 to 14 carbon atoms), a hydroxyalkyl group (preferably 1 to 15 carbon
- each group of R 201 , R 202 and R 203 may have, at least one of the carbon atoms forming the ring may be a carbonyl carbon.
- Substituent which may be possessed by the groups R 201, R 202 and R 203 may further have a substituent group, examples of such further substituents are R 201, R 202 And the same examples as the above-mentioned examples of the substituent that each group of R 203 may have, an alkyl group and a cycloalkyl group are preferable.
- R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
- aryl group, alkyl group and cycloalkyl group are the same as the aryl group, alkyl group and cycloalkyl group described as the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 in the aforementioned compound (PZI). is there.
- the aryl group of R 204 and R 205 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
- Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan).
- thiophene residues groups formed by the loss of one hydrogen atom from thiophene
- indole residues groups formed by the loss of one hydrogen atom from indole
- benzofuran residues A group formed by losing one hydrogen atom from benzofuran
- a benzothiophene residue a group formed by losing one hydrogen atom from benzothiophene
- the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have a substituent.
- this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (PZI) may have.
- Z ⁇ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z ⁇ in the general formula (PZI).
- Preferable specific examples of the acid generating structure (a) include specific examples described in paragraphs [0145] to [0148] of JP2013-80002A.
- the acid generating structure (a) is more preferably a group represented by the following general formula (6).
- L 61 represents a divalent linking group
- Ar 61 represents an arylene group.
- R 201 , R 202 and R 203 have the same meanings as R 201 , R 202 and R 203 in the general formula (PZI), respectively.
- Examples of the divalent linking group for L 61 include an alkylene group, a cycloalkylene group, —O—, —SO 2 —, —CO—, —N (R) —, —S—, —CS—, and these Combinations are listed.
- R represents an aryl group, an alkyl group, or cycloalkyl.
- the total number of carbon atoms of the divalent linking group of L 61 is preferably 1 to 15, and more preferably 1 to 10.
- the alkylene group for L 61 is preferably an alkylene group having 1 to 12 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, and a dodecanylene group.
- Preferred examples of the cycloalkylene group represented by L 61 include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group.
- Preferred groups for L 61 are a carbonyl group, a methylene group, * —CO— (CH 2 ) n —O—, * —CO— (CH 2 ) n —O—CO—, * — (CH 2 ) n —COO. —, * — (CH 2 ) n —CONR—, or * —CO— (CH 2 ) n —NR—, particularly preferably a carbonyl group, * —CH 2 —COO—, * —CO—CH 2 -O-, * -CO-CH 2 -O -CO-, * -CH 2 -CONR-, or * a -CO-CH 2 -NR-.
- n represents an integer of 1 to 10.
- n is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and most preferably 1.
- * represents the connecting site on the main chain side, that is, the connecting site with the O atom in the formula.
- Ar 61 represents an arylene group and may have a substituent.
- Ar 61 may have an alkyl group (preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms, more preferably carbon atoms).
- a halogen atom preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, more preferably a fluorine atom.
- the aromatic ring of Ar 61 may be an aromatic hydrocarbon ring (for example, benzene ring or naphthalene ring) or an aromatic heterocyclic ring (for example, quinoline ring), and preferably has 6 to 18 carbon atoms. More preferably, it has 6 to 12 carbon atoms.
- Ar 61 is preferably an unsubstituted or alkyl group or a fluorine atom is an arylene group substituted, and more preferably a phenylene group or a naphthylene group.
- R 201, R 202 and R 203 are the same as those described for R 201, R 202 and R 203 in formula (PZI).
- a method for synthesizing the monomer corresponding to the repeating unit (A1) having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain is not particularly limited.
- the repeating unit And a method of synthesizing by exchanging an acid anion having a polymerizable unsaturated bond corresponding to the above and a known onium salt halide.
- a metal ion salt for example, sodium ion, potassium ion, etc.
- an ammonium salt ammonium, triethylammonium salt, etc.
- An onium salt having a chloride ion, a bromide ion, an iodide ion, etc. is stirred in the presence of water or methanol to carry out an anion exchange reaction, such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, tetrahydroxyfuran, etc.
- an anion exchange reaction such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, tetrahydroxyfuran, etc.
- the repeating unit (A1) having a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain also introduces an acid anion moiety into the side chain by a polymer reaction and introduces an onium salt by salt exchange Can also be synthesized.
- repeating unit (A1) having a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain are described in paragraphs [0168] to [0210] of JP2013-80002A. Specific examples described in the above can be given.
- the content of the repeating unit (A1) having a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain is 1 to
- the range is preferably 40 mol%, more preferably 2 to 30 mol%, particularly preferably 4 to 25 mol%.
- the resin (A) used in the present invention preferably further has the following repeating units (hereinafter, also referred to as “other repeating units”) as repeating units other than the above repeating units.
- other repeating units include styrene, alkyl-substituted styrene, alkoxy-substituted styrene, halogen-substituted styrene, O-alkylated styrene, O-acylated styrene, hydrogenated hydroxystyrene, and anhydrous maleic acid.
- Acid acrylic acid derivative (acrylic acid, acrylic ester, etc.), methacrylic acid derivative (methacrylic acid, methacrylic ester, etc.), N-substituted maleimide, acrylonitrile, methacrylonitrile, vinyl naphthalene, vinyl anthracene, substituted Inden etc. which may be sufficient can be mentioned.
- the resin (A) may or may not have these other repeating units, but when it is included, the content of these other repeating units in the resin (A) constitutes the resin (A). It is generally 1 to 30 mol%, preferably 1 to 20 mol%, more preferably 2 to 10 mol%, still more preferably 5 to 10 mol%, based on all repeating units.
- Resin (A) can be synthesized by a known radical polymerization method, anion polymerization method, or living radical polymerization method (such as an iniferter method).
- a vinyl monomer can be dissolved in a suitable organic solvent, and a polymer can be obtained by usually reacting under a cooling condition using a metal compound (such as butyl lithium) as an initiator.
- a metal compound such as butyl lithium
- Examples of the resin (A) include polyphenol compounds produced by condensation reaction of aromatic ketones or aromatic aldehydes and compounds containing 1 to 3 phenolic hydroxyl groups (for example, JP 2008-145539), calixarene derivatives (For example, Japanese Patent Application Laid-Open No. 2004-18421), a Noria derivative (for example, Japanese Patent Application Laid-Open No. 2009-222920), and a polyphenol derivative (for example, Japanese Patent Application Laid-Open No. 2008-94782) can be applied, and they may be synthesized by modification with a polymer reaction.
- polyphenol compounds produced by condensation reaction of aromatic ketones or aromatic aldehydes and compounds containing 1 to 3 phenolic hydroxyl groups for example, JP 2008-145539
- calixarene derivatives for example, Japanese Patent Application Laid-Open No. 2004-18421
- a Noria derivative for example, Japanese Patent Application Laid-Open No. 2009-222920
- a polyphenol derivative for example, Japanese Patent Application
- the resin (A) is preferably synthesized by modifying a polymer synthesized by a radical polymerization method or an anionic polymerization method by a polymer reaction.
- the weight average molecular weight of the resin (A) is preferably 1000 to 200000, more preferably 2000 to 50000, and still more preferably 2000 to 15000.
- the dispersity (molecular weight distribution) (Mw / Mn) of the resin (A) is preferably 2.0 or less, and preferably 1.0 to 1.80 from the viewpoint of improving sensitivity and resolution. 0.0 to 1.60 is more preferable, and 1.0 to 1.20 is most preferable. Use of living polymerization such as living anionic polymerization is preferable because the degree of dispersion (molecular weight distribution) of the resulting polymer compound becomes uniform.
- the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin were measured by GPC (solvent: tetrahydrofuran, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40).
- the content of the resin (A) in the composition of the present invention is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, particularly preferably 50 to 85% by mass, based on the total solid content of the composition. Used in
- resin (A) Specific examples of the resin (A) are shown below, but the present invention is not limited thereto.
- composition of the present invention contains a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter abbreviated as “acid generator”, “photoacid generator”, or “compound (B)”). Also good.
- acid generator include onium compounds. Examples of such onium compounds include sulfonium salts, iodonium salts, phosphonium salts, and the like.
- the acid generator includes a compound that generates sulfonic acid, imidic acid or methide acid upon irradiation with actinic rays or radiation.
- the acid generator in the form include a sulfonium salt, an iodonium salt, a phosphonium salt, an oxime sulfonate, and an imide sulfonate.
- the acid generator used in the present invention not only a low molecular compound but also a compound in which a group capable of generating an acid upon irradiation with actinic rays or radiation is introduced into the main chain or side chain of a polymer compound can be used. Further, as described above, when a group that generates an acid upon irradiation with actinic rays or radiation is present in the repeating unit that is a copolymerization component of the alkali-soluble resin (A) used in the present invention, It does not matter if the acid generator (B) of a different molecule from the alkali-soluble resin (A) of the present invention is not included.
- the acid generator is preferably a compound that generates an acid upon irradiation with an electron beam or extreme ultraviolet rays.
- preferred onium compounds include sulfonium compounds represented by the following general formula (7) or iodonium compounds represented by the general formula (8).
- R a1 , R a2 , R a3 , R a4 and R a5 each independently represent an organic group.
- X ⁇ represents an organic anion
- R a1 to R a3 of the general formula (7) and R a4 and R a5 of the general formula (8) each independently represent an organic group, preferably at least one of R a1 to R a3 ,
- at least one of R a4 and R a5 is an aryl group.
- the aryl group a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
- Examples of the organic anion X ⁇ in the general formulas (7) and (8) include a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, and a tris (alkylsulfonyl) methide anion.
- Rc 1 , Rc 2 , Rc 3 and Rc 4 each represents an organic group.
- the organic anion of X ⁇ corresponds to sulfonic acid, imide acid, methide acid, etc., which are acids generated by irradiation with actinic rays or radiation such as electron beams and extreme ultraviolet rays.
- Examples of the organic group of R c1 to R c4 include an alkyl group, a cycloalkyl group, an aryl group, or a group in which a plurality of these are connected. More preferably among these organic groups, the alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, a cycloalkyl group substituted with a fluorine atom or a fluoroalkyl group, a phenyl group substituted with a fluorine atom or a fluoroalkyl group It is.
- a plurality of the organic groups represented by R c2 to R c4 may be connected to each other to form a ring, and examples of the group in which the plurality of organic groups are connected include an alkylene group substituted with a fluorine atom or a fluoroalkyl group. Is preferred. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. However, the terminal group preferably does not contain a fluorine atom as a substituent.
- the acid generator is preferably a compound that generates an acid represented by the following general formula (IIIB) or (IVB) upon irradiation with actinic rays or radiation. Since it is a compound that generates an acid represented by the following general formula (IIIB) or (IVB) and has a cyclic organic group, the resolution and roughness performance can be further improved. Moreover, the effect of this invention can be heightened more according to the synergistic effect with a crosslinking agent (C1).
- the X ⁇ organic anion may be an anion that generates an organic acid represented by the following general formula (IIIB) or (IVB).
- Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- R 1 and R 2 each independently represents a hydrogen atom or an alkyl group.
- L each independently represents a divalent linking group.
- Cy represents a cyclic organic group.
- Rf represents a group containing a fluorine atom.
- x represents an integer of 1 to 20.
- y represents an integer of 0 to 10.
- z represents an integer of 0 to 10.
- Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
- the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
- Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
- Xf is more preferably a fluorine atom or CF 3 .
- both Xf are fluorine atoms.
- R 1 and R 2 are each independently a hydrogen atom or an alkyl group.
- the alkyl group as R 1 and R 2 may have a substituent, and preferably has 1 to 4 carbon atoms.
- R 1 and R 2 are preferably a hydrogen atom.
- L represents a divalent linking group.
- the divalent linking group include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, and the like. (Preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a divalent linking group in which a plurality of these are combined. .
- —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO 2 —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.
- Cy represents a cyclic organic group.
- the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
- the alicyclic group may be monocyclic or polycyclic.
- the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
- an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, is a PEB (heating after exposure) step. It is preferable from the viewpoint of suppression of in-film diffusibility and improvement of MEEF (Mask Error Enhancement Factor).
- MEEF Mesk Error Enhancement Factor
- the aryl group may be monocyclic or polycyclic.
- Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
- a naphthyl group having a relatively low light absorbance at 193 nm is preferable.
- the heterocyclic group may be monocyclic or polycyclic, but polycyclic can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring that does not have aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
- heterocyclic ring in the heterocyclic group a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.
- lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the aforementioned resin (A).
- the cyclic organic group may have a substituent.
- substituents include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic).
- alkyl group which may be linear or branched, preferably 1 to 12 carbon atoms
- a cycloalkyl group monocyclic, polycyclic or spirocyclic.
- Well preferably having 3 to 20 carbon atoms
- aryl group preferably having 6 to 14 carbon atoms
- hydroxyl group alkoxy group
- ester group amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid
- An ester group is mentioned.
- the carbon constituting the cyclic organic group may be a carbonyl carbon.
- X is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1.
- y is preferably 0 to 4, more preferably 0.
- z is preferably 0 to 8, more preferably 0 to 4, and still more preferably 1.
- Examples of the group containing a fluorine atom represented by Rf include an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom. .
- alkyl group, cycloalkyl group and aryl group may be substituted with a fluorine atom or may be substituted with another substituent containing a fluorine atom.
- Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom
- other substituents containing a fluorine atom include, for example, alkyl substituted with at least one fluorine atom. Groups.
- alkyl group, cycloalkyl group and aryl group may be further substituted with a substituent which does not contain a fluorine atom.
- substituent the thing which does not contain a fluorine atom among what was demonstrated about Cy previously can be mentioned, for example.
- Examples of the alkyl group having at least one fluorine atom represented by Rf include those described above as an alkyl group substituted with at least one fluorine atom represented by Xf.
- Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include a perfluorocyclopentyl group and a perfluorocyclohexyl group.
- Examples of the aryl group having at least one fluorine atom represented by Rf include a perfluorophenyl group.
- a particularly preferred embodiment is an embodiment in which x is 1, 2 and Xf is a fluorine atom, y is 0 to 4, all R 1 and R 2 are hydrogen atoms, and z is 1.
- x is 1, 2 and Xf is a fluorine atom
- y is 0 to 4
- all R 1 and R 2 are hydrogen atoms
- z is 1.
- there are few fluorine atoms it is difficult to be unevenly distributed on the surface when the resist film is formed, and it is easy to disperse uniformly in the resist film.
- the compound (B) that generates an acid has a volume of 130 to 3 or more from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution and pattern shape. It is preferable that the compound generate an acid (more preferably sulfonic acid) having a size of more than 1, more preferably a compound that generates an acid having a volume of 190 3 or more (more preferably sulfonic acid). preferably more than that 270 ⁇ 3 or more in size (more preferably sulfonic acid) of the acid is a compound which generates an, it (more preferably sulfonic acid) acid volume 400 ⁇ 3 or more in size is a compound capable of generating an Is particularly preferred.
- the volume is preferably 2000 3 or less, and more preferably 1500 3 or less.
- the volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
- the calculated value of the volume is appended to a part of the example (unit 3 3 ).
- required here is a volume value of the acid which the proton couple
- the acid generator preferably onium compound used in the present invention
- a group in which an acid is generated by irradiation with actinic rays or radiation is introduced into the main chain or side chain of the polymer compound.
- a molecular type acid generator can also be used, and is described as a repeating unit having a photoacid generating group in the above description of the alkali-soluble resin (A).
- the content of the acid generator in the composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 0.5% based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. 20% by mass.
- An acid generator can be used individually by 1 type or in combination of 2 or more types.
- the composition of the present invention preferably contains a basic compound as an acid scavenger.
- a basic compound By using a basic compound, a change in performance over time from exposure to post-heating can be reduced.
- Such basic compounds are preferably organic basic compounds, and more specifically, aliphatic amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, and sulfonyl groups.
- An amine oxide compound (a compound having a methyleneoxy unit and / or an ethyleneoxy unit is preferable, for example, a compound described in JP-A-2008-102383), an ammonium salt (preferably a hydroxide or a carboxylate). More specifically, a tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable from the viewpoint of LER.
- a compound whose basicity is increased by the action of an acid can also be used as one kind of basic compound.
- amines include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecylamine , Hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N-dihexylaniline, 2,6- Diisopropylaniline, 2,4,6-tri (t-butyl) aniline, triethanolamine, N, N-dihydroxyethylaniline, tris (methoxyethoxyethyl) amine, and columns 3, 60 of US
- Compounds having a nitrogen-containing heterocyclic structure include 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, N-hydroxyethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl ) Sebacate, 4-dimethylaminopyridine, antipyrine, hydroxyantipyrine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] -undec-7-ene And tetrabutylammonium hydroxide.
- Photodegradable basic compounds (initially basic nitrogen atoms act as a base and show basicity, but are decomposed by irradiation with actinic rays or radiation to have amphoteric compounds having basic nitrogen atoms and organic acid sites.
- a compound in which basicity is reduced or eliminated by generating ionic compounds and neutralizing them in the molecule for example, Japanese Patent No. 3577743, Japanese Patent Application Laid-Open No. 2001-215589, Japanese Patent Application Laid-Open No. 2001-166476, An onium salt described in JP-A-2008-102383
- a photobase generator for example, a compound described in JP 2010-243773 A
- ammonium salts are preferable from the viewpoint of improving resolution.
- a basic compound represented by the following general formula (N-II) (hereinafter also referred to as “compound (D1)”) is also preferred.
- A represents a sulfur atom or an iodine atom.
- R 1 represents a hydrogen atom or an organic group. When a plurality of R 1 are present, R 1 may be the same or different.
- R represents an (o + 1) valent organic group. When a plurality of R are present, R may be the same or different.
- X represents a single bond or a linking group. When two or more X exists, X may be the same or different.
- a N represents a basic site containing a nitrogen atom. When a plurality of A N are present, A N may be the same or different.
- n is an integer of 1 to 3
- n 1 or 2
- o represents an integer of 1 to 10.
- Y ⁇ represents an anion (details are as described below as the anion part of the compound (D1)).
- R 1, X, R, at least two A N are bonded to each other, may form a ring.
- Examples of the (o + 1) -valent organic group represented by R include a chain (linear, branched) or cyclic aliphatic hydrocarbon group, heterocyclic hydrocarbon group, and aromatic hydrocarbon group.
- An aromatic hydrocarbon group is preferable.
- R is an aromatic hydrocarbon group, those bonded at the p-position (1,4-position) of the aromatic hydrocarbon group are preferred.
- the linking group represented by X has the same meaning as the linking group represented by X in the general formula (NI) described above, and the same specific examples can be given.
- the basic site represented by A N is a site where the pKa of the conjugate acid of the cation site of compound (D1) is -3 or more.
- This pKa is preferably in the range of -3 to 15, more preferably in the range of 0 to 15.
- this pKa means the calculated value calculated
- the basic moiety includes, for example, a structure selected from the group consisting of an amino group (a group obtained by removing one hydrogen atom from ammonia, primary amine, or secondary amine; the same applies hereinafter) and a nitrogen-containing heterocyclic group.
- the amino group is preferably an aliphatic amino group.
- the aliphatic amino group means a group obtained by removing one hydrogen atom from an aliphatic amine.
- all of the atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms.
- an electron-withdrawing functional group such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom
- an electron-withdrawing functional group such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom
- the amino group is preferably, for example, —N (R A ) (R B ).
- R A and R B each independently represent a hydrogen atom or an organic group, and R A and R B may be bonded to each other to form a ring.
- the organic group represented by R A or R B include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic hydrocarbon group, an alkoxycarbonyl group, and a lactone group.
- Alkyl group represented by R 1 may be linear, it may be branched. The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, and still more preferably 1 to 20 carbon atoms.
- alkyl groups examples include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t- Examples thereof include a butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group.
- the alkenyl group represented by R 1 may be linear or branched.
- the alkenyl group has preferably 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms, and still more preferably 3 to 20 carbon atoms.
- Examples of such alkenyl groups include vinyl groups, allyl groups, and styryl groups.
- the aliphatic cyclic group represented by R 1 is, for example, a cycloalkyl group.
- the cycloalkyl group may be monocyclic or polycyclic.
- Preferred examples of the aliphatic cyclic group include monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
- the aromatic hydrocarbon group represented by R 1 is preferably one having 6 to 14 carbon atoms. Examples of such a group include aryl groups such as a phenyl group and a naphthyl group.
- the aromatic hydrocarbon group represented by R 1 is preferably a phenyl group.
- the heterocyclic hydrocarbon group represented by R 1 may have aromaticity or may not have aromaticity. This heterocyclic hydrocarbon group preferably has aromaticity.
- the heterocyclic ring contained in the above group may be monocyclic or polycyclic.
- Examples of such heterocycle include imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole ring, purine ring, isoquinoline ring, 4H-quinolidine ring.
- R 1 is preferably an aromatic hydrocarbon group, or two R 1 are bonded to form a ring.
- R 1, X, R, at least two ring which may be formed by combining each other A N is preferably 4 to 7-membered ring, more preferably a 5- or 6-membered ring, 5-membered A ring is particularly preferable.
- the ring skeleton may contain a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom.
- examples of the substituent include the following. That is, examples of the substituent include a halogen atom (—F, —Br, —Cl, or —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an amino group, and an acyloxy group.
- a halogen atom —F, —Br, —Cl, or —I
- examples of the substituent include a halogen atom (—F, —Br, —Cl, or —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an amino group, and an acyloxy group.
- a hydroxyl group, an alkoxy group, a cyano group, an aryl group, an alkenyl group, an alkynyl group, an alkyl group, and the like are preferable.
- o is preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1.
- At least one of n Rs in the formula is preferably an aromatic hydrocarbon group.
- X in at least one of o number of — (X—A N ) groups bonded to at least one of the aromatic hydrocarbon groups is a carbon atom at the bond to the aromatic hydrocarbon group.
- a linking group is preferred. That is, the compounds in this embodiment (D1), a basic moiety represented by A N is through a carbon atom directly bonded to the aromatic hydrocarbon groups represented by R, bonded to the aromatic hydrocarbon group ing.
- the aromatic hydrocarbon group represented by R may include a heterocyclic ring as the aromatic ring in the aromatic hydrocarbon group.
- the aromatic ring may be monocyclic or polycyclic.
- the aromatic ring group preferably has 6 to 14 carbon atoms. Examples of such a group include aryl groups such as a phenyl group, a naphthyl group, and an anthryl group.
- examples of the heterocyclic ring include thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, and triazole.
- the aromatic hydrocarbon group represented by R is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.
- the aromatic hydrocarbon group represented by R may further have a substituent other than the group represented by — (X—A N ) described below.
- a substituent what was enumerated previously as a substituent in R ⁇ 1 > can be used, for example.
- the linking group as X in the at least one — (XA N ) group substituted on the aromatic ring R has a carbon atom bonded to the aromatic hydrocarbon group represented by R. If it is, it will not be specifically limited.
- the linking group includes, for example, an alkylene group, a cycloalkylene group, an arylene group, —COO—, —CO—, or a combination thereof.
- R ′ represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
- the alkylene group that can be contained in the linking group represented by X may be linear or branched.
- the alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.
- the cycloalkylene group that may be contained in the linking group represented by X may be monocyclic or polycyclic.
- the cycloalkylene group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of such a cycloalkylene group include a 1,4-cyclohexylene group.
- the number of carbon atoms of the arylene group that can be contained in the linking group represented by X is preferably 6 to 20, and more preferably 6 to 10.
- Examples of such an arylene group include a phenylene group and a naphthylene group.
- At least one X is preferably represented by the following general formula (N-III) or (N-IV).
- R 2 and R 3 represent a hydrogen atom, an alkyl group, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group, or a heterocyclic hydrocarbon group.
- R 2 and R 3 may be bonded to each other to form a ring.
- At least one of R 2 and R 3 may be bonded to E to form a ring.
- E represents a linking group or a single bond.
- J represents an oxygen atom or a sulfur atom.
- E represents a linking group or a single bond.
- R 2 and R 3 examples of the groups represented by R 2 and R 3 and the substituents they may further include are the same as those described above for R 1 .
- the ring that can be formed by combining R 2 and R 3 and the ring that can be formed by combining at least one of R 2 and R 3 with E is preferably a 4- to 7-membered ring. A 6-membered ring is more preferable.
- R 2 and R 3 are preferably each independently a hydrogen atom or an alkyl group.
- the linking group represented by E is, for example, an alkylene group, a cycloalkylene group, an arylene group, —COO—, —CO—, —O—, —S—, —OCO—, —S ( ⁇ O) —, — S ( ⁇ O) 2 —, —OS ( ⁇ O) 2 —, —NR—, or a combination thereof is included.
- R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, for example.
- the linking group represented by E is an alkylene bond, ester bond, ether bond, thioether bond, urethane bond
- the linking group represented by E is more preferably an alkylene bond, an ester bond, or an ether bond.
- the compound (D1) may be a compound having a plurality of sites containing nitrogen atoms.
- the compound (D1) may be a compound in which at least one R 1 in the general formula (N-II) has a structure represented by the general formula (NI).
- the compound (D1) represented by the general formula (N-II) is represented by the following general formula (NV).
- R 14 s each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group.
- R 14 s each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group.
- R 14 s each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl
- R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R 15 may be bonded to each other to form a ring, and the atoms constituting the ring may include heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom. These groups may have a substituent.
- l represents an integer of 0-2.
- r represents an integer of 0 to 8.
- the alkyl group for R 14 and R 15 is linear or branched and preferably has 1 to 10 carbon atoms.
- Examples of the cycloalkyl group for R 14 and R 15 include monocyclic or polycyclic cycloalkyl groups.
- the alkoxy group for R 14 is preferably linear or branched and has 1 to 10 carbon atoms.
- the alkoxycarbonyl group for R 14 is preferably linear or branched and has 2 to 11 carbon atoms.
- Examples of the group having a cycloalkyl group as R 14 include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.
- the alkyl group of the alkyl group of R 14, include the same specific examples as the alkyl group as R 14, R 15 described above.
- the alkylsulfonyl group and cycloalkylsulfonyl group for R 14 are linear, branched, or cyclic and preferably have 1 to 10 carbon atoms.
- each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.
- a 5-membered or 6-membered ring formed by two R 15 together with a sulfur atom in the general formula (NV) is particularly preferable.
- a 5-membered ring that is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring
- This divalent R 15 may have a substituent.
- substituents examples include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group. Group, alkoxycarbonyloxy group and the like. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.
- R 15 in the general formula (NV) is preferably a methyl group, an ethyl group, a naphthyl group, or a divalent group in which two R 15 are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.
- a divalent group in which two R 15 are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is particularly preferable.
- R 14 may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
- l is preferably 0 or 1, and more preferably 1.
- r is preferably from 0 to 2.
- the compound (D1) represented by the general formula (N-II) is represented by the following general formula (N-VI).
- A represents a sulfur atom or an iodine atom.
- Ar each independently represents an aromatic hydrocarbon group.
- X 1 each independently represents a divalent linking group.
- R 12 each independently represents a hydrogen atom or an organic group.
- Y ⁇ represents an anion (details are as described below as the anion part of the compound (D1)).
- the alkyl group as R 11, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group, and specific examples and preferred examples of the heterocyclic hydrocarbon group, as R 1 in formula (N-II) Specific examples and preferred examples of the alkyl group, alkenyl group, aliphatic cyclic group, aromatic hydrocarbon group, and heterocyclic hydrocarbon group are the same.
- Specific examples and preferred examples of the aromatic hydrocarbon group as Ar are the same as the specific examples and preferred examples of the aromatic hydrocarbon group as R in the general formula (N-II).
- Specific examples and preferred examples of the divalent linking group as X 1 are the same as the specific examples and preferred examples of the linking group as X in the general formula (N-II).
- Specific examples and preferred examples of the organic group as R 12 are the same as the specific examples and preferred examples of the organic group as R A and R B in the general formula (NI).
- X is an alkylene group (for example, a methylene group) and two R 12 are bonded to each other to form a ring
- PEB post-exposure heating
- PED post-exposure line width
- the anion part of the compound (D1) is not particularly limited.
- the anion contained in the compound (D1) is preferably a non-nucleophilic anion.
- the non-nucleophilic anion is an anion having an extremely low ability to cause a nucleophilic reaction, and an anion capable of suppressing degradation with time due to intramolecular nucleophilic reaction. Thereby, the temporal stability of the composition according to the present invention is improved.
- non-nucleophilic anion examples include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.
- sulfonate anion examples include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
- carboxylate anion examples include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.
- the aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms, such as methyl Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group,
- the alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.
- substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group A hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), a cycloalkyl group (preferably having a carbon number of 3 to 15), an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyl
- Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.
- Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.
- the aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like.
- the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent.
- substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom and alkyl as in the aromatic sulfonate anion Group, cycloalkyl group, alkoxy group, alkylthio group and the like.
- the sulfonylimide anion include saccharin anion.
- the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, Examples thereof include an isobutyl group, a sec-butyl group, a pentyl group, and a neopentyl group.
- substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like.
- Alkyl groups substituted with fluorine atoms are preferred.
- two alkyl groups in the bis (alkylsulfonyl) imide anion are bonded to each other to form a cyclic structure.
- the cyclic structure formed is preferably a 5- to 7-membered ring.
- non-nucleophilic anions examples include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.
- non-nucleophilic anion examples include an aliphatic sulfonate anion in which the ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom.
- a substituted bis (alkylsulfonyl) imide anion and a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom are preferred.
- the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, Pentafluorobenzenesulfonate anion, 3,5-bis (trifluoromethyl) benzenesulfonate anion.
- the anion moiety of the compound (D1) As a preferred embodiment of the anion moiety of the compound (D1), the structure exemplified as the preferred anion structure of the acid generator (B) described above (for example, the organic acids represented by the general formulas (IIIB) and (IVB) described above) The structure of the anion etc. which arises) can be mentioned. Further, the compound (D1) has a fluorine content represented by (total mass of all fluorine atoms contained in the compound) / (total mass of all atoms contained in the compound) of 0.30 or less. It is preferably 0.25 or less, more preferably 0.20 or less, particularly preferably 0.15 or less, and most preferably 0.10 or less.
- a basic compound may be used independently and may be used in combination of 2 or more type.
- the content of the basic compound used in the present invention is preferably 0.01 to 20% by mass, more preferably 0.03 to 15% by mass, based on the total solid content of the composition of the present invention. 05 to 13% by mass is more preferable, and 5 to 13% by mass is particularly preferable.
- the composition of the present invention may further contain a surfactant in order to improve applicability.
- surfactants include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Fluorine such as nonionic surfactants such as sorbitan fatty acid esters, MegaFac F171 (manufactured by Dainippon Ink and Chemicals), Florard FC430 (manufactured by Sumitomo 3M), Surfinol E1004 (manufactured by Asahi Glass), PF656 and PF6320 manufactured by OMNOVA Surfactants and organosiloxane polymers.
- the amount of the surfactant used is preferably 0.0001 to 5 mass with respect to the total amount of the composition (excluding the solvent). %, More preferably 0.0005 to 4% by mass.
- the composition of the present invention preferably contains an organic carboxylic acid.
- organic carboxylic acid compounds include aliphatic carboxylic acid, alicyclic carboxylic acid, unsaturated aliphatic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid, benzoic acid derivative, phthalic acid, terephthalic acid, isophthalic acid , 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, and the like, but when electron beam exposure is performed in a vacuum, the resist film surface volatilizes and draws.
- aromatic organic carboxylic acids among which, for example, benzoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid are preferable as they may contaminate the inside of the chamber. .
- the amount of the organic carboxylic acid is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. 3 parts by mass.
- composition of the present invention may further comprise a dye, a plasticizer, an acid proliferating agent (WO95 / 29968, WO98 / 24000, JP-A-8-305262, No. 9-34106, JP-A-8-248561, JP-A-8-503082, JP-A-5,445,917, JP-A-8-503081, JP-A-5-503081 534,393, US Pat. No. 5,395,736, US Pat. No. 5,741,630, US Pat. No. 5,334,489, US Pat. No. 5,582 No. 956, US Pat. No. 5,578,424, US Pat. No. 5,453,345, US Pat. No.
- the composition of the present invention may contain a carboxylic acid onium salt.
- the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt.
- the carboxylic acid onium salt is preferably a carboxylic acid iodonium salt or a carboxylic acid sulfonium salt.
- it is preferable that the carboxylate residue of the carboxylic acid onium salt does not contain an aromatic group or a carbon-carbon double bond.
- a particularly preferred anion moiety is a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable.
- the alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.
- solvent used in the composition of the present invention examples include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), propylene glycol monomethyl ether acetate.
- PGME propylene glycol monomethyl ether
- PMEA also known as 1-methoxy-2-acetoxypropane
- propylene glycol monomethyl ether propionate propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl ⁇ -methoxyisobutyrate
- butyric acid Ethyl, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol Le, N- methylpyrrolidone, N, N- dimethylformamide, .gamma.-butyrolactone, N, N- dimethylacetamide, propylene carbonate, and ethylene carbonate is preferred.
- These solvents are used alone or in combination.
- the solid content of the actinic ray-sensitive or radiation-sensitive resin composition is dissolved in the above solvent and is dissolved at a solid content concentration of 1 to 40% by mass. More preferably, it is 1 to 30% by mass, and further preferably 3 to 20% by mass.
- the present invention also relates to an actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.
- the composition is formed by coating on a support such as a substrate.
- the thickness of the actinic ray-sensitive or radiation-sensitive film is preferably 0.02 to 0.1 ⁇ m.
- spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. are applied on the substrate, but spin coating is preferred, and the number of rotations is 1000 to 3000 rpm is preferred.
- the coating film is prebaked at 60 to 150 ° C. for 1 to 20 minutes, preferably at 80 to 120 ° C. for 1 to 10 minutes to form a thin film.
- a silicon wafer can be used as the material constituting the substrate to be processed and its outermost layer.
- the material that becomes the outermost layer include Si, SiO 2 , SiN, SiON, TiN, and WSi. , BPSG, SOG, organic antireflection film, and the like.
- the present invention also relates to a mask blank provided with an actinic ray-sensitive or radiation-sensitive film obtained as described above.
- the transparent substrate used is quartz, fluoride, A transparent substrate such as calcium can be mentioned.
- a light-shielding film, an antireflection film, a phase shift film, and additional functional films such as an etching stopper film and an etching mask film are laminated on the substrate.
- a film containing a transition metal such as silicon or chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium is laminated.
- silicon or a material containing oxygen and / or nitrogen in silicon as a main constituent material
- silicon compound material containing a transition metal-containing material as a main constituent material
- a transition metal in particular, one or more selected from chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium, etc., or a material further containing one or more elements selected from oxygen, nitrogen, and carbon
- the transition metal compound material is exemplified.
- the light shielding film may be a single layer, but more preferably has a multilayer structure in which a plurality of materials are applied.
- the thickness of the film per layer is not particularly limited, but is preferably 5 nm to 100 nm, and more preferably 10 nm to 80 nm.
- the thickness of the entire light shielding film is not particularly limited, but is preferably 5 nm to 200 nm, and more preferably 10 nm to 150 nm.
- actinic ray-sensitive or radiation-sensitive film is then irradiated with actinic rays or radiation (such as an electron beam), and preferably baked (usually 80 to 150 ° C., more preferably 90 to 130 ° C., usually 1 to 20). Development for 1 minute to 10 minutes, preferably 1 to 10 minutes). Thereby, a good pattern can be obtained. Then, using this pattern as a mask, etching processing, ion implantation, and the like are performed as appropriate to create a semiconductor microcircuit, an imprint mold structure, a photomask, and the like.
- actinic rays or radiation such as an electron beam
- Japanese Patent No. 4109085 Japanese Patent Application Laid-Open No. 2008-162101, and “Nanoimprint Basics and Technology Development / Application Deployment” -Nanoimprint substrate technology and latest technology development-edited by Yoshihiko Hirai (Frontier Publishing) ".
- the usage pattern of the composition of the present invention and the resist pattern forming method will be described below.
- the present invention includes "exposing the actinic ray-sensitive or radiation-sensitive film” or “exposing a mask blank having an actinic ray-sensitive or radiation-sensitive film” and "exposed actinic ray”
- the present invention also relates to a pattern forming method including “developing a light-sensitive or radiation-sensitive film” or “developing a mask blank having an actinic ray-sensitive or radiation-sensitive film”.
- the exposure is preferably performed using an electron beam or extreme ultraviolet rays.
- exposure (pattern formation process) on the actinic ray-sensitive or radiation-sensitive film is first performed in a pattern on the actinic ray-sensitive or radiation-sensitive film of the present invention. It is preferable to perform (EUV) irradiation. Exposure in the case of electron beam 0.1 ⁇ 20 ⁇ C / cm 2, preferably about 3 ⁇ 10 ⁇ C / cm 2 or so, extreme case of ultraviolet 0.1 ⁇ 20mJ / cm 2, preferably about 3 ⁇ 15mJ / cm 2 of about It exposes so that it may become. Next, post-exposure baking (post-exposure baking) is performed on a hot plate at 60 to 150 ° C. for 1 to 20 minutes, preferably at 80 to 120 ° C.
- the developer is preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass aqueous alkaline solution such as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TBAH), preferably 0.1%.
- TMAH tetramethylammonium hydroxide
- TBAH tetrabutylammonium hydroxide
- the development is performed by a conventional method such as a dip method, a puddle method, or a spray method for ⁇ 3 minutes, more preferably 0.5 to 2 minutes.
- An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer.
- the pH of the alkali developer is usually from 10.0 to 15.0. In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.
- An appropriate amount of alcohol and / or surfactant can be added to the developer as necessary.
- the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
- fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720,
- the surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant.
- the amount of the surfactant used is usually from 0.001 to 5% by mass, preferably from 0.005 to 2% by mass, more preferably from 0.01 to 0.5% by mass, based on the total amount of the developer.
- a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
- dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
- paddle a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time
- spray method a method of spraying the developer on the substrate surface
- the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm 2 or less, More preferably, it is 1.5 mL / sec / mm 2 or less, More preferably, it is 1 mL / sec / mm 2 or less.
- the flow rate is no particular lower limit on the flow rate, but 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput.
- the developer discharge pressure (mL / sec / mm 2 ) is a value at the developing nozzle outlet in the developing device.
- Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
- a step of stopping development may be performed while substituting with another solvent.
- pure water can be used as the rinsing liquid in the rinsing treatment performed after alkali development and an appropriate amount of a surfactant can be added.
- the actinic ray-sensitive or radiation-sensitive film in the unexposed part is dissolved, and the exposed part is developed because the polymer compound is crosslinked. It is difficult to dissolve in the liquid, and the target pattern is formed on the substrate.
- the pattern forming method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8, Pages 4815-4823).
- DSA Directed Self-Assembly
- the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, Japanese Patent Application Laid-Open Nos. 3-270227 and 2013-164509.
- the present invention also relates to a photomask obtained by a method including exposing the actinic ray-sensitive or radiation-sensitive film included in the mask blank and developing the exposed film. The steps described above are applied as exposure and development.
- the photomask is suitably used for semiconductor manufacturing.
- the photomask in the present invention may be a light transmission type mask used in ArF excimer laser or the like, or a light reflection type mask used in reflection lithography using EUV light as a light source.
- the present invention also relates to a semiconductor device manufacturing method including the pattern forming method described above, and a semiconductor device manufactured by this manufacturing method.
- the semiconductor device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).
- FIG. 1 shows a 1 H-NMR (acetone-d6) chart of the compound (C-5).
- crosslinking agents (C) other than the crosslinking agents (C-5) and (C-11) were also synthesized in the same manner as described above.
- Alkali-soluble resin As the alkali-soluble resins, the following resins (A-1) to (A-8) were used.
- the composition ratio (molar ratio), weight average molecular weight (Mw), and dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn): PDI) are shown below.
- the weight average molecular weight Mw (polystyrene conversion), the number average molecular weight Mn (polystyrene conversion), and the degree of dispersion Mw / Mn (PDI) were calculated by GPC (solvent: THF) measurement.
- the composition ratio (molar ratio) was calculated by 1 H-NMR measurement.
- E-1 Benzoic acid [surfactant]
- F-1 PF6320 (manufactured by OMNOVA)
- S1 Propylene glycol monomethyl ether acetate
- S2 Propylene glycol monomethyl ether [Preparation of support] A 6-inch wafer deposited with Cr oxide (prepared with a shielding film used for ordinary photomask blanks) was prepared.
- a resist solution was applied onto the 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron. Subsequently, it dried on the hotplate for 90 seconds at 110 degreeC, and obtained the resist film with a film thickness of 80 nm. That is, resist-coated mask blanks were obtained.
- the resist film was subjected to pattern irradiation using an electron beam lithography apparatus (manufactured by Elionix Co., Ltd .; ELS-7500, acceleration voltage 50 KeV). After the irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution as a developer for 60 seconds, rinsed with pure water for 30 seconds and dried.
- an electron beam lithography apparatus manufactured by Elionix Co., Ltd .; ELS-7500, acceleration voltage 50 KeV
- methylol group concentration (mmol / g) means the total concentration (mmol / g) of hydroxymethyl group or alkoxymethyl group of the crosslinking agent (C) with respect to 1 g of solid content in the resist composition. Means.
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Abstract
Description
[1] フェノール性水酸基を有するアルカリ可溶性樹脂(A)、及び、ヒドロキシメチル基又はアルコキシメチル基を分子内に合計で2以上有する架橋剤(C)、を含有する感活性光線性又は感放射線性樹脂組成物であって、架橋剤(C)は架橋剤(C1)を含み、分子量が420以上であり、且つ、ヒドロキシメチル基又はアルコキシメチル基を分子内に合計で2~4個有し、架橋剤(C1)の含有量が、架橋剤(C)の全量に対して、60モル%~100モル%であり、架橋剤(C)が有するヒドロキシメチル基又はアルコキシメチル基の合計の濃度が、感活性光線性又は感放射線性樹脂組成物中の固形分1gに対して0.30mmol/g以上である感活性光線性又は感放射線性樹脂組成物。
R1は、各々独立に、水素原子、アルキル基、アリール基、ヒドロキシメチル基、アルコキシメチル基、又は-CH2-O-R11で表される基を表し、R11は、アリール基又はアシル基を表す。但し、分子全体において、2個以上4個以下のR1は、ヒドロキシメチル基又はアルコキシメチル基である。
R2は、水素原子、アルキル基、アリール基、又は-CO-Aで表される基を表し、Aは、アルキル基、アルコキシ基、N(R22)2を表し、R22は、炭素数4以下のアルキル基を表す。R2は、nが2以上の場合は各々独立に、水素原子、アルキル基、アリール基、又は-CO-Aで表される基を表す。
Z1は、nが1の場合は水素原子を表し、nが2以上の場合は連結基又は単結合を表す。
nは1~4の整数を表す。
X1及びX2は、各々独立に、水素原子、アルキル基、シクロアルキル基、ヒドロキシメチル基又はアルコキシメチル基を表す。但し、2つのX1の少なくとも一方は、ヒドロキシメチル基又はアルコキシメチル基である。
Y1は、2つのX1が共にヒドロキシメチル基又はアルコキシメチル基である場合は、炭素原子、窒素原子又は酸素原子を表し、1つのX1がヒドロキシメチル基でもアルコキシメチル基でもない場合、Y1は窒素原子であり、且つ、X2はヒドロキシメチル基又はアルコキシメチル基である。
Y2は、単結合、アルキレン基又はシクロアルキレン基を表す。
Z2は、有機基を表す。
nは、Y1が炭素原子のときn=2であり、Y1が窒素原子のときn=1であり、Y1が酸素原子のとき、n=0である。
X1、X2及びY2のいずれか二つが結合し、環を形成していてもよい。
R1は、各々独立に、水素原子、アルキル基、アリール基、ヒドロキシメチル基、アルコキシメチル基、又は-CH2-O-R11で表される基を表し、R11は、アリール基又はアシル基を表す。但し、分子全体において、2個以上のR1は、ヒドロキシメチル基又はアルコキシメチル基である。
Zbは、一般式(I-b)中の炭素原子と共に環を形成するのに必要な原子群を表し、この環は置換基を有していてもよい。
[5] 架橋剤(C1)は、下記一般式(I-c)で表される化合物である[1]~[4]のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
Rは、各々独立に、アルキル基又はシクロアルキル基を表す。
R1cは、各々独立に、アルキル基を表す。
Zcは、式中の炭素原子と共に環を形成するのに必要な原子群を表し、この環は置換基を有していてもよい。
Aは、硫黄原子又はヨウ素原子を表し、
R1は、水素原子又は有機基を表し、R1が複数存在する場合、R1は同一であっても異なっていてもよく、
Rは、(o+1)価の有機基を表し、Rが複数存在する場合、Rは同一であっても異なっていてもよく、
Xは、単結合又は連結基を表し、Xが複数存在する場合、Xは同一であっても異なっていてもよく、
ANは、窒素原子を含んだ塩基性部位を表し、ANが複数存在する場合、ANは同一であっても異なっていてもよく、
Aが硫黄原子である場合、nは、1~3の整数であり、mは、m+n=3なる関係を満たす整数であり、
Aがヨウ素原子である場合、nは、1又は2であり、mは、m+n=2なる関係を満たす整数であり、
oは、1~10の整数を表し、
Y-は、アニオンを表し、
R1、X、R、ANの少なくとも2つは、互いに結合して、環を形成していてもよい。
[9] [8]に記載の感活性光線性又は感放射線性膜を備えたマスクブランクス。
[10] [9]に記載のマスクブランクスが備える感活性光線性又は感放射線性膜を露光すること、露光した感活性光線性又は感放射線性膜を現像することを含む方法により製造されたフォトマスク。
- 該膜を露光すること、及び
- 該露光された膜を、現像液を用いて現像してパターンを形成すること
を含むパターン形成方法。
[12] 前記露光がX線、電子線又はEUVを用いて行われる、[11]に記載のパターン形成方法。
[14] [13]に記載の電子デバイスの製造方法によって製造された電子デバイス。
以下、本発明の実施形態について詳細に説明する。
本発明の感活性光線性又は感放射線性樹脂組成物は、後述するフェノール性水酸基を有するアルカリ可溶性樹脂と、分子量が420以上で且つ、ヒドロキシメチル基又はアルコキシメチル基を分子内に合計で2~4個有する架橋剤(以下、「架橋剤(C1)」ともいう)を含有する。
本発明の組成物は、本発明の組成物に含有される架橋剤(C)の全量に対し、架橋剤(C1)を60モル%~100モル%の割合で含有し、且つ、架橋剤(C)が有するヒドロキシメチル基又はアルコキシメチル基の合計濃度が、本発明の組成物中の固形分1gに対して0.30mmol/g以上となる。ここで、「架橋剤(C)」とは、ヒドロキシメチル基又はアルコキシメチル基を分子内に合計で2以上有する架橋剤を意味し、本発明の架橋剤(C1)も含まれる。
架橋剤(C1)は、上述の通り、分子量が420以上で且つ、ヒドロキシメチル基又はアルコキシメチル基を分子内に合計で2~4個有する化合物である。
本発明の一形態において、架橋剤(C1)におけるヒドロキシメチル基又はアルコキシメチル基の数は、2個であることが好ましく、また、ヒドロキシメチル基又はアルコキシメチル基は、芳香族環またはヘテロ原子に結合していることが好ましい。
R1は、各々独立に、水素原子、アルキル基、アリール基、ヒドロキシメチル基、アルコキシメチル基、又は-CH2-O-R11で表される基を表し、R11は、アリール基又はアシル基を表す。但し、分子全体において、2個以上4個以下のR1は、ヒドロキシメチル基又はアルコキシメチル基である。
R2は、水素原子、アルキル基、アリール基、又は-CO-Aで表される基を表し、Aは、アルキル基、アルコキシ基、N(R22)2を表し、R22は、炭素数4以下のアルキル基を表す。R2は、nが2以上の場合は各々独立に、水素原子、アルキル基、アリール基、又は-CO-Aで表される基を表す。
Z1は、nが1の場合は水素原子を表し、nが2以上の場合は連結基又は単結合を表す。
nは1~4の整数を表す。
Z1は、上記の通り、nが1の場合は水素原子を表し、nが2以上の場合は連結基を表す。Z1は、2~4価の連結基であることが好ましく、2価の連結基であることがより好ましい。
Z1により表される連結基は、特に限定されるものではなく、例えばZ1が2価の連結基の場合の具体例としては、アルキレン基、アリーレン基、又はこれらの2以上を組み合わせた基が挙げられ、これら連結基は更に置換基を有していてもよい。
R1は、一般式(I)のR1と同義である。
R3及びR4により表される有機基としては、例えば、アルキル基、シクロアルキル基、アリール基等が挙げられ、また、R3及びR4が互いに結合して形成して以下に詳述する環を形成していることが好ましい。
架橋剤(C1)は、例えば、一般式(I-B)中のR3及びR4が結合して、下記一般式(I-d)で表されるフルオレン構造を形成していることが好ましい。
R7及びR8は、各々独立に、置換基を表す。該置換基としては、例えば、アルキル基、シクロアルキル基、アルコキシ基、アリール基、アルコキシメチル基、アシル基、アルコキシカルボニル基、ニトロ基、ハロゲン原子、又はヒドロキシ基等が挙げられる。
R1は、一般式(I)のR1と同義である。
Zbは、式中の炭素原子と共に環を形成するのに必要な原子群を表し、この環は置換基を有していてもよい。
Zbが式中の炭素原子と共に形成する環については、上述した一般式(I-B)の説明において、R3及びR4が互いに結合して形成する環について説明したものと同様である。
また、本発明の一形態において、架橋剤(C)は、下記一般式(I-c)で表されることが好ましい。
Rは、各々独立に、アルキル基又はシクロアルキル基を表す。
R1cは、各々独立に、アルキル基を表す。
Zcは、式中の炭素原子と共に環を形成するのに必要な原子群を表し、この環は置換基を有していてもよい。
また、本発明の他の形態において、架橋剤(C1)は、下記一般式(I-e)、(I-f)又は(I-g)で表されることが好ましい。式中、R1は、一般式(I)のR1と同義である。
X1及びX2は、各々独立に、水素原子、アルキル基、シクロアルキル基、ヒドロキシメチル基又はアルコキシメチル基を表す。但し、2つのX1の少なくとも一方は、ヒドロキシメチル基又はアルコキシメチル基である。
Z2は、有機基を表す。
nは、Y1が炭素原子のときn=2であり、Y1が窒素原子のときn=1であり、Y1が酸素原子のときn=0である。
X1およびX2としてのアルキル基は、置換基を有していてもよい。
X1およびX2としてのシクロアルキル基は、置換基を有していてもよい。
上述したように、本発明の組成物中の固形分1gに対する架橋剤(C1)が有するヒドロキシメチル基又はアルコキシメチル基の合計濃度が、0.30mmol/g以上となる割合で、架橋剤(C1)を含有する。本発明の一形態において、本発明の組成物中の固形分1gに対する架橋剤(C)が有するヒドロキシメチル基又はアルコキシメチル基の合計濃度は、0.30~1.00mmol/gであることが好ましく、0.40~0.90mmol/gであることがより好ましく、0.60~0.80mmol/gであることがさらに好ましい。
架橋剤(C)の含有量は、本発明の感活性光線性又は感放射線性樹脂組成物の固形分を基準として、好ましくは1~50質量%であり、より好ましくは2~40質量%であり、さらに好ましくは5~20質量%であり、特に好ましくは10~15質量%である。
本発明の感活性光線性又は感放射線性樹脂組成物は、フェノール性水酸基を有するアルカリ可溶性樹脂(以下、「樹脂(A)」ともいう)を含有する。
本発明におけるフェノール性水酸基とは、芳香環基の水素原子をヒドロキシ基で置換してなる基である。該芳香環基の芳香環は単環又は多環の芳香環であり、ベンゼン環やナフタレン環等が挙げられる。
R2は、水素原子、置換基を有していてもよいメチル基、又はハロゲン原子(好ましくはフッ素原子)を表し;
B’は、単結合又は2価の連結基を表し;
Ar’は、芳香族環を表し;
mは1以上の整数を表す。
R2は、水素原子又はメチル基であることが好ましく、水素原子であることが現像性の理由から好ましい。
B’は、単結合、カルボニルオキシ基(-C(=O)-O-)又は-C(=O)-NH-を表すことが好ましく、単結合又はカルボニルオキシ基(-C(=O)-O-)を表すことがより好ましく、単結合であることがドライエッチング耐性向上の観点で特に好ましい。
R12は、水素原子又はメチル基を表す。
Arは、芳香族環を表す。
R12は、水素原子又はメチル基を表し、水素原子であることが現像性の理由から好ましい。
より具体的には、非酸分解性の炭化水素構造を有する基は、酸及びアルカリに安定な基であることが好ましい。酸及びアルカリに安定な基とは、酸分解性及びアルカリ分解性を示さない基を意味する。ここで酸分解性とは、光酸発生剤が発生する酸及び後述する酸発生構造(a)が発生する酸の作用によって、分解反応を起こす性質を意味する。
炭化水素構造を有する基とは、炭化水素構造を有する一価の基である限り特に限定されないが、総炭素数が5~40であることが好ましく、7~30であることがより好ましい。炭化水素構造は、環内に不飽和結合を有していてもよい。
これらの炭化水素構造の化学式を以下に表示する。
炭化水素構造を有する基としては、上記の炭化水素構造の任意の一つの水素原子を結合手とした一価の基であることが好ましい。
一般式(1)のArの芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フルオレン環、フェナントレン環などの炭素数6~18の置換基を有していてもよい芳香族炭化水素環、又は、例えば、チオフェン環、フラン環、ピロール環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、トリアジン環、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアジアゾール環、チアゾール環等のヘテロ環を含む芳香環ヘテロ環を挙げることができる。中でも、ベンゼン環、ナフタレン環が解像性の観点で好ましく、ベンゼン環が最も好ましい。
Lは、単結合、カルボニルオキシ基(-C(=O)-O-)又は-C(=O)-NH-を表すことが好ましく、単結合又はカルボニルオキシ基(-C(=O)-O-)を表すことがより好ましく、単結合であることがドライエッチング耐性向上の観点で特に好ましい。
一般式(4)で表される繰り返し単位を有する樹脂(A)を使用すると、樹脂(A)のTgが高くなり、非常に硬いレジスト膜を形成するため、酸の拡散性やドライエッチング耐性をより確実に制御できる。
Yは単結合又は2価の連結基を表す。
X2は非酸分解性の炭化水素基を表す。
一般式(4)におけるR13は水素原子又はメチル基を表すが、水素原子が特に好ましい。
このような炭化水素基は、鎖状、分岐の炭化水素基、単環型の脂環炭化水素基を有する基、若しくは、多環型の脂環炭化水素基であり、有橋式であってもよい。単環型の脂環炭化水素基としては、炭素数3~8のシクロアルキル基が好ましく、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロブチル基、シクロオクチル基等を挙げることができ、これらの基を複数有してもよい。単環型の脂環炭化水素基を複数有する場合は、単環型の脂環炭化水素基を2~4個有することが好ましく、2個有することが特に好ましい。
一般式(4)における-O-Y-X2の置換位置はベンゼン環のポリマー主鎖との結合位置に対して、パラ位でもメタ位でもオルト位でもよいが、パラ位が好ましい。
一般式(4’)におけるR13は水素原子又はメチル基を表すが、水素原子が特に好ましい。
一般式(4’)におけるアダマンチルエステル基の置換位置はベンゼン環のポリマー主鎖との結合位置に対して、パラ位でもメタ位でもオルト位でもよいが、パラ位が好ましい。
繰り返し単位(Q)は、置換基を有していてもよいメチロール基を少なくとも1つ含む構造である。
ここで、「メチロール基」とは、下記一般式(M)で表される基であり、本発明の一形態において、ヒドロキシメチル基又はアルコキシメチル基であることが好ましい。
R1は、水素原子、メチル基、又はハロゲン原子を表す。
R2及びR3は、水素原子、アルキル基又はシクロアルキル基を表す。
Lは、2価の連結基もしくは単結合を表す。
Yは、メチロール基を除く1価の置換基を表す。
Zは、水素原子又は置換基を表す。
mは、0~4の整数を表す。
nは、1~5の整数を表す。
m+nは5以下である。
mが2以上である場合、複数のYは互いに同一であっても異なっていてもよい。
nが2以上である場合、複数のR2、R3及びZは互いに同一であっても異なっていてもよい。
また、Y、R2、R3及びZの2つ以上が互いに結合して環構造を形成していてもよい。ここで、「Y、R2、R3及びZの2つ以上が互いに結合して環構造を形成する」とは、同じ記号で表される基が複数ある場合には同じ記号で表される基同士で結合して環構造を形成していてもよく、あるいは、異なる記号で表される基が互いに結合して環を形成していてもよいことを意味する。
R1は、水素原子又はメチル基であることが好ましい。
Lで表される2価の連結基は、置換基を有していてもよく、この置換基としては、Yで表される1価の置換基が有する置換基として後述するものと同様のものが挙げられる。
また、mが2以上の時、複数のYが単結合又は連結基を介して互いに結合し、環構造を形成していてもよい。この場合の連結基としては、エーテル結合、チオエーテル結合、エステル結合、アミド結合、カルボニル基、アルキレン基等が挙げられる。
ハロアルキル基としては、少なくとも1つ以上の水素原子がフッ素原子、塩素原子、臭素原子、及びヨウ素原子で置換された炭素数1~12のアルキル基、シクロアルキル基が挙げられる。具体例としては、フルオロメチル基、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ウンデカフルオロシクロヘキシル基が挙げられる。
アルカノイル基としては、炭素数2~20のアルカノイル基が好ましく、例えば、アセチル基、プロパノイル基、ブタノイル基、トリフルオロメチルカルボニル基、ペンタノイル基、ベンゾイル基、1-ナフトイル基、2-ナフトイル基、4-メチルスルファニルベンゾイル基、4-フェニルスルファニルベンゾイル基、4-ジメチルアミノベンゾイル基、4-ジエチルアミノベンゾイル基、2-クロロベンゾイル基、2-メチルベンゾイル基、2-メトキシベンゾイル基、2-ブトキシベンゾイル基、3-クロロベンゾイル基、3-トリフルオロメチルベンゾイル基、3-シアノベンゾイル基、3-ニトロベンゾイル基、4-フルオロベンゾイル基、4-シアノベンゾイル基及び4-メトキシベンゾイル基が挙げられる。
アリールチオ基としては、炭素数6~30のアリールチオ基が挙げられ、例えば、フェニルチオ基、1-ナフチルチオ基、2-ナフチルチオ基、トリルチオ基、メトキシフェニルチオ基、ナフチルチオ基、クロロフェニルチオ基、トリフルオロメチルフェニルチオ基、シアノフェニルチオ基及びニトロフェニルチオ基が挙げられる。
R1、R2、R3、Y、Z、m及びnは、前記一般式(Q-1)で定義した通りである。
Arは、芳香環を表す。
W1及びW2は、2価の連結基又は単結合を表す。
Arで表される芳香環の具体例としては、上記一般式(Q-1)におけるLが芳香環である場合の具体例と同様のものが挙げられ、好ましい範囲も同様である。
上記一般式(3’)において、W3は、2価の連結基である。W3で表される2価の連結基としては、炭素数6~18の置換基を有しても良い単環もしくは多環の芳香族炭化水素環、-C(=O)-、直鎖状若しくは分岐状のアルキレン基(好ましくは炭素数1~10、より好ましくは1~6)、シクロアルキレン基(好ましくは炭素数3~10、より好ましくは5~10)、-O-、環状ラクトン構造又はこれらを組み合わせた2価の連結基が挙げられる。
上記一般式(2’)及び(3’)において、gは0又は1である。
上記一般式(1-b)~(1-c)において、
Y”は、水素原子又は1価の置換基を表す。1価の置換基としては、上述したYで表される1価の置換基と同様のものが挙げられる。ただし、Y”は、メチロール基であってもよい。
R4は、水素原子又は1価の置換基を表す。1価の置換基の具体例は、一般式(Q-1)におけるZが1価の置換基である場合と同様のものが挙げられる。
fは1~6の整数を表す。好ましい範囲は、一般式(2’)で述べた通りである。
mは0又は1であり、nは1~3の整数を表す。
繰り返し単位(Q)の具体例としては、下記構造が挙げられる。
R41は上述したように水素原子又はメチル基であり、水素原子がより好ましい。
R201~R203は、各々独立に、有機基を表す。
R201~R203としての有機基の炭素数は、一般的に1~30、好ましくは1~20である。
これら他の繰り返し単位を形成するための重合性モノマーの例としてはスチレン、アルキル置換スチレン、アルコキシ置換スチレン、ハロゲン置換スチレン、O-アルキル化スチレン、O-アシル化スチレン、水素化ヒドロキシスチレン、無水マレイン酸、アクリル酸誘導体(アクリル酸、アクリル酸エステル等)、メタクリル酸誘導体(メタクリル酸、メタクリル酸エステル等)、N-置換マレイミド、アクリロニトリル、メタクリロニトリル、ビニルナフタレン、ビニルアントラセン、置換基を有しても良いインデン等を挙げることができる。
樹脂(A)の重量平均分子量は、好ましくは1000~200000であり、更に好ましくは2000~50000であり、更により好ましくは2000~15000である。
本発明の組成物における樹脂(A)の含有率は、組成物の全固形分に対して、好ましくは30~95質量%、より好ましくは40~90質量%、特に好ましくは50~85質量%で用いられる。
本発明の組成物は、活性光線又は放射線の照射により酸を発生する化合物(以下、「酸発生剤」、「光酸発生剤」又は「化合物(B)」と略称する)を含有していてもよい。
酸発生剤の好ましい形態として、オニウム化合物を挙げることができる。そのようなオニウム化合物としては、例えば、スルホニウム塩、ヨードニウム塩、ホスホニウム塩などを挙げることができる。
Ra1、Ra2、Ra3、Ra4及びRa5は、各々独立に、有機基を表す。
Xfは、各々独立に、フッ素原子、又は、少なくとも1つのフッ素原子で置換されたアルキル基を表す。
R1及びR2は、各々独立に、水素原子、又は、アルキル基を表す。
Lは、各々独立に、2価の連結基を表す。
Cyは、環状の有機基を表す。
Rfは、フッ素原子を含んだ基を表す。
xは、1~20の整数を表す。
yは、0~10の整数を表す。
zは、0~10の整数を表す。
酸発生剤は、1種単独で又は2種以上を組合せて使用することができる。
本発明の組成物には、前記成分の他に、塩基性化合物を酸捕捉剤として含有することが好ましい。塩基性化合物を用いることにより、露光から後加熱までの経時による性能変化を小さくすることできる。このような塩基性化合物としては、有機塩基性化合物であることが好ましく、より具体的には、脂肪族アミン類、芳香族アミン類、複素環アミン類、カルボキシル基を有する含窒素化合物、スルホニル基を有する含窒素化合物、ヒドロキシ基を有する含窒素化合物、ヒドロキシフェニル基を有する含窒素化合物、アルコール性含窒素化合物、アミド誘導体、イミド誘導体等が挙げられる。アミンオキサイド化合物(メチレンオキシ単位及び/又はエチレンオキシ単位を有するものが好ましく、例えば特開2008-102383号公報に記載の化合物が挙げられる。)、アンモニウム塩(好ましくはヒドロキシド又はカルボキシレートである。より具体的にはテトラブチルアンモニウムヒドロキシドに代表されるテトラアルキルアンモニウムヒドロキシドがLERの観点で好ましい。)も適宜用いられる。
Aは、硫黄原子又はヨウ素原子を表す。
R1は、水素原子又は有機基を表す。R1が複数存在する場合、R1は同一であっても異なっていてもよい。
Rは、(o+1)価の有機基を表す。Rが複数存在する場合、Rは同一であっても異なっていてもよい。
Xは、単結合又は連結基を表す。Xが複数存在する場合、Xは同一であっても異なっていてもよい。
ANは、窒素原子を含んだ塩基性部位を表す。ANが複数存在する場合、ANは同一であっても異なっていてもよい。
Aが硫黄原子である場合、nは、1~3の整数であり、mは、m+n=3なる関係を満たす整数である。
Aがヨウ素原子である場合、nは、1又は2であり、mは、m+n=2なる関係を満たす整数である。
oは、1~10の整数を表す。
Y-は、アニオンを表す(詳細は、化合物(D1)のアニオン部として後述する通りである)。
R1、X、R、ANの少なくとも2つは、互いに結合して、環を形成していてもよい。
Xにより表される連結基は、上述した一般式(N-I)中のXにより表される連結基と同義であり、同様の具体例が挙げられる。
R1により表されるアルキル基は、直鎖状であってもよく、分岐鎖状であってもよい。このアルキル基の炭素数は、1~50であることが好ましく、1~30であることがより好ましく、1~20であることが更に好ましい。このようなアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、オクタデシル基、イソプロピル基、イソブチル基、sec-ブチル基、t-ブチル基、1-エチルペンチル基、及び、2-エチルヘキシル基が挙げられる。
R1により表される脂肪族環式基は、例えば、シクロアルキル基である。シクロアルキル基は、単環式であってもよく、多環式であってもよい。この脂肪族環式基としては、好ましくは、シクロプロピル基、シクロペンチル基及びシクロヘキシル基等の炭素数3~8の単環のシクロアルキル基が挙げられる。
R1により表される複素環式炭化水素基は、芳香族性を有していてもよく、芳香族性を有していなくてもよい。この複素環式炭化水素基は、芳香族性を有していることが好ましい。
R1、X、R、ANの少なくとも2つが互いに結合して形成してもよい環は、4~7員環であることが好ましく、5又は6員環であることがより好ましく、5員環であることが特に好ましい。また、環骨格中に、酸素原子、硫黄原子、窒素原子などのヘテロ原子を含んでいても良い。
一般式(N-II)において、oは、1~4の整数であることが好ましく、1又は2であることがより好ましく、1であることが更に好ましい。
即ち、この態様における化合物(D1)では、ANにより表される塩基性部位が、Rにより表される芳香族炭化水素基に直結した炭素原子を介して、上記芳香族炭化水素基に結合している。
芳香環基は、炭素数が6~14であることが好ましい。このような基としては、例えば、フェニル基、ナフチル基、及びアントリル基等のアリール基が挙げられる。芳香環基が複素環を含んでいる場合、複素環としては、例えば、チオフェン環、フラン環、ピロール環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、トリアジン環、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアジアゾール環、及びチアゾール環が挙げられる。
Rにより表される芳香族炭化水素基は、以下に説明する-(X-AN)により表される基以外に、置換基を更に備えていてもよい。置換基としては、例えば、先にR1における置換基として列挙したものを用いることができる。
Xにより表される連結基が含み得るシクロアルキレン基は、単環式であってもよく、多環式であってもよい。このシクロアルキレン基の炭素数は、3~20であることが好ましく、3~10であることがより好ましい。このようなシクロアルキレン基としては、例えば、1,4-シクロヘキシレン基が挙げられる。
Xにより表される連結基が含み得るアリーレン基の炭素数は、6~20であることが好ましく、6~10であることがより好ましい。このようなアリーレン基としては、例えば、フェニレン基及びナフチレン基が挙げられる。
R2及びR3は、水素原子、アルキル基、アルケニル基、脂肪族環式基、芳香族炭化水素基、又は複素環式炭化水素基を表す。R2とR3とは、互いに結合して、環を形成していてもよい。R2及びR3の少なくとも一方は、Eと互いに結合して、環を形成していてもよい。
Eは、連結基又は単結合を表す。
Jは、酸素原子、又は、硫黄原子を表す。
Eは、連結基又は単結合を表す。
R14は複数存在する場合は各々独立して、水酸基、アルキル基、シクロアルキル基、アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基、又はシクロアルキル基を有する基を表す。これらの基は置換基を有してもよい。
rは0~8の整数を表す。
rとしては、0~2が好ましい。
Aは、硫黄原子又はヨウ素原子を表す。
R11は、各々独立に、アルキル基、アルケニル基、脂肪族環式基、芳香族炭化水素基、又は複素環式炭化水素基を表す。m=2の場合、2つのR11が互いに結合して、環を形成していてもよい。
Arは、各々独立に、芳香族炭化水素基を表す。
X1は、各々独立に、2価の連結基を表す。
R12は、各々独立に、水素原子又は有機基を表す。
前記Aが硫黄原子である場合、mは、1~3の整数であり、nは、m+n=3なる関係を満たす整数である。
前記Aがヨウ素原子である場合、mは、1又は2の整数であり、nは、m+n=2なる関係を満たす整数である。
Y-は、アニオンを表す(詳細は、化合物(D1)のアニオン部として後述する通りである)。
Arとしての芳香族炭化水素基の具体例及び好ましい例は、上記一般式(N-II)におけるRとしての芳香族炭化水素基の具体例及び好ましい例と同様である。
R12としての有機基の具体例及び好ましい例は、上記一般式(N-I)におけるRA及びRBとしての有機基の具体例及び好ましい例と同様である。
スルホン酸アニオンとしては、例えば、脂肪族スルホン酸アニオン、芳香族スルホン酸アニオン、カンファースルホン酸アニオンなどが挙げられる。
カルボン酸アニオンとしては、例えば、脂肪族カルボン酸アニオン、芳香族カルボン酸アニオン、アラルキルカルボン酸アニオンなどが挙げられる。
芳香族スルホン酸アニオンにおける芳香族基としては、好ましくは炭素数6~14のアリール基、例えば、フェニル基、トリル基、ナフチル基等を挙げることができる。
芳香族カルボン酸アニオンにおける芳香族基としては、芳香族スルホン酸アニオンにおけると同様のアリール基を挙げることができる。
アラルキルカルボン酸アニオンにおけるアラルキル基としては、好ましくは炭素数6~12のアラルキル基、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ナフチルエチル基、ナフチルブチル基等を挙げることができる。
スルホニルイミドアニオンとしては、例えば、サッカリンアニオンを挙げることができる。
非求核性アニオンとしては、スルホン酸のα位がフッ素原子で置換された脂肪族スルホン酸アニオン、フッ素原子又はフッ素原子を有する基で置換された芳香族スルホン酸アニオン、アルキル基がフッ素原子で置換されたビス(アルキルスルホニル)イミドアニオン、アルキル基がフッ素原子で置換されたトリス(アルキルスルホニル)メチドアニオンが好ましい。非求核性アニオンとして、より好ましくは炭素数4~8のパーフロロ脂肪族スルホン酸アニオン、フッ素原子を有するベンゼンスルホン酸アニオン、更により好ましくはノナフロロブタンスルホン酸アニオン、パーフロロオクタンスルホン酸アニオン、ペンタフロロベンゼンスルホン酸アニオン、3,5-ビス(トリフロロメチル)ベンゼンスルホン酸アニオンである。
また、化合物(D1)は、(化合物中に含まれる全フッ素原子の質量の合計)/(化合物中に含まれる全原子の質量の合計)により表されるフッ素含有率が0.30以下であることが好ましく、0.25以下であることがより好ましく、0.20以下であることが更に好ましく、0.15以下であることが特に好ましく、0.10以下であることが最も好ましい。
本発明で使用される塩基性化合物の含有量は、本発明の組成物の全固形分に対して、0.01~20質量%が好ましく、0.03~15質量%がより好ましく、0.05~13質量%がさらに好ましく、5~13質量%が特に好ましい。
本発明の組成物は、更に、塗布性を向上させるため界面活性剤を含有してもよい。界面活性剤の例としては、特に限定されるものではないが、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アルキルアリルエーテル類、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、ソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタン脂肪酸エステルなどのノニオン系界面活性剤、メガファックF171(大日本インキ化学工業製)やフロラードFC430(住友スリーエム製)やサーフィノールE1004(旭硝子製)、OMNOVA社製のPF656及びPF6320、等のフッ素系界面活性剤、オルガノシロキサンポリマーが挙げられる。
感活性光線性又は感放射線性樹脂組成物が界面活性剤を含有する場合、界面活性剤の使用量は、該組成物の全量(溶剤を除く)に対して、好ましくは0.0001~5質量%、より好ましくは0.0005~4質量%である。
本発明の組成物には、前記成分の他に、有機カルボン酸を含有することが好ましい。このような有機カルボン酸化合物として、脂肪族カルボン酸、脂環式カルボン酸、不飽和脂肪族カルボン酸、オキシカルボン酸、アルコキシカルボン酸、ケトカルボン酸、安息香酸誘導体、フタル酸、テレフタル酸、イソフタル酸、2-ナフトエ酸、1-ヒドロキシ-2-ナフトエ酸、2-ヒドロキシ-3-ナフトエ酸などを挙げることができるが、電子線露光を真空化で行なう際にはレジスト膜表面より揮発して描画チャンバー内を汚染してしまう恐れがあるので、好ましい化合物としては、芳香族有機カルボン酸、その中でも例えば安息香酸、1-ヒドロキシ-2-ナフトエ酸、2-ヒドロキシ-3-ナフトエ酸が好適である。
本発明の組成物は、カルボン酸オニウム塩を含有してもよい。カルボン酸オニウム塩としては、カルボン酸スルホニウム塩、カルボン酸ヨードニウム塩、カルボン酸アンモニウム塩などを挙げることができる。特に、カルボン酸オニウム塩としては、カルボン酸ヨードニウム塩、カルボン酸スルホニウム塩が好ましい。更に、本発明においては、カルボン酸オニウム塩のカルボキシレート残基が芳香族基、炭素-炭素2重結合を含有しないことが好ましい。特に好ましいアニオン部としては、炭素数1~30の直鎖、分岐、単環若しくは多環環状アルキルカルボン酸アニオンが好ましい。更に好ましくはこれらのアルキル基の一部又は全てがフッ素置換されたカルボン酸のアニオンが好ましい。またアルキル鎖中に酸素原子を含んでいても良い。これにより220nm以下の光に対する透明性が確保され、感度、解像力が向上し、疎密依存性、露光マージンが改良される。
本発明の組成物に使用される溶剤としては、例えば、エチレングリコールモノエチルエーテルアセテート、シクロヘキサノン、2-ヘプタノン、プロピレングリコールモノメチルエーテル(PGME、別名1-メトキシ-2-プロパノール)、プロピレングリコールモノメチルエーテルアセテート(PGMEA、別名1-メトキシ-2-アセトキシプロパン)、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルアセテート、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、β-メトキシイソ酪酸メチル、酪酸エチル、酪酸プロピル、メチルイソブチルケトン、酢酸エチル、酢酸イソアミル、乳酸エチル、トルエン、キシレン、酢酸シクロヘキシル、ジアセトンアルコール、N-メチルピロリドン、N,N-ジメチルホルムアミド、γ-ブチロラクトン、N,N-ジメチルアセトアミド、プロピレンカーボネート、エチレンカーボネートなどが好ましい。これらの溶剤は単独若しくは組合せて用いられる。
本発明は、「上記感活性光線性又は感放射線性膜を露光すること」又は「感活性光線性又は感放射線性膜を備えるマスクブランクスを露光すること」、及び、「露光された感活性光線性又は感放射線性膜を現像すること」又は「感活性光線性又は感放射線性膜を備えるマスクブランクスを現像すること」を含む、パターン形成方法にも関する。本発明において、前記露光が電子線又は極紫外線を用いて行われることが好ましい。
界面活性剤の使用量は現像液の全量に対して、通常0.001~5質量%、好ましくは0.005~2質量%、更に好ましくは0.01~0.5質量%である。
本発明の半導体デバイスは、電気電子機器(家電、OA・メディア関連機器、光学用機器及び通信機器等)に、好適に、搭載されるものである。
9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン(和光純薬)18.8g、50%ジメチルアミン水溶液19.8g、パラホルムアルデヒド6.6g、エタノール10mLの混合物を80℃で2時間攪拌した。エタノールを留去した後、酢酸エチル50mLと水50mLをこの混合物に加えて分液操作を行い、有機層を水50mLで2回洗浄した。得られた有機層を硫酸マグネシウムで乾燥後ろ過し、ろ液の溶媒を留去することで、粗生成物として(C-5A)23.4g(収率95%)を得た。
上記で得られた化合物(C-5A)23.4gに無水酢酸37.2gを加え、80℃で6時間攪拌した。放冷した後、酢酸と無水酢酸を留去し、化合物(C-5B)27.1gを得た。得られた化合物(C-5B)はこれ以上の精製は行うことなく、化合物(C-5)の合成に使用した。
上記で得られた化合物(C-5B)27.1gにメタノール58gと炭酸カリウム6.9gを加え、この混合物を60℃で2時間攪拌した。放冷した後、メタノールを留去した。酢酸エチル100mLと水100mLをこの混合物に加えて分液操作を行い、有機層を1N塩酸水溶液100mLで洗浄し、さらに水100mLで3回洗浄した。得られた有機層を硫酸マグネシウムで乾燥し、乾燥剤をろ過し、ろ液の溶媒を留去することで、化合物(C-5)を19.8g得た(トータル収率85%)。図1に、化合物(C-5)の1H-NMR(acetone-d6)チャートを示す。
フラスコ中で、化合物1(4g)、ケトプロフェン(10g)及びアセトニトリル(80g)を混合した後、この混合液に、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(15g)と、ジメチルアミノピリジン(0.24g)とを加え、室温で3時間攪拌した。得られた化合物を含む反応液を水200gに注ぎ、酢酸エチル200gを加えて抽出を行った。次いで、得られた有機層を水洗(水200g×3回)した後、濃縮し、化合物C-11Aの粗生成物12gを得た。
特開2012-31233号公報の段落0044~0047に記載の方法を用いて、12gの化合物C-11Aから15gの粗生成物C-11を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィーにて精製し、3.3gの化合物C-11を得た。
アルカリ可溶性樹脂として、下記に示す樹脂(A-1)~(A-8)を使用した。組成比(モル比)、重量平均分子量(Mw)及び分散度(重量平均分子量(Mw)/数平均分子量(Mn):PDI)を以下に示す。
E-1:安息香酸
〔界面活性剤〕
F-1:PF6320(OMNOVA(株)製)
〔溶剤〕
S1:プロピレングリコールモノメチルエーテルアセテート
S2:プロピレングリコールモノメチルエーテル
〔支持体の準備〕
酸化Cr蒸着した6インチウェハー(通常のフォトマスクブランクスに使用する遮蔽膜処理を施したもの)を準備した。
下記表に示す成分を溶剤に溶解させ、それぞれについて固形分濃度3.5質量%の溶液を調製し、これを0.03μmのポアサイズを有するポリテトラフルオロエチレンフィルターで精密濾過してレジスト溶液を得た。
上記6インチウェハー上に東京エレクトロン製スピンコーターMark8を用いてレジスト溶液を塗布した。次いで、110℃、90秒間ホットプレート上で乾燥して、膜厚80nmのレジスト膜を得た。すなわち、レジスト塗布マスクブランクスを得た。
このレジスト膜に電子線描画装置((株)エリオニクス社製;ELS-7500、加速電圧50KeV)を用いて、パターン照射を行った。照射後に、110℃、90秒間ホットプレート上で加熱し、現像液として2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液に60秒間浸漬した後、30秒間、純水でリンスして乾燥した。
得られたレジストパターンについて、下記の方法によって、解像力、ラインエッジラフネス(LER)、CDU、及びエッチング耐性を評価した。
得られたパターンの断面形状を、走査型電子顕微鏡((株)日立製作所製S-4300)を用いて観察した。線幅100nm(ライン:スペース=1:1)のレジストパターンを解像するときの露光量(電子線照射量)における限界解像力(ラインとスペース(ライン:スペース=1:1)とが分離解像する最小の線幅)を解像力(nm)とした。
上記の感度を示す露光量で、線幅100nmのラインパターン(L/S=1/1)を形成した。そして、その長さ方向50μmにおける任意の30点について、走査型電子顕微鏡((株)日立製作所製S-9220)を用いて、エッジがあるべき基準線からの距離を測定した。そして、この距離の標準偏差を求め、3σを算出した。値が小さいほど良好な性能であることを示す。
上記の感度を示す露光量で線幅100nm(ライン:スペース=1:1)のレジストパターンを形成したレジスト膜を、HITACHI U-621でAr/C4F6/O2ガス(体積比率100/4/2の混合ガス)を用いて15秒間ドライエッチングを行った。その後レジスト残膜率を測定し、以下の指標に基づいてドライエッチング耐性を評価した。
良好(B):残膜率95%未満90%以上
不良(C):残膜率90%未満
〔線幅の面内均一性(CDU)〕
ラインアンドスペース1:1パターンの線幅が100nmとなる露光量において、各ラインパターン中の100個の線幅を測定し、その測定結果から算出した平均値の標準偏差(σ)の3倍値(3σ)を求めて線幅の面内均一性(CDU)(nm)を評価した。以上から求められる3σは、その値が小さいほど、当該レジスト膜に形成された各ラインCDの面内均一性(CDU)が高いことを意味する。
Claims (14)
- フェノール性水酸基を有するアルカリ可溶性樹脂(A)、及び、
ヒドロキシメチル基又はアルコキシメチル基を分子内に合計で2以上有する架橋剤(C)、
を含有する感活性光線性又は感放射線性樹脂組成物であって、
架橋剤(C)は架橋剤(C1)を含み、
架橋剤(C1)は、分子量が420以上であり、且つ、ヒドロキシメチル基又はアルコキシメチル基を分子内に合計で2~4個有し、
架橋剤(C1)の含有量が、架橋剤(C)の全量に対して、60モル%~100モル%であり、
架橋剤(C)が有するヒドロキシメチル基又はアルコキシメチル基の合計の濃度が、前記感活性光線性又は感放射線性樹脂組成物中の固形分1gに対して0.30mmol/g以上である感活性光線性又は感放射線性樹脂組成物。
- 架橋剤(C1)は、下記一般式(I)又は(II)で表される化合物である請求項1に記載の感活性光線性又は感放射線性樹脂組成物。
R1は、各々独立に、水素原子、アルキル基、アリール基、ヒドロキシメチル基、アルコキシメチル基、又は-CH2-O-R11で表される基を表し、R11は、アリール基又はアシル基を表す。但し、分子全体において、2個以上4個以下のR1は、ヒドロキシメチル基又はアルコキシメチル基である。
R2は、水素原子、アルキル基、アリール基、又は-CO-Aで表される基を表し、Aは、アルキル基、アルコキシ基、N(R22)2を表し、R22は、炭素数4以下のアルキル基を表す。R2は、nが2以上の場合は各々独立に、水素原子、アルキル基、アリール基、又は-CO-Aで表される基を表す。
Z1は、nが1の場合は水素原子を表し、nが2以上の場合は連結基又は単結合を表す。
nは1~4の整数を表す。
一般式(II)中、
X1及びX2は、各々独立に、水素原子、アルキル基、シクロアルキル基、ヒドロキシメチル基又はアルコキシメチル基を表す。但し、2つのX1の少なくとも一方は、ヒドロキシメチル基又はアルコキシメチル基である。
Y1は、2つのX1が共にヒドロキシメチル基又はアルコキシメチル基である場合は、炭素原子、窒素原子又は酸素原子を表し、1つのX1がヒドロキシメチル基でもアルコキシメチル基でもない場合、Y1は窒素原子であり、且つ、X2はヒドロキシメチル基又はアルコキシメチル基である。
Y2は、単結合、アルキレン基又はシクロアルキレン基を表す。
Z2は、有機基を表す。
nは、Y1が炭素原子のときn=2であり、Y1が窒素原子のときn=1であり、Y1が酸素原子のときn=0である。
X1、X2及びY2のいずれか二つが結合し、環を形成していてもよい。
- 架橋剤(C1)は、ヒドロキシメチル基又はアルコキシメチル基を分子内に合計で2個有する化合物である請求項1又は2に記載の感活性光線性又は感放射線性樹脂組成物。
- 更に、塩基性物質(D)として下記一般式(N-II)で表される化合物、
を少なくとも含有する請求項1~5のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
Aは、硫黄原子又はヨウ素原子を表す。
R1は、水素原子又は有機基を表し、R1が複数存在する場合、R1は同一であっても異なっていてもよい。
Rは、(o+1)価の有機基を表し、Rが複数存在する場合、Rは同一であっても異なっていてもよい。
Xは、単結合又は連結基を表し、Xが複数存在する場合、Xは同一であっても異なっていてもよい。
ANは、窒素原子を含んだ塩基性部位を表し、ANが複数存在する場合、ANは同一であっても異なっていてもよい。
Aが硫黄原子である場合、nは1~3の整数であり、mはm+n=3なる関係を満たす整数である。
Aがヨウ素原子である場合、nは1又は2であり、mはm+n=2なる関係を満たす整数である。
oは1~10の整数を表し、Y-はアニオンを表し、R1、X、R、ANの少なくとも2つは互いに結合して環を形成していてもよい。
- 更に、活性光線又は放射線の照射により酸を発生する化合物、
を含有する請求項1~6のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 請求項1~7のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成された感活性光線性又は感放射線性膜。
- 請求項8に記載の感活性光線性又は感放射線性膜を備えたマスクブランクス。
- 請求項9に記載のマスクブランクスが備える感活性光線性又は感放射線性膜を露光すること、及び、
露光した感活性光線性又は感放射線性膜を現像すること、
を含む方法により製造されたフォトマスク。
- - 請求項1~7のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物を用いて感活性光線性又は感放射線性膜を形成すること、
- 該膜を露光すること、及び
- 該露光された膜を、現像液を用いて現像してパターンを形成すること、
を含むパターン形成方法。
- 前記露光がX線、電子線又はEUVを用いて行われる、請求項11に記載のパターン形成方法。
- 請求項11又は12に記載のパターン形成方法を含む電子デバイスの製造方法。
- 請求項13に記載の電子デバイスの製造方法によって製造された電子デバイス。
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JP6122754B2 (ja) * | 2013-09-30 | 2017-04-26 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、感活性光線性又は感放射線性膜を備えたマスクブランクス、パターン形成方法、及び電子デバイスの製造方法 |
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US20160282720A1 (en) | 2016-09-29 |
KR20160090352A (ko) | 2016-07-29 |
EP3106920A4 (en) | 2017-04-26 |
CN105900013B (zh) | 2019-12-24 |
KR101958690B1 (ko) | 2019-03-15 |
US10120281B2 (en) | 2018-11-06 |
JP6313604B2 (ja) | 2018-04-18 |
JP2015148688A (ja) | 2015-08-20 |
KR20180038072A (ko) | 2018-04-13 |
EP3106920B1 (en) | 2019-07-10 |
TWI657111B (zh) | 2019-04-21 |
TW201531514A (zh) | 2015-08-16 |
CN105900013A (zh) | 2016-08-24 |
EP3106920A1 (en) | 2016-12-21 |
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