WO2019044270A1 - 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、固体撮像素子の製造方法 - Google Patents
感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、固体撮像素子の製造方法 Download PDFInfo
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Classifications
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method of manufacturing a solid-state imaging device.
- Charge-coupled devices CCDs or complementary metal oxide semiconductors (CMOSs), which are solid-state imaging devices for color images, are used for video cameras, digital still cameras, mobile phones with camera functions, and the like.
- CMOSs complementary metal oxide semiconductors
- These solid-state imaging devices have light receiving portions arranged in a two-dimensional array, and the light receiving portions photoelectrically convert incident light to generate an electrical image signal.
- the light receiving portion itself has sensitivity to the long wavelength near infrared region (wavelength about 2500 nm) in addition to the visible light region (380 nm to 780 nm) in general.
- the solid-state imaging device further includes, on the light receiving surface, a plurality of types of color filter layers having different transmission wavelength regions, an infrared light transmission filter layer, and the like.
- the semiconductor substrate in which the electrical storage layer which has a sensitivity to a predetermined wavelength was formed is used for the light-receiving part.
- the storage layer usually forms a pattern on a semiconductor substrate using a resist composition, and uses this pattern as a mask to implant ions (impurities) into a non-mask region of the semiconductor substrate using an ion implantation apparatus. It is formed.
- ions impurities
- ion implantation hereinafter also referred to as “ion implantation”
- the impurity needs to be implanted at a deep position of the semiconductor substrate.
- thick film patterns are used.
- a resist composition capable of forming a thick film pattern “a resist composition for forming a thick film resist film having a film thickness of 1 to 15 ⁇ m, and a resin whose alkali solubility is increased by the action of acid”
- Component (A) and acid generator component (B) which generates an acid upon exposure are dissolved in an organic solvent (S), and the organic solvent (S) is 10 to 95% by mass of propylene glycol monomethyl ether, and the like
- the inventors of the present invention attempted ion implantation (impurity) into a semiconductor substrate using a thick film pattern formed by the positive resist composition described in Patent Document 1 as a mask. As a result, it was confirmed that when ions were to be implanted to a depth sufficient to give practically sufficient sensitivity to infrared light, ion leakage occurred in the mask region of the semiconductor substrate. That is, it was confirmed that the emitted ions permeated through the mask and were also implanted into the semiconductor substrate under the mask.
- An actinic ray-sensitive or radiation-sensitive resin composition for forming a pattern used as a mask in an ion implantation step, A resin containing a repeating unit having an acid degradable group, A photoacid generator, An additive having a melting point or glass transition temperature of less than 25 ° C. and a molecular weight of 180 or more, An actinic ray-sensitive or radiation-sensitive resin composition, wherein the content of the additive is 1% by mass or more based on the total solid content in the composition.
- the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the film density is 1.05 g / cm 3 or more.
- Ions for forming a light receiving portion for the infrared light transmission filter in the manufacture of a solid-state imaging device in which the ion implantation step includes an infrared light transmission filter that selectively transmits an infrared light component The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], which is an implantation step.
- a method for manufacturing a solid-state imaging device comprising the pattern forming method according to [11], An ion implantation step of forming a light receiving portion that senses infrared light by implanting ions in a non-mask area of the substrate using the pattern formed on the substrate as a mask; Removing the pattern from the substrate; And an infrared light transmission filter layer disposing step of disposing an infrared light transmission filter layer on the ion-implanted region of the substrate.
- the actinic-ray-sensitive or radiation-sensitive resin composition which can form the pattern which can suppress the ion leak in an ion implantation process can be provided. Further, according to the present invention, it is possible to provide a resist film using the actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method. Further, according to the present invention, it is possible to provide a method of manufacturing a solid-state imaging device using the above-mentioned pattern forming method.
- actinic ray or radiation refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV light), X-rays, and electron beams (EB). Means Electron Beam) and the like.
- light herein is meant actinic radiation or radiation.
- the “exposure” in the present specification includes not only exposure by the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X rays, EUV light, etc., but also electron beams and Also includes drawing by particle beam such as ion beam.
- “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.
- (meth) acrylate represents acrylate and methacrylate.
- weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (hereinafter, also referred to as “molecular weight distribution”) (Mw / Mn) of a resin are GPC (Gel Permeation Chromatography) devices ( GPC measurement by Tosoh HLC-8120GPC (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: Tosoh TSK gel Multipore HXL-M, column temperature: 40 ° C., flow rate: 1.0 mL / min, detection Instrument: It is defined as a polystyrene conversion value by a differential index detector (Refractive Index Detector).
- the notation not describing substitution and non-substitution also includes a group having a substituent as well as a group having no 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).
- organic group in the present specification means a group containing at least one carbon atom.
- the type of substituent, the position of the substituent, and the number of substituents when “it may have a substituent” is not particularly limited.
- the number of substituents may, for example, be one, two, three or more.
- Examples of the substituent may include monovalent nonmetal atomic groups other than hydrogen atoms, and may be selected, for example, from the following substituent group T.
- substituent T halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group Alkyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl
- the characteristic point of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention includes a point that the specific additive is contained in a predetermined amount with respect to the total solid content in the composition.
- the present inventors have confirmed that the residual solvent remaining inside the pattern formed by the actinic ray-sensitive or radiation-sensitive resin composition correlates with the problem of the ion leakage. Specifically, the film density of the pattern decreases as the amount of residual solvent remaining inside the pattern decreases, and as a result, it is considered that ion leakage occurs in the ion implantation step.
- the present inventors solved the problems of the above-mentioned findings by blending a predetermined amount of the specific additive described above in the actinic ray-sensitive or radiation-sensitive resin composition.
- the specific additive has an effect of improving the plasticity of the resist film in the resist film (in other words, the coating film of the actinic ray sensitive or radiation sensitive resin composition). Therefore, the solvent remaining in the resist film is easily volatilized due to the presence of the specific additive, and as a result, it is presumed that the film density of the formed pattern is excellent.
- the ions Leakage can be suppressed.
- the composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development. Among them, a positive resist composition is preferable, and a resist composition for alkali development is preferable.
- the composition of the present invention is typically a chemically amplified resist composition.
- the composition of the present invention contains a resin containing a repeating unit having an acid decomposable group (hereinafter also referred to as "resin (A)").
- resin (A) typically, when an alkaline developer is employed as a developer, a positive pattern is suitably formed, and an organic developer is employed as a developer. Preferably, a negative pattern is formed.
- the glass transition temperature (Tg (° C.)) of the resin (A) is preferably 170 ° C. or lower in that the film density of the formed pattern is more excellent and the ion leakage in the ion implantation step is further suppressed. And 140 ° C. or less are more preferable. In addition, normally, the lower limit of the glass transition temperature of resin (A) is 100 degreeC or more.
- the glass transition temperature of the resin (A) can be determined by using a catalog value or a literature value if there is one, and if not, it can be measured by differential scanning calorimetry (DSC).
- the glass transition temperature can be calculated by following formula (1).
- Formula (1) 1 / (273 + Tg) .
- Tgi Glass transition temperature (° C.) of homopolymer of monomer i
- the resin (A) contains a repeating unit having an acid decomposable group (hereinafter, also referred to as “repeating unit X1”).
- the acid-degradable group a group which is decomposed by the action of an acid to form a polar group is preferable.
- a polar group a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, (alkylsulfonyl) (alkyl carbonyl) methylene group, (alkyl sulfonyl) (alkyl carbonyl) imide group , Bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group, tris (alkyl carbonyl) methylene group, and tris (alkyl sulfonyl) methylene group Acid groups (groups dissociable in 2.38 mass% tetramethylammonium hydroxide aqueous solution), and alcoholic hydroxyl groups.
- the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and is a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) bonded directly to an aromatic ring, and an electron attractive group such as a fluorine atom at the ⁇ position as a hydroxyl group.
- a hydroxyl group phenolic hydroxyl group
- an electron attractive group such as a fluorine atom at the ⁇ position as a hydroxyl group.
- aliphatic alcohols substituted with sex groups eg, hexafluoroisopropanol group etc.
- the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 or less.
- Preferred polar groups include carboxy group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group), and sulfonic acid group.
- a preferred group as the acid-degradable group is a group in which a hydrogen atom of a polar group is substituted by a group (leaving group) which is released by the action of an acid.
- a group (leaving group) capable of leaving by the action of an acid e.g., -C (R 36) (R 37) (R 38), - C (R 36) (R 37) (OR 39), and - C (R 01 ) (R 02 ) (OR 39 ) and the like.
- each of R 36 to R 39 independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may combine with each other to form a ring.
- Each of R 01 and R 02 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- the cycloalkyl group of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic.
- the monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- the polycyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 6 to 20, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinel group and a tricyclodecanyl group, Tetracyclododecyl group, and androstanyl group etc. are mentioned.
- at least one carbon atom in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.
- the aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having a carbon number of 6 to 10, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.
- the aralkyl group of R 36 to R 39 , R 01 and R 02 is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
- the alkenyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkenyl group having a carbon number of 2 to 8, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
- the ring formed by bonding R 36 and R 37 to each other is preferably a cycloalkyl group (monocyclic or polycyclic).
- the cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. .
- a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is preferable, and an acetal group or a tertiary alkyl ester group is more preferable.
- the resin (A) may have a repeating unit represented by the following general formula (AI) as the repeating unit X1 preferable.
- Xa 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
- T represents a single bond or a divalent linking group.
- Rx 1 to Rx 3 independently represents an alkyl group or a cycloalkyl group. Any two of Rx 1 to Rx 3 may be combined to form a ring structure or may not be formed.
- Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-.
- Rt represents an alkylene group, a cycloalkylene group or an arylene group.
- T is preferably a single bond or -COO-Rt-.
- Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and more preferably -CH 2 -,-(CH 2 ) 2- or-(CH 2 ) 3- . More preferably, T is a single bond.
- Xa 1 is preferably a hydrogen atom or an alkyl group.
- the alkyl group of Xa 1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
- the alkyl group of Xa 1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a trifluoromethyl group.
- the alkyl group of Xa 1 is preferably a methyl group.
- the alkyl group of Rx 1 , Rx 2 and Rx 3 may be linear or branched and may be methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, An isobutyl group or t-butyl group is preferable.
- the carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
- a part of carbon-carbon bonds may be a double bond.
- the cycloalkyl group of Rx 1 , Rx 2 and Rx 3 is a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, or norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, etc. And polycyclic cycloalkyl groups are preferred.
- the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 includes a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a norbornane ring, a tetracyclo ring Polycyclic cycloalkyl rings such as decane ring, tetracyclododecane ring and adamantane ring are preferred. Among them, a cyclopentyl ring, a cyclohexyl ring or an adamantane ring is more preferable. As a ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 , a structure shown below is also preferable.
- the resin (A) has, as the repeating unit X1, the repeating units described in paragraphs ⁇ 0336> to ⁇ 0369> of US Patent Application Publication 2016/0070167 A1.
- resin (A) is decomposed by the action of the acid described in paragraph ⁇ 0363> to ⁇ 0364> of US Patent Application Publication No. 2016/0070167 A1 as the repeating unit X1 to form an alcoholic hydroxyl group. It may have a repeating unit.
- Resin (A) is a repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group as the repeating unit X1 It is also preferable to have
- the phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group.
- the aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
- Formula (Y1) -C (Rx 1 ) (Rx 2 ) (Rx 3 )
- Formula (Y3) - C (R 36) (R 37) (OR 38)
- Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Among them, Rx 1 to Rx 3 are more preferably each independently a repeating unit representing a linear or branched alkyl group, and Rx 1 to Rx 3 are each independently linear. It is further preferred that the repeating unit represents an alkyl group. Two of Rx 1 to Rx 3 may be combined to form a single ring or multiple rings.
- the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having a carbon number of 1 to 4, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. .
- the cycloalkyl group of Rx 1 to Rx 3 is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic ring such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.
- a cycloalkyl group of The cycloalkyl group formed by combining two of Rx 1 to Rx 3 is a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl Groups and polycyclic cycloalkyl groups such as adamantyl groups are preferred.
- a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is such that, for example, one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group It may be replaced.
- a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group It may be replaced.
- Rx 1 is a methyl group or an ethyl group
- Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group is preferable.
- R 36 and R 37 each independently represent a hydrogen atom or a monovalent organic group.
- R 38 represents a monovalent organic group.
- R 37 and R 38 may bond to each other to form a ring.
- Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
- R 36 is preferably a hydrogen atom.
- Ar represents an aromatic hydrocarbon group.
- Rn represents an alkyl group, a cycloalkyl group or an aryl group.
- Rn and Ar may bond to each other to form a non-aromatic ring.
- Ar is more preferably an aryl group.
- a repeating unit having a structure (acid-degradable group) in which a phenolic hydroxyl group is protected by a leaving group a structure in which a hydrogen atom in the phenolic hydroxyl group is protected by a group represented by formulas (Y1) to (Y4) What has is preferable.
- a repeating unit having a structure (acid-degradable group) in which a phenolic hydroxyl group is protected by a leaving group a repeating unit represented by the following general formula (AII) is preferable.
- Each of R 61 , R 62 and R 63 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 62 may combine with Ar 6 to form a ring, and in this case, R 62 represents a single bond or an alkylene group.
- X 6 represents a single bond, -COO-, or -CONR 64- .
- R 64 represents a hydrogen atom or an alkyl group.
- L 6 represents a single bond or an alkylene group.
- Ar 6 represents an (n + 1) -valent aromatic hydrocarbon group, and when it forms a ring by bonding to R 62, it represents an (n + 2) -valent aromatic hydrocarbon group.
- Y 2 each independently represents a hydrogen atom or a group capable of leaving under the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid.
- the groups leaving by the action of the acid as Y 2 are preferably of the formulas (Y1) to (Y4).
- n represents an integer of 1 to 4;
- Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, Examples thereof include an alkoxycarbonyl group (having 2 to 6 carbon atoms) and the like, and those having 8 or less carbon atoms are preferable.
- substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, Examples thereof include an alkoxycarbonyl group (having 2 to 6 carbon atoms) and the like, and those having 8 or less carbon atoms are preferable.
- Specific examples of the repeating unit represented by formula (AII) are shown below, but the present invention is not limited thereto.
- the resin (A) may contain the repeating unit X1 singly or in combination of two or more.
- the content of the repeating unit X1 (if there is a plurality of repeating units X1, the total thereof) is preferably 5 mol% or more, and 10 mol% or more with respect to all repeating units of the resin (A). More preferably, 20 mol% or more is more preferable.
- the upper limit of the content of the repeating unit X1 is, for example, 50 mol% or less, and preferably 40 mol% or less, based on all repeating units of the resin (A).
- the resin (A) may contain other repeating units in addition to the repeating unit X1.
- the other repeating unit which resin (A) may contain is explained in full detail.
- -Repeating unit which has phenolic hydroxyl group It is preferable that resin (A) contains the repeating unit (henceforth "the repeating unit X2") which has phenolic hydroxyl group other than repeating unit X1 mentioned above.
- repeating unit X2 does not have an acid decomposable group.
- the resin (A) is more excellent in dissolution rate at the time of alkali development by containing the repeating unit X2.
- repeating unit X2 a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit is mentioned. Among them, as the repeating unit X2, a repeating unit represented by the following general formula (I) is preferable.
- R 41 , R 42 and R 43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may combine with Ar 4 to form a ring, and in this case, R 42 represents a single bond or an alkylene group.
- X 4 represents a single bond, -COO-, or -CONR 64-
- R 64 represents a hydrogen atom or an alkyl group.
- L 4 represents a single bond or a divalent linking group.
- Ar 4 represents an (n + 1) -valent aromatic hydrocarbon group, and when it bonds to R 42 to form a ring, it represents an (n + 2) -valent aromatic hydrocarbon group.
- n represents an integer of 1 to 5;
- X 4 is -COO- or -CONR 64- .
- the alkyl group represented by R 41 , R 42 and R 43 in the general formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group or an n-butyl group which may have a substituent, Alkyl groups having 20 or less carbon atoms such as sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl are preferable, alkyl groups having 8 or less carbon atoms are more preferable, and alkyl groups having 3 or less carbon atoms are preferable. More preferable.
- the cycloalkyl group represented by R 41 , R 42 and R 43 in the general formula (I) may be monocyclic or polycyclic.
- a monocyclic or monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent is preferable.
- a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom represented by R ⁇ 41> , R ⁇ 42> and R 43 in General formula (I), A fluorine atom is preferable.
- the alkyl group contained in the alkoxycarbonyl group represented by R 41 , R 42 and R 43 in the general formula (I) is preferably the same as the alkyl group in the above R 41 , R 42 and R 43 .
- Preferred examples of the substituent in each of the above-mentioned groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, an ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group and an acyl.
- Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the number of carbon atoms of the substituent is preferably 8 or less.
- Ar 4 represents an (n + 1) -valent aromatic hydrocarbon group.
- the bivalent aromatic hydrocarbon group in the case where n is 1 may have a substituent, and for example, an arylene having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group
- Groups or aromatic hydrocarbon groups containing a heterocycle such as, for example, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole are preferred.
- n + 1) -valent aromatic hydrocarbon group in the case where n is an integer of 2 or more include any of (n-1) any of the above-mentioned specific examples of the divalent aromatic hydrocarbon group. Preferred examples include groups formed by removing a hydrogen atom.
- the (n + 1) -valent aromatic hydrocarbon group may further have a substituent.
- Examples of the substituent that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group and (n + 1) -valent aromatic hydrocarbon group may have include, for example, R 41 , R 42 and R 43 in General Formula (I) The alkyl group mentioned; Alkoxy group such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; Aryl group such as phenyl group; and the like.
- R 64 represents a hydrogen atom or an alkyl group
- the alkyl group for R 64 in, which may have a substituent, a methyl group, an ethyl group, a propyl group
- Alkyl groups having 20 or less carbon atoms such as isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, are preferable, and alkyl groups having 8 or less carbons are more preferable .
- X 4 a single bond, —COO— or —CONH— is preferable, and a single bond or —COO— is more preferable.
- the divalent linking group as L 4 is preferably an alkylene group, and as the alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, which may have a substituent, And alkylene groups having 1 to 8 carbon atoms such as an octylene group are preferable.
- Ar 4 an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferable, and a benzene ring group, a naphthalene ring group or a biphenylene ring group is more preferable.
- the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar 4 is preferably a benzene ring group.
- repeating unit X2 is not limited to this.
- a represents 1 or 2.
- the resin (A) may contain the repeating unit X2 singly or in combination of two or more.
- the content of the repeating unit X2 (the total number of the repeating units X2 if present) is preferably 40 mol% or more, and 50 mol% to all repeating units in the resin (A). The above is more preferable, 60 mol% or more is more preferable, 85 mol% or less is preferable, and 80 mol% or less is more preferable.
- Non-acid-degradable linear alkyl group having 2 or more carbon atoms which may contain a hetero atom
- Resin (A) contains a hetero atom in that the residual solvent can be more easily volatilized. It is preferable to include a repeating unit having a non-acid-degradable linear alkyl group having 2 or more carbon atoms (hereinafter also referred to as "repeating unit X3").
- non-acid-degradable means having the property that elimination / decomposition reaction does not occur by the acid which a photo-acid generator generate
- non-acid-degradable linear alkyl group means, more specifically, a linear alkyl group which does not separate from the resin (A) by the action of the acid generated by the photoacid generator, or photoacid generation There may be mentioned linear alkyl groups which are not decomposed by the action of the acid generated by the agent.
- the repeating unit X3 is preferably a repeating unit derived from a monomer having a glass transition temperature (Tg (° C.)) of 50 ° C. or less (preferably 30 ° C. or less) when it is a homopolymer.
- Tg glass transition temperature
- the lower limit value is not particularly limited, but is often ⁇ 80 ° C. or higher.
- the above glass transition temperature can be measured by a differential scanning calorimetry (DSC) method if there is a catalog value or a literature value if there is one.
- the non-acid-degradable linear alkyl group having 2 or more carbon atoms which may contain a hetero atom is not particularly limited, and examples thereof include linear (linear and branched) alkyl groups having 2 to 20 carbon atoms. And alkyl groups, and chained alkyl groups having 2 to 20 carbon atoms including hetero atoms.
- the chain alkyl group having 2 to 20 carbon atoms containing a hetero atom for example, one or more of —CH 2 — is —O—, —S—, —CO—, —NR 6 —, or The chain
- R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- the non-acid-degradable linear alkyl group having 2 or more carbon atoms which may contain a hetero atom include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group.
- the carbon number of the non-acid-degradable chain-like alkyl group having 2 or more carbon atoms which may contain a hetero atom is preferably 2 to 10, and more preferably 2 to 10 in that the film density of the formed pattern is more excellent. 8 is more preferable.
- the non-acid-degradable linear alkyl group having 2 or more carbon atoms may have a substituent (for example, the substituent exemplified as the substituent T may be mentioned).
- a repeating unit represented by the following general formula (1) is preferable as the repeating unit X3 in that the film density of the pattern to be formed is more excellent.
- R 1 represents a hydrogen atom, a halogen atom or an alkyl group.
- R 2 represents a non-acid-degradable linear alkyl group having 2 or more carbon atoms which may contain a hetero atom.
- the halogen atom represented by R 1 is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- the alkyl group (which may be linear, branched or cyclic) represented by R 1 is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms, Specifically, methyl group, ethyl group, tert-butyl group and the like can be mentioned. Among them, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. Among them, a hydrogen atom or a methyl group is preferable as R 1 .
- non-acid-degradable linear alkyl group having 2 or more carbon atoms which may contain a hetero atom represented by R 2 are as described above.
- Examples of the monomer constituting the repeating unit X3 include ethyl acrylate ( ⁇ 22 ° C.), n-propyl acrylate ( ⁇ 37 ° C.), isopropyl acrylate ( ⁇ 5 ° C.), n-butyl acrylate ( ⁇ 55 ° C.), n -Butyl methacrylate (20 ° C), n-hexyl acrylate (-57 ° C), 2-ethylhexyl acrylate (-70 ° C), isononyl acrylate (-82 ° C), lauryl methacrylate (-65 ° C), 2 -Hydroxyethyl acrylate (-15 ° C), 2-hydroxypropyl methacrylate (26 ° C), succinic acid 1- [2- (methacryloyloxy) ethyl] (9 ° C), 2-ethylhexyl methacrylate (-10 ° C), sec-butyl acrylate (-
- the resin (A) may contain the repeating unit X3 singly or in combination of two or more.
- the content of the repeating unit X3 (the total of the repeating units X3 when there are a plurality of repeating units X3) is preferably 5 mol% or more, and more preferably 5 to 30 moles with respect to all repeating units of the resin (A). % Is more preferable, and 5 to 20 mol% is more preferable.
- the resin (A) has at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure It is preferable to include the repeating unit (hereinafter, also referred to as “repeating unit X4”) that it has.
- the lactone structure or sultone structure may have a lactone structure or a sultone structure, and a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure is preferable.
- a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure is preferable.
- another ring structure is fused to a 5- to 7-membered ring lactone structure to form a bicyclo structure or spiro structure, or a 5- to 7-membered ring in a form to form a bicyclo structure or spiro structure
- More preferred are those in which other ring structures are fused to a sultone structure.
- the resin (A) has a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21), or any one of the following general formulas (SL1-1) to (SL1-3) More preferably, it contains a repeating unit having a sultone structure represented. Also, a lactone structure or a sultone structure may be directly bonded to the main chain.
- Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1) And lactone structures represented by the formula -21) or sultone structures represented by the general formula (SL1-1).
- the lactone structure moiety or the sultone structure moiety may or may not have a substituent (Rb 2 ).
- Preferred examples of the substituent (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group And a halogen atom, a hydroxyl group, a cyano group, an acid decomposable group and the like, and an alkyl group having 1 to 4 carbon atoms, a cyano group or an acid decomposable group is preferable.
- n 2 represents an integer of 0 to 4; When n 2 is 2 or more, plural substituents (Rb 2 ) may be the same or different. Moreover, two or more substituents (Rb 2 ) may be combined to form a ring.
- a repeating unit having a lactone structure or a sultone structure As a repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III) is preferable.
- A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).
- n is the number of repetition of the structure represented by -R 0 -Z- and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R 0 -Z- is absent, resulting in a single bond.
- R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof. If R 0 is plural, R 0 each independently represents a alkylene group, a cycloalkylene group, or a combination thereof.
- Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
- each Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
- R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
- R 7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
- the alkylene group or cycloalkylene group of R 0 may have a substituent.
- Z an ether bond or an ester bond is preferable, and an ester bond is more preferable.
- the resin (A) may have a repeating unit having a carbonate structure.
- the carbonate structure is preferably a cyclic carbonate structure.
- the repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).
- R A 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
- n represents an integer of 0 or more.
- R A 2 represents a substituent. When n is 2 or more, R A 2 independently represents a substituent.
- A represents a single bond or a divalent linking group.
- Z represents an atomic group which forms a monocyclic or polycyclic structure with a group represented by —O—C (OO) —O— in the formula.
- the resin (A) have, as the repeating unit X4, the repeating units described in paragraphs ⁇ 0370> to ⁇ 0414> of US Patent Application Publication 2016/0070167 A1.
- the resin (A) may contain the repeating unit X4 singly or in combination of two or more.
- the following monomers are also suitably used as a raw material of the resin (A).
- the content of the repeating unit X4 contained in the resin (A) (the total number of the repeating units X4 if present) is preferably 5 to 30 mol%, relative to all repeating units in the resin (A). -30 mol% is more preferable, and 20-30 mol% is more preferable.
- the resin (A) preferably contains a repeating unit having an aromatic ring other than the repeating unit X1 and the repeating unit X2 (hereinafter, also referred to as “repeating unit X5”).
- repeating unit X5 for example, a repeating unit represented by the following general formula (III) is preferable.
- R 41 , R 42 , R 43 , X 4 , L 4 and Ar 4 are represented by the general formula (I) exemplified for the repeating unit X 2
- R 41 , R 42 , R 43 , X 4 , L 4 and Ar 4 in the repeating unit has the same meaning, and preferred embodiments are also the same.
- a raw material monomer of the repeating unit represented by General formula (III) a benzyl (meth) acrylate, styrene, etc. are mentioned.
- the resin (A) may contain the repeating unit X5 singly or in combination of two or more.
- the content of the repeating unit X5 (if there is a plurality of repeating units X5, the total content thereof) is preferably 5 mol% or more, more preferably 5 to 30 moles, with respect to all repeating units of the resin (A). % Is more preferable, and 5 to 20 mol% is more preferable.
- the resin (A) is, besides the above-mentioned repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or further, generally necessary characteristics of resist, resolution, heat resistance, sensitivity, etc. May have various repeating structural units for the purpose of adjusting.
- Such repeating structural units include, but are not limited to, repeating structural units corresponding to predetermined monomers.
- the predetermined monomer has, for example, one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. Compounds etc. may be mentioned.
- addition polymerizable unsaturated compounds copolymerizable with the monomers corresponding to the above-mentioned various repeating structural units may be used.
- the content molar ratio of each repeating structural unit is appropriately set to adjust various performances.
- the weight average molecular weight of the resin (A) is preferably 5,000 to 30,000, more preferably 10,000 to 25,000, and still more preferably 13,000 to 20,000.
- the degree of dispersion (Mw / Mn) is usually 1.1 to 2.2, preferably 1.1 to 2.0, more preferably 1.1 to 1.7, still more preferably 1.1 to 1.4. preferable.
- Resin (A) may be used individually by 1 type, and may use 2 or more types together.
- the content of the resin (A) is generally 20% by mass or more in many cases, preferably 40% by mass or more, and 60% by mass or more based on the total solid content of the composition. More preferably, 80 mass% or more is still more preferable.
- the upper limit in particular is not restrict
- the composition of the present invention contains a specific additive (hereinafter also referred to as "specific additive (B)").
- the specific additive (B) has a melting point or glass transition temperature of less than 25 ° C., and a molecular weight of 180 or more.
- at least one of the melting point and the glass transition temperature may be less than 25 ° C.
- the melting point and the glass transition temperature (Tg (° C.)) of the specific additive (B) are preferably 25 ° C. or less, more preferably 0 ° C. or less, in that the film density of the formed pattern is more excellent.
- the lower limit thereof is, for example, -100 ° C. or higher.
- the above-mentioned melting point and glass transition temperature can be measured by a differential scanning calorimetry (DSC) method if there is a catalog value or a literature value, if any.
- the molecular weight of the specific additive (B) is preferably 200 or more in that the film density of the pattern to be formed is more excellent. Also, the upper limit thereof is, for example, 400 or less.
- the weight average molecular weight is preferably 200 or more in that the film density of the pattern to be formed is more excellent.
- the upper limit value is, for example, 400 or less.
- the specific additive (B) is not particularly limited as long as the above conditions are satisfied, but it is preferably water-soluble from the viewpoint of being easily soluble in an alkali developer at the time of development.
- water solubility means that the solubility (25 degreeC) with respect to water is 300 g / L or more.
- a specific additive (B) it is preferable to have the reactive group which can react with the polar group in resin especially ,.
- the reactive group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, and an amino group. Since the specific additive (B) has the above-mentioned reactive group, the resist film is exposed and developed, and then the above-mentioned specific additive (B) is combined with the resin by the above-mentioned reactive group and taken into the film. The film density of the pattern is better.
- the compound which has a poly (oxyalkylene) structure is mentioned, for example.
- the number of carbon atoms in the oxyalkylene unit is preferably 2 to 6, and more preferably 2 to 3.
- the average addition number of oxyalkylene units is preferably 2 to 10, and more preferably 2 to 6.
- Specific examples of the specific additive (B) include the following.
- the specific additive (B) may be used alone or in combination of two or more.
- the content of the specific additive (B) is 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more based on the total solid content of the composition.
- the upper limit is 30 mass% or less, for example, and 25 mass% or less is preferable.
- the composition of the present invention contains a photoacid generator (hereinafter, also referred to as "photoacid generator (C)").
- the photoacid generator is a compound that generates an acid upon irradiation with an actinic ray or radiation.
- a compound capable of generating an organic acid upon irradiation with an actinic ray or radiation is preferable. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.
- photoacid generator known compounds which generate an acid upon irradiation with an actinic ray or radiation can be appropriately selected and used alone or as a mixture thereof.
- the known compounds disclosed in paragraphs ⁇ 0323> to ⁇ 0402> of the specification can be suitably used as the photoacid generator (C).
- the compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is preferable, for example.
- Each of R 201 , R 202 and R 203 independently represents an organic group.
- the carbon number of the organic group as R 201 , R 202 and R 203 is generally 1 to 30, preferably 1 to 20.
- two of R 201 to R 203 may be combined 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 bonding of two of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —.
- Z - represents an anion.
- Preferred embodiments of the cation in the general formula (ZI) include the corresponding groups in the compound (ZI-1), the compound (ZI-2), the compound (ZI-3) and the compound (ZI-4) described later .
- the photoacid generator (C) may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of R 201 ⁇ R 203 of the compound represented by formula (ZI), and at least one of R 201 ⁇ R 203 of another compound represented by formula (ZI), a single bond Alternatively, it may be a compound having a structure bonded via a linking group.
- the compound (ZI-1) is an arylsulfonium compound in which at least one of R 201 to R 203 in the general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation.
- the arylsulfonium compound all of R 201 to R 203 may be aryl groups, or a part of R 201 to R 203 may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.
- arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
- the aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom or the like.
- the heterocyclic structure pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, benzothiophene residue and the like can be mentioned.
- the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
- the alkyl or cycloalkyl group which the arylsulfonium compound optionally has is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms.
- Preferred examples of the cycloalkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group and cyclohexyl group.
- the aryl group, alkyl group and cycloalkyl group of R201 to R203 are each independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, carbon) And may have an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.
- the compound (ZI-2) is a compound in which each of R 201 to R 203 in formula (ZI) independently represents an organic group having no aromatic ring.
- the aromatic ring also includes an aromatic ring containing a hetero atom.
- the carbon number of the organic group having no aromatic ring as R 201 to R 203 is generally 1 to 30, preferably 1 to 20.
- Each of R201 to R203 independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group or 2-oxocycloalkenyl group. It is an alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.
- alkyl group and cycloalkyl group of R201 to R203 a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, A butyl group and a pentyl group) or a cycloalkyl group having a carbon number of 3 to 10 (eg, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) is preferable.
- R 201 to R 203 may be further substituted by a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.
- the compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a phenacylsulfonium salt structure.
- Each of R 1c to R 5c independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom or a hydroxyl group.
- R 6c and R 7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
- R x and R y independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.
- R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y respectively combine to form a ring structure
- Each of the ring structures may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond or an amide bond.
- Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring in which two or more of these rings are combined.
- the ring structure includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
- Examples of the group formed by bonding any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include a butylene group and a pentylene group.
- the group formed by combining R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
- As an alkylene group a methylene group, ethylene group, etc. are mentioned.
- Zc - represents an anion.
- the compound (ZI-4) is represented by the following general formula (ZI-4).
- R 14 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. These groups may have a substituent. When there are a plurality of R 14 's , they each independently represent the above-mentioned group such as a hydroxyl group. Each R 15 independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent.
- Two R 15 s may be bonded to each other to form a ring.
- the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
- Z - represents an anion.
- the alkyl group of R 13 , R 14 and R 15 is linear or branched.
- the carbon number of the alkyl group is preferably 1 to 10.
- the alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group.
- each of R 204 to R 207 independently represents an aryl group, an alkyl group or a cycloalkyl group.
- the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group of R 204 to R 207 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 skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
- the alkyl group and cycloalkyl group of R 204 to R 207 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, A butyl group and a pentyl group) or a cycloalkyl group having a carbon number of 3 to 10 (eg, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) is preferable.
- the aryl group, alkyl group and cycloalkyl group of R 204 to R 207 may each independently have a substituent.
- substituents which the aryl group, alkyl group and cycloalkyl group of R 204 to R 207 may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to carbon atoms) 15), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
- Z - represents an anion.
- o represents an integer of 1 to 3
- p represents an integer of 0 to 10.
- q represents an integer of 0 to 10;
- Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- the carbon number of this alkyl group is preferably 1 to 10, and more preferably 1 to 4.
- a perfluoroalkyl group is preferable.
- Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xf be a fluorine atom.
- R 4 and R 5 independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R 4 and R 5 are present, R 4 and R 5 may be the same or different.
- the alkyl group represented by R 4 and R 5 may have a substituent, and preferably has 1 to 4 carbon atoms.
- R 4 and R 5 are preferably hydrogen atoms.
- Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as specific examples and preferred embodiments of Xf in the general formula (3).
- L represents a divalent linking group.
- L may be the same or different.
- -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.
- W represents an organic group containing a cyclic structure.
- a cyclic organic group is preferable.
- an alicyclic group an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example.
- the alicyclic group may be monocyclic or polycyclic.
- monocyclic alicyclic group monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are mentioned, for example.
- polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
- polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and 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 preferable.
- the aryl group may be monocyclic or polycyclic. Examples of this aryl group include phenyl group, naphthyl group, phenanthryl group and anthryl group.
- the heterocyclic group may be monocyclic or polycyclic. The polycyclic type can suppress the diffusion of the acid more.
- 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.
- the hetero ring having no aromaticity includes, for example, tetrahydropyran ring, lactone ring, sultone ring and decahydroisoquinoline ring.
- lactone ring and sultone ring include lactone structure and sultone structure exemplified in the above-mentioned resin.
- a heterocycle in the heterocycle group a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferable.
- the cyclic organic group may have a substituent.
- this substituent for example, an alkyl group (which may be linear or branched and having 1 to 12 carbon atoms is preferable), a cycloalkyl group (monocyclic, polycyclic, and spirocyclic) Any of them, preferably having 3 to 20 carbon atoms, aryl (preferably having 6 to 14 carbons), hydroxyl, alkoxy, ester, amide, urethane, ureido, thioether, sulfonamide And sulfonate ester groups.
- the carbon constituting the cyclic organic group may be carbonyl carbon.
- SO 3 -- CF 2 -CH 2 -OCO- (L) q'-W SO 3 -- CF 2 -CHF-CH 2 -OCO- (L) q'-W, SO 3 - -CF 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W, or, SO 3 - -CF 2 -CH (CF 3 ) -OCO- (L) q'-W is preferred.
- L, q and W are the same as in the general formula (3).
- the anion represented by Formula (4) is also preferable.
- Each of X B1 and X B2 independently represents a hydrogen atom or a monovalent organic group having no fluorine atom.
- X B1 and X B2 are preferably hydrogen atoms.
- Each of X B3 and X B4 independently represents a hydrogen atom or a monovalent organic group.
- At least one of X B3 and X B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both of X B3 and X B4 are a fluorine atom or a monovalent organic group having a fluorine atom Is more preferred. More preferably, both X B3 and X B4 are an alkyl group substituted with a fluorine atom.
- L, q and W are the same as in the general formula (3).
- Z in the general formula (ZI) -, Z in the general formula (ZII) -, Zc in formula (ZI-3) -, and Z in the general formula (ZI-4) - may be a benzenesulfonic acid anion Preferably, it is a benzenesulfonic acid anion substituted by a branched alkyl group or a cycloalkyl group.
- Ar represents an aryl group, and may further have a substituent other than a sulfonate anion and a-(D-B) group.
- substituent which may further have include a fluorine atom and a hydroxyl group.
- N represents an integer of 0 or more. As n, 1 to 4 is preferable, 2 to 3 is more preferable, and 3 is more preferable.
- D represents a single bond or a divalent linking group.
- the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more of these.
- B represents a hydrocarbon group
- D is a single bond and B is an aliphatic hydrocarbon structure.
- B is more preferably isopropyl or cyclohexyl.
- the photoacid generator may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of a polymer. Also, the form of the low molecular weight compound and the form incorporated into a part of the polymer may be used in combination.
- the photoacid generator is preferably in the form of a low molecular weight compound. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.
- the photoacid generator When the photoacid generator is in a form incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) described above, or may be incorporated into a resin different from the resin (A) .
- a photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
- the content of the photoacid generator (if there is more than one type in total, the total thereof) is preferably 0.1 to 35% by mass with respect to the total solid content of the composition. 25% by mass is more preferable, 1 to 20% by mass is further preferable, and 1 to 15% by mass is particularly preferable.
- the composition of the present invention preferably contains an acid diffusion control agent (D).
- the acid diffusion control agent (D) traps an acid generated from a photoacid generator or the like at the time of exposure, and acts as a quencher to suppress the reaction of the acid decomposable resin in the unexposed area by the extra generated acid.
- basic compound (DA), basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation
- onium salt (DC) which becomes a relatively weak acid with respect to an acid generator
- nitrogen atom And an onium salt compound (DE) having a nitrogen atom in the cation part can be used as an acid diffusion control agent.
- known acid diffusion control agents can be suitably used.
- paragraphs ⁇ 0627> to ⁇ 0664> of U.S. Patent Application Publication 2016/0070167 A1; paragraphs ⁇ 0095> to ⁇ 0187> of U.S. Patent Application Publication 2015/0004544 A1, U.S. Patent Application Publication 2016/0237190 A1 The known compounds disclosed in paragraphs ⁇ 0403> to ⁇ 0423> of the specification and paragraphs ⁇ 0259> to ⁇ 0328> of US Patent Application Publication 2016/0274458 A1 are suitable as the acid diffusion control agent (D) It can be used for
- the basic compound (DA) is preferably a compound having a structure represented by the following formulas (A) to (E).
- R 200 , R 201 and R 202 which may be the same or different, each independently represent a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl Represents a group (having 6 to 20 carbon atoms).
- R 201 and R 202 may bond to each other to form a ring.
- R 203 , R 204 , R 205 and R 206 which may be the same or different, each independently represent an alkyl group having 1 to 20 carbon atoms.
- the alkyl group in the general formulas (A) and (E) may have a substituent or may not be substituted.
- As the alkyl group having a substituent as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
- the alkyl group in the general formulas (A) and (E) is more preferably unsubstituted.
- the basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine or the like, and has an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, Compounds having a trialkylamine structure, an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, or aniline derivatives having a hydroxyl group and / or an ether bond are more preferable.
- a basic compound (DB) (hereinafter also referred to as "compound (DB)") whose basicity is reduced or eliminated by irradiation with actinic rays or radiation has a proton acceptor functional group, and an actinic ray or radiation. It is a compound which is decomposed by irradiation with radiation to decrease, disappear, or change from proton acceptor property to acidity.
- the proton acceptor functional group is a functional group having a group or an electron that can electrostatically interact with a proton, and is, for example, a functional group having a macrocyclic structure such as cyclic polyether or ⁇ conjugated
- the nitrogen atom having a noncovalent electron pair not contributing to the ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.
- Examples of preferable partial structures of the proton acceptor functional group include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
- the compound (DB) decomposes upon irradiation with an actinic ray or radiation to reduce or eliminate the proton acceptor property, or generates a compound which has been changed from the proton acceptor property to the acidity.
- the reduction or disappearance of the proton acceptor property or the change from the proton acceptor property to the acidity is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group, and is specifically described Means that when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
- the proton acceptor property can be confirmed by performing pH measurement.
- the acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) upon irradiation with an actinic ray or radiation preferably satisfies pKa ⁇ 1, more preferably ⁇ 13 ⁇ pKa ⁇ 1, It is more preferable to satisfy 13 ⁇ pKa ⁇ -3.
- the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chemical Handbook (II) (revised 4th edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
- the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C. using an infinite dilution aqueous solution.
- values based on Hammett's substituent constant and a database of known literature values can also be obtained by calculation. All the pKa values described in the present specification indicate values calculated by using this software package.
- an onium salt (DC) that is relatively weak to the photoacid generator can be used as an acid diffusion control agent.
- the photoacid generator is irradiated with an actinic ray or radiation.
- the weak acid is released by salt exchange to form an onium salt having a strong acid anion. In this process, since the strong acid is exchanged to a weak acid with lower catalytic ability, apparently, the acid is inactivated to control the acid diffusion.
- R 51 is a hydrocarbon group which may have a substituent
- Z 2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, the carbon adjacent to S) Fluorine atom is not substituted)
- R 52 is an organic group
- Y 3 is a linear, branched or cyclic alkylene group or arylene group
- R f is a fluorine atom
- each of M + is independently an ammonium cation, a sulfonium cation or an iodonium cation.
- Preferred examples of the sulfonium cation or iodonium cation represented as M + include the sulfonium cation exemplified in the general formula (ZI) and the iodonium cation exemplified in the general formula (ZII).
- a compound having a cation site and an anion site in the same molecule and a cation site and an anion site linked by a covalent bond (the onium salt (DC) to be a relatively weak acid with respect to the photoacid generator
- DCA the onium salt
- the compound (DCA) is preferably a compound represented by any one of the following formulas (C-1) to (C-3).
- R 1 , R 2 and R 3 each independently represent a substituent having 1 or more carbon atoms.
- L 1 represents a divalent linking group or a single bond linking a cation site and an anion site.
- -X - it is, -COO -, -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, and -N.
- R represents a monovalent substituent having at least one of R 1 , R 2 , R 3 , R 4 and L 1 may be combined with each other to form a ring structure.
- two of R 1 to R 3 may be combined to represent one divalent substituent, which may be bonded to an N atom via a double bond.
- an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylamino group A carbonyl group, and an arylamino carbonyl group etc. are mentioned.
- it is an alkyl group, a cycloalkyl group or an aryl group.
- L 1 as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, or two of them Examples thereof include groups formed by combining species or more.
- L 1 an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these is preferable.
- the low molecular weight compound (DD) having a nitrogen atom and having a group capable of leaving by the action of an acid has a group leaving by the action of an acid on the nitrogen atom It is preferable that it is an amine derivative which it has.
- a group leaving by the action of an acid an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group is preferable, and a carbamate group or a hemiaminal ether group is more preferable. .
- the molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.
- the compound (DD) may have a carbamate group having a protecting group on the nitrogen atom.
- the protective group constituting the carbamate group is represented by the following general formula (d-1).
- Each Rb independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group (preferably Preferably, it represents 1 to 10 carbon atoms, or an alkoxyalkyl group (preferably 1 to 10 carbon atoms).
- R b may be linked to each other to form a ring.
- the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R b are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group etc., an alkoxy group, or It may be substituted by a halogen atom.
- Rb The same applies to the alkoxyalkyl group represented by Rb.
- R b a linear or branched alkyl group, a cycloalkyl group or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
- a ring which two Rb mutually connects and forms alicyclic hydrocarbon, aromatic hydrocarbon, heterocyclic hydrocarbon, its derivative (s), etc. are mentioned.
- Specific structures of the group represented by formula (d-1) include, but are not limited to, the structures disclosed in paragraph ⁇ 0466> of US Patent Publication No. US 2012/0135348 A1.
- the compound (DD) preferably has a structure represented by the following general formula (6).
- l represents an integer of 0 to 2
- m represents an integer of 1 to 3
- l + m 3 is satisfied.
- Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
- two Ras may be the same or different, and two Ras may be mutually linked to form a heterocyclic ring with the nitrogen atom in the formula.
- the hetero ring may contain a hetero atom other than the nitrogen atom in the formula.
- Rb has the same meaning as Rb in formula (d-1), and the preferred examples are also the same.
- each of the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra is independently substituted with an alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb. It may be substituted by the same group as the group described above as a preferable group.
- alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above group) of the above Ra include the same groups as the specific examples described above for Rb.
- Be Specific examples of particularly preferable compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph ⁇ 0475> of US Patent Application Publication 2012/0135348 A1.
- the onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter, also referred to as a "compound (DE)”) is preferably a compound having a basic site containing a nitrogen atom in the cation part.
- the basic moiety is preferably an amino group, more preferably an aliphatic amino group. More preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly linked to the nitrogen atom.
- Preferred specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph ⁇ 0203> of US Patent Application Publication No. 2015/0309408 A1.
- an acid diffusion control agent (D) may be used individually by 1 type, and may use 2 or more types together.
- the content of the acid diffusion control agent (D) in the composition (the total amount of two or more, if present) is preferably 0.01 to 10% by mass, based on the total solid content of the composition, and 0.01 to 10% 5 mass% is more preferable.
- the composition of the present invention preferably contains a solvent.
- known resist solvents can be appropriately used.
- paragraphs ⁇ 0665> to ⁇ 0670> of U.S. Patent Application Publication 2016 / 0070167A1; paragraphs ⁇ 0210> to ⁇ 0235> of U.S. Patent Application Publication 2015 / 0004544A1, U.S. Patent Application Publication 2016 / 0237190A1 Known solvents disclosed in paragraphs ⁇ 0424> to ⁇ 0426> of the specification and paragraphs ⁇ 0357> to ⁇ 0366> of US Patent Application Publication 2016/0274458 A1 can be suitably used.
- solvents examples include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, cyclic lactone (preferably having a carbon number of 4 to 10), Examples thereof include organic solvents such as a monoketone compound (preferably having a carbon number of 4 to 10) which may have a ring, an alkylene carbonate, an alkyl alkoxyacetate, and an alkyl pyruvate.
- a monoketone compound preferably having a carbon number of 4 to 10
- a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure and a solvent containing no hydroxyl group may be used.
- the solvent containing a hydroxyl group and the solvent containing no hydroxyl group the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (PGME ), Propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred.
- alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol Monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferable, and propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, ethyl ethoxy propionate, cyclohexanone , Cyclopentanone or 2-heptanone are more preferred.
- PMEA propylene glycol Monomethyl ether acetate
- ethyl ethoxy propionate 2-heptanone
- ⁇ -butyrolactone cyclohexanone
- Propylene carbonate is also preferred as the solvent containing no hydroxyl group.
- the mixing ratio (mass ratio) of the hydroxyl group-containing solvent to the hydroxyl group-free solvent is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. .
- a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in view of coating uniformity.
- the solvent preferably contains propylene glycol monomethyl ether acetate, and may be propylene glycol monomethyl ether acetate alone or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.
- the composition of the present invention may contain a compound which crosslinks the resin by the action of an acid (hereinafter also referred to as "crosslinker (F)").
- a well-known compound can be used suitably as a crosslinking agent (F).
- known compounds disclosed in paragraphs ⁇ 0379> to ⁇ 0431> of US Patent Application Publication No. 2016/0147154 A1 and in paragraphs ⁇ 0064> to ⁇ 0141> of US Patent Application Publication No. 2016/0282720 A1. Can be suitably used as the crosslinking agent (F).
- the crosslinking agent (F) is a compound having a crosslinkable group capable of crosslinking the resin, and as the crosslinkable group, a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, And oxetane rings.
- the crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring.
- the crosslinking agent (F) is preferably a compound (including a resin) having two or more crosslinkable groups.
- the crosslinking agent (F) is more preferably a phenol derivative, a urea compound (a compound having a urea structure) or a melamine compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
- a crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
- the content of the crosslinking agent (F) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 30% by mass, relative to the total solid content of the resist composition.
- the composition of the present invention preferably comprises a surfactant.
- a fluorine-based and / or silicon-based surfactant specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom
- a fluorine-based and / or silicon-based surfactant specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom
- composition of the present invention contains a surfactant
- a surfactant when an exposure light source of 250 nm or less, particularly 220 nm or less, is used, a pattern with less adhesion and development defects can be obtained with good sensitivity and resolution.
- the fluorine-based and / or silicon-based surfactant the surfactants described in paragraph ⁇ 0276> of US Patent Application Publication No. 2008/0248425 can be mentioned.
- other surfactants can also be used.
- surfactants may be used alone or in combination of two or more.
- the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, with respect to the total solid content of the composition. preferable.
- composition of the present invention may further contain an acid multiplying agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali soluble resin, a dissolution inhibitor, a dissolution accelerator and the like.
- the solid content concentration of the composition of the present invention is usually 1.0% by mass or more, and 10% by mass or more is preferable, 20% by mass is more preferable, and 30% by mass is more preferable because a thick film pattern can be formed. More preferable.
- the upper limit in particular is not restrict
- solid content concentration is a mass percentage of the mass of the other resist component except a solvent with respect to the total mass of a composition.
- the composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering it, and then applying it on a predetermined support (substrate).
- a predetermined organic solvent preferably the above-mentioned mixed solvent
- 0.05 micrometer or less is more preferable, and 0.03 micrometer or less is still more preferable.
- the filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In filter filtration, as disclosed in, for example, Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Application Laid-Open No.
- cyclic filtration may be performed, and a plurality of types of filters are connected in series or in parallel. May be connected to
- the composition may also be filtered multiple times. Furthermore, the composition may be subjected to a degassing treatment and the like before and after the filter filtration.
- the composition of the present invention preferably has a viscosity of 100 to 500 mPa ⁇ s.
- the viscosity of the composition of the present invention is more preferably 100 to 300 mPa ⁇ s in that it is more excellent in coatability.
- the viscosity can be measured by an E-type viscometer.
- the film thickness of the resist film (in other words, the coating film of the actinic ray-sensitive or radiation-sensitive resin composition) comprising the composition of the present invention is, for example, 2 ⁇ m or more, and the ion leakage in the ion implantation step 5 micrometers or more are more preferable, and 7 micrometers or more are still more preferable at the point which is more excellent.
- the upper limit is not particularly limited, and is, for example, 15 ⁇ m or less.
- a pattern can be formed from the composition of this invention so that it may mention later.
- the film thickness of the pattern to be formed is, for example, 2 ⁇ m or more, preferably 5 ⁇ m or more, and more preferably 7 ⁇ m or more in that ion leakage in the ion implantation step is more excellent.
- the upper limit is not particularly limited, and is, for example, 15 ⁇ m or less.
- the film density of the pattern to be formed, in that it can further suppress ion leakage at the ion implantation step 1.05 g / cm 3 or more preferably, 1.10 g / cm 3 or more is more preferable.
- the film density is obtained by applying the composition of the present invention on a substrate to form a coating film, and then baking the coating film at 150 ° C. for 90 seconds for a film thickness of 9 ⁇ m. Intended.
- the composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition which changes its property in response to irradiation with an actinic ray or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), production of circuit substrates such as liquid crystals or thermal heads, production of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition.
- IC Integrated Circuit
- the pattern formed in the present invention can also be used in an ion implantation process, an etching process, a bump electrode formation process, a rewiring formation process, MEMS (Micro Electro Mechanical Systems), and the like.
- the composition of the present invention is a light receiving portion for the above infrared light transmission filter (in other words, infrared light in the manufacture of a solid-state imaging device including an infrared light transmission filter that selectively transmits infrared light components).
- it is used in an ion implantation process for forming a light sensing portion (light sensing portion).
- the present invention also relates to a method of forming a pattern using the actinic ray-sensitive or radiation-sensitive resin composition.
- the pattern formation method of the present invention will be described.
- the resist film of the present invention in other words, the coating film of the actinic ray sensitive or radiation sensitive resin composition
- the resist film of the present invention will also be described.
- the pattern formation method of the present invention is (I) forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition described above (resist film forming step); (Ii) exposing the resist film (irradiating with an actinic ray or radiation) (exposure step), And (iii) developing the exposed resist film with a developer (developing step).
- the pattern formation method of the present invention is not particularly limited as long as it includes the steps (i) to (iii), and may further include the following steps.
- the exposure method in the exposure step may be immersion exposure.
- the pattern formation method of the present invention preferably includes (iv) a preheating (PB: PreBake) step before (ii) the exposure step.
- the pattern forming method of the present invention preferably includes (v) a post exposure baking (PEB) step after (ii) the exposure step and (iii) before the development step.
- PEB post exposure baking
- the pattern formation method of the present invention may include (ii) multiple exposure steps.
- the pattern formation method of the present invention may include (iv) a preheating step a plurality of times.
- the pattern formation method of the present invention may include (v) a post-exposure heating step a plurality of times.
- the (i) film formation step, (ii) exposure step, and (iii) development step described above can be carried out by a generally known method.
- a resist underlayer film for example, SOG (Spin On Glass), SOC (Spin On Carbon), and an antireflective film
- SOG Spin On Glass
- SOC Spin On Carbon
- an antireflective film may be formed between the resist film and the support.
- a material which comprises a resist underlayer film well-known organic type or inorganic type material can be used suitably.
- a protective film (top coat) may be formed on the upper layer of the resist film.
- a well-known material can be used suitably as a protective film.
- composition for protective film formation indicated by US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A can be suitably used.
- a composition for protective film formation what contains the acid diffusion control agent mentioned above is preferable.
- the support is not particularly limited, and is generally used in a process of manufacturing a semiconductor such as an IC or a process of manufacturing a circuit substrate such as a liquid crystal or a thermal head, and other lithography processes of photofabrication.
- Substrate can be used.
- Specific examples of the support include inorganic substrates such as silicon, SiO 2 , and SiN.
- the heating temperature is preferably 70 to 130 ° C., and more preferably 80 to 120 ° C. in any of the (iv) pre-heating step and (v) post-exposure heating step.
- the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds in any of the (iv) pre-heating step and (v) post-exposure heating step.
- the heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed using a hot plate or the like.
- the light source wavelength used in the exposure step is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams.
- far ultraviolet light is preferable, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.
- KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm), and an electron beam or the like
- KrF excimer laser, ArF excimer laser , EUV or electron beam is preferable, and a KrF excimer laser is more preferable.
- the developing solution used in the developing step may be either an alkaline developing solution or a developing solution containing an organic solvent (hereinafter, also referred to as "organic developing solution").
- alkali developing solution quaternary ammonium salts represented by tetramethyl ammonium hydroxide are used as the alkali developing solution, but in addition to this, alkaline aqueous solutions such as inorganic alkali, primary to tertiary amines, alcohol amines, and cyclic amines are also used. It is usable.
- the alkali developer may contain an appropriate amount of an alcohol and / or a surfactant.
- the alkali concentration of the alkali developer is usually 0.1 to 20% by mass.
- the pH of the alkaline developer is usually 10-15.
- the time for developing using an alkaline developer is usually 10 to 300 seconds.
- the alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.
- the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Is preferred.
- ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.
- ester solvents for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl 3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, butyl lactate, butane And butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
- the solvents disclosed in paragraphs ⁇ 0715> to ⁇ 0718> of US Patent Application Publication No. 2016/0070167 A1 can be used.
- a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water.
- the water content of the developer as a whole is preferably less than 50% by weight, more preferably less than 20% by weight, still more preferably less than 10% by weight, and particularly preferably substantially free of water.
- the content of the organic solvent to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, with respect to the total amount of the developer. % Is particularly preferred.
- the organic developer may contain an appropriate amount of a known surfactant, as necessary.
- the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, with respect to the total amount of the developer.
- the organic developer may contain the acid diffusion control agent described above.
- a developing method for example, a method of immersing the substrate in a bath filled with a developer for a certain time (dip method), a method of raising the developer on the substrate surface by surface tension and standing still for a certain time (paddle method) The method of spraying the developer on the surface (spray method) or the method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispense method), etc. are mentioned.
- alkali developing step The step of developing using an aqueous alkali solution (alkali developing step) and the step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined.
- organic solvent developing step since pattern formation can be performed without dissolving only the region of intermediate exposure intensity, a finer pattern can be formed.
- the rinse liquid used for the rinse process after the image development process using an alkaline developing solution can use a pure water, for example.
- the pure water may contain an appropriate amount of surfactant.
- a process of removing the developer or rinse solution adhering on the pattern with a supercritical fluid may be added.
- heat treatment may be performed to remove moisture remaining in the pattern after the rinse treatment or treatment with a supercritical fluid.
- the rinse solution used for the rinse process after the development process using the developing solution containing an organic solvent does not have a restriction
- the solution containing a common organic solvent can be used.
- a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Is preferred. Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amide-based solvent, and the ether-based solvent include the same as those described in the developer containing an organic solvent.
- a rinse solution containing a monohydric alcohol is more preferable.
- Examples of the monohydric alcohol used in the rinse step include linear, branched or cyclic monohydric alcohol. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 Heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methyl isobutyl carbinol.
- Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol. .
- a plurality of each component may be mixed, or may be mixed with an organic solvent other than the above. 10 mass% or less is preferable, 5 mass% or less is more preferable, and 3 mass% or less is still more preferable. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
- the substrate subjected to development using an organic developer is washed using a rinse solution containing an organic solvent.
- the rinse solution may contain an appropriate amount of surfactant.
- the method of cleaning treatment is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotation coating method), and immersing the substrate in a bath filled with the rinse liquid for a fixed time Examples include a method (dip method) or a method of spraying a rinse liquid on a substrate surface (spray method). Above all, it is preferable to carry out cleaning treatment by spin coating, and after cleaning, rotate the substrate at a rotational speed of 2,000 to 4,000 rpm (revolution per minute) to remove the rinse solution from the substrate.
- the heating step Post Bake
- the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C.
- the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention for example, resist solvent, developer, rinse solution, composition for forming an antireflective film, or It is preferable that the composition for top coat formation etc. does not contain impurities, such as a metal component, an isomer, and a residual monomer.
- the content of these impurities contained in the various materials described above is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and substantially not including it (the detection limit of the measuring device or less) Is particularly preferred.
- the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
- a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable.
- the filter may be one previously washed with an organic solvent.
- plural types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination.
- the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.
- the filter one having a reduced elution product as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Laid-Open No. 2016-201426) is preferable.
- removal of impurities by adsorbent may be performed, and filter filtration and adsorbent may be used in combination.
- a known adsorbent can be used as the adsorbent.
- an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
- the metal adsorbent examples include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).
- filter filtration is performed on the materials constituting the various materials, which select the materials having a low metal content as the materials constituting the various materials.
- the inside of the apparatus may be lined with Teflon (registered trademark) or the like, and distillation may be carried out under conditions that minimize contamination as much as possible.
- the preferable conditions in the filter filtration performed with respect to the raw material which comprises various materials are the same as the above-mentioned conditions.
- a method of improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention.
- a method of improving the surface roughness of the pattern for example, the method of processing the pattern by plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned.
- Japanese Patent Application Publication No. 2004-235468 Japanese Patent Laid-Open No. 2004-2354608
- US Patent Application Publication No. 2010/0020297 Proc. Of SPIE Vol.
- a known method may be applied as described in 8328 83280 N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement”.
- a method of manufacturing a solid-state imaging device is a method of manufacturing a solid-state imaging device including the pattern forming method described above, (I) an ion implantation step (ion implantation step) of forming a light receiving portion for sensing infrared light by implanting ions into a non-masked area of the substrate using a pattern formed on the substrate as a mask; (Ii) removing the pattern from the substrate (mask removing step); (Iii) An infrared light transmission filter layer disposing step (infrared light transmission filter layer disposing step) of disposing an infrared light transmission filter layer on the ion-implanted region of the substrate.
- the film thickness of a pattern used as a mask is, for example, 2 ⁇ m or more, more preferably 5 ⁇ m or more, and still more preferably 7 ⁇ m or more.
- the upper limit is not particularly limited, and is, for example, 15 ⁇ m or less.
- a well-known method can be used about (i) ion implantation process.
- Japanese Patent No. 5241883 can be referred to.
- a well-known method can be used about (ii) mask removal process and (iii) infrared-light transmission filter layer arrangement
- positioning process For example, JP-A-2015-063593 can be referred to.
- the 25 types of resist compositions contained (Na, K, Ca, Fe, Cu, Mg, Mn, Al, Li, Cr, Ni, Sn, Zn, Ag, As, Au, Ba, Cd,
- the amounts of metal impurity components of Co, Pb, Ti, V, W, Mo, and Zr were measured with an ICP-MS apparatus (inductively coupled plasma mass spectrometer) “Agilent 7500 cs” manufactured by Agilent Technologies. Each content was less than 10 ppb.
- Table 1 shows weight average molecular weights (Mw), degrees of dispersion (Mw / Mn) and glass transition temperatures (Tg (° C.)) of the resins A to E.
- the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of the resins A to E were measured by GPC (carrier: tetrahydrofuran (THF)) (the polystyrene conversion value).
- the compositional ratio (mol% ratio) of the resins AE was measured by 13 C-NMR (nuclear magnetic resonance).
- the glass transition temperatures (Tg (° C.)) of the resins A to E were measured by the DSC method.
- the DSC device “Thermal analysis DSC differential scanning calorimeter Q1000 type” manufactured by TA Instruments Japan Co., Ltd. was used, and the temperature rising rate was measured as 10 ° C./min.
- ⁇ Surfactant> The structures of the surfactants shown in Table 1 are shown below. ⁇ Megafuck R-41, made by DIC ⁇ solvent> The solvents shown in Table 1 are shown below.
- PGMEA Propylene glycol monomethyl ether acetate
- content (mass%) of each component means content with respect to a total solid.
- a reflection preventing layer is formed on an 8-inch Si substrate (manufactured by Advanced Materials Technology (hereinafter, also referred to as “substrate”) subjected to hexamethyldisilazane treatment using a spin coater “ACT-8” manufactured by Tokyo Electron.
- substrate manufactured by Advanced Materials Technology (hereinafter, also referred to as “substrate”) subjected to hexamethyldisilazane treatment using a spin coater “ACT-8” manufactured by Tokyo Electron.
- the resist composition was dropped while the substrate was at rest without providing the After dropping, the substrate is rotated, the rotation speed is maintained at 500 rpm for 3 seconds, then maintained at 100 rpm for 2 seconds, maintained at 500 rpm for 3 seconds, and maintained at 100 rpm again for 2 seconds, then the film thickness setting rotation
- the temperature was raised to several (the number of revolutions to obtain a film thickness of 9 ⁇ m) and maintained for 60 seconds. After that, heat drying was performed at 150 ° C. for 90 seconds on a hot plate to form a film having a thickness of 9 ⁇ m.
- the film density was calculated by performing the following measurement on the obtained film having a film thickness of 9 ⁇ m.
- the volume V (cm 3 ) of the film is calculated from the film area on the substrate (the area of the region where the film is formed) and the film thickness (9 ⁇ m).
- the total mass W1 (g) of the substrate and the film is measured.
- the film on the substrate is removed (dissolved and / or peeled off) using methanol, and the mass W2 (g) of the substrate after film removal is measured.
- a resist composition is provided on an 8-inch Si substrate (manufactured by Advanced Materials Technology (hereinafter, also referred to as “substrate”)) using a spin coater “ACT-8” manufactured by Tokyo Electron, without providing an antireflective layer.
- substrate manufactured by Advanced Materials Technology (hereinafter, also referred to as “substrate”)
- spin coater “ACT-8” manufactured by Tokyo Electron
- the substrate is rotated, the rotation speed is maintained at 500 rpm for 3 seconds, then maintained at 100 rpm for 2 seconds, maintained at 500 rpm for 3 seconds, and maintained at 100 rpm again for 2 seconds, then the film thickness setting rotation
- the temperature was raised to several (the number of revolutions to obtain a film thickness of 9 ⁇ m) and maintained for 60 seconds. After that, heat drying was performed at 150 ° C.
- a reflection preventing layer is formed on an 8-inch Si substrate (manufactured by Advanced Materials Technology (hereinafter, also referred to as “substrate”) subjected to hexamethyldisilazane treatment using a spin coater “ACT-8” manufactured by Tokyo Electron.
- substrate manufactured by Advanced Materials Technology
- ACT-8 spin coater manufactured by Tokyo Electron.
- the resist composition prepared above was dropped in a state where the substrate was at rest without providing.
- the substrate After dropping, the substrate is rotated, the rotation speed is maintained at 500 rpm for 3 seconds, then maintained at 100 rpm for 2 seconds, maintained at 500 rpm for 3 seconds, and maintained at 100 rpm again for 2 seconds, then the film thickness setting rotation
- the temperature was raised to a certain value (rotational speed to achieve the film thickness described in Table 2) and maintained for 60 seconds. Thereafter, heating and drying were performed at 150 ° C. for 90 seconds on a hot plate to form a resist film having a film thickness ( ⁇ m) shown in Table 2.
- a wafer with a resist film was obtained which has a substrate and a solid film of a resist film formed on the substrate.
- the resist film-coated wafer was used as an evaluation wafer without exposure and development.
- ion implantation was performed on the evaluation wafer to evaluate ion leakage to the substrate. Specifically, phosphorus was implanted under the conditions of a dose amount of 2 ⁇ 10 13 cm ⁇ 2 and an energy of 80 KeV by an ion implantation method, and then the mask was peeled and removed. After this, the injection amount of phosphorus to the substrate was quantified by dynamic secondary ion mass spectrometry (SIMS) analysis. In addition, each value of an Example and a comparative example normalized and showed the value of Example 1 as 1 (reference
- SIMS dynamic secondary ion mass spectrometry
- a reflection preventing layer is formed on an 8-inch Si substrate (manufactured by Advanced Materials Technology (hereinafter, also referred to as “substrate”) subjected to hexamethyldisilazane treatment using a spin coater “ACT-8” manufactured by Tokyo Electron.
- substrate manufactured by Advanced Materials Technology
- ACT-8 spin coater manufactured by Tokyo Electron.
- the resin composition prepared above was dropped in a state where the substrate was at rest without providing. After dropping, the substrate is rotated, the rotation speed is maintained at 500 rpm for 3 seconds, then maintained at 100 rpm for 2 seconds, maintained at 500 rpm for 3 seconds, and maintained at 100 rpm again for 2 seconds, then the film thickness setting rotation
- the temperature was raised to a certain value (rotational speed to achieve the film thickness described in Table 2) and maintained for 60 seconds.
- TMAH tetramethylammonium hydroxide
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Abstract
Description
これら固体撮像素子は、二次元配列された受光部を有し、この受光部で入射光を光電変換して電気的な画像信号を生成する。受光部自体は、可視光領域(380nm~780nm)全般に加え、更に長波長の近赤外領域(波長約2500nm)まで感度を有する。固体撮像素子は、受光面上に、更に、透過波長領域が異なる複数種類のカラーフィルタ層、及び赤外光透過フィルタ層等を含む。
また、本発明は、上記感活性光線性又は感放射線性樹脂組成物を用いたレジスト膜、及びパターン形成方法を提供することも課題とする。
また、本発明は、上記パターン形成方法を用いた固体撮像素子の製造方法を提供することも課題とする。
すなわち、以下の構成により上記目的を達成できることを見出した。
酸分解性基を有する繰り返し単位を含む樹脂と、
光酸発生剤と、
融点又はガラス転移温度が25℃未満であり、且つ、分子量が180以上の添加剤と、を含み、
上記添加剤の含有量が、組成物中の全固形分に対して1質量%以上である、感活性光線性又は感放射線性樹脂組成物。
〔2〕 上記パターンの膜厚が、5μm以上である、〔1〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔3〕 上記パターンの膜厚が、7μm以上である、〔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。
〔4〕 組成物中の固形分濃度が20質量%以上である、〔1〕~〔3〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔5〕 基板上に上記感活性光線性又は感放射線性樹脂組成物を塗布して塗膜を形成した後、上記塗膜を150℃にて90秒間ベークして得られる膜厚9μmの膜の膜密度が、1.05g/cm3以上である、〔1〕~〔4〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔6〕 上記膜密度が、1.10g/cm3以上である、〔5〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔7〕 上記樹脂のガラス転移温度が、170℃以下である、〔1〕~〔6〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔8〕 上記添加剤が、水溶性である、〔1〕~〔7〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔9〕 上記イオンインプランテーション工程が、赤外光成分を選択的に透過する赤外光透過フィルタを含む固体撮像素子の製造における、上記赤外光透過フィルタ用の受光部を形成するためのイオンインプランテーション工程である、〔1〕~〔8〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
〔10〕 〔1〕~〔9〕のいずれかに記載の感活性光線性又は感放射線性樹脂組成物により形成されたレジスト膜。
〔11〕 〔1〕~〔9〕のいずれか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レジスト膜を形成するレジスト膜形成工程と、
上記レジスト膜を露光する露光工程と、
露光された上記レジスト膜を、現像液を用いて現像する現像工程と、を含むパターン形成方法。
〔12〕 〔11〕に記載のパターン形成方法を含む、固体撮像素子の製造方法であって、
基板上に形成された上記パターンをマスクとして上記基板の非マスク領域にイオンを注入することにより、赤外光を感知する受光部を形成するイオンインプランテーション工程と、
上記パターンを上記基板上から除去する工程と、
上記基板のイオン注入された領域の上に赤外光透過フィルタ層を配置する、赤外光透過フィルタ層配置工程と、を含む固体撮像素子の製造方法。
また、本発明によれば、上記感活性光線性又は感放射線性樹脂組成物を用いたレジスト膜、及びパターン形成方法を提供できる。
また、本発明によれば、上記パターン形成方法を用いた固体撮像素子の製造方法を提供できる。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に制限されない。
本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光:Extreme Ultraviolet)、X線、及び電子線(EB:Electron Beam)等を意味する。本明細書中における「光」とは、活性光線又は放射線を意味する。
本明細書中における「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線、X線、及びEUV光等による露光のみならず、電子線、及びイオンビーム等の粒子線による描画も含む。
本明細書において、「~」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
本明細書において、樹脂の重量平均分子量(Mw)、数平均分子量(Mn)、及び分散度(以下、「分子量分布」ともいう。)(Mw/Mn)は、GPC(Gel Permeation Chromatography)装置(東ソー製HLC-8120GPC)によるGPC測定(溶剤:テトラヒドロフラン、流量(サンプル注入量):10μL、カラム:東ソー社製TSK gel Multipore HXL-M、カラム温度:40℃、流速:1.0mL/分、検出器:示差屈折率検出器(Refractive Index Detector))によるポリスチレン換算値として定義される。
(置換基T)
置換基Tとしては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等のハロゲン原子;メトキシ基、エトキシ基及びtert-ブトキシ基等のアルコキシ基;フェノキシ基及びp-トリルオキシ基等のアリールオキシ基;メトキシカルボニル基、ブトキシカルボニル基及びフェノキシカルボニル基等のアルコキシカルボニル基;アセトキシ基、プロピオニルオキシ基及びベンゾイルオキシ基等のアシルオキシ基;アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基及びメトキサリル基等のアシル基;メチルスルファニル基及びtert-ブチルスルファニル基等のアルキルスルファニル基;フェニルスルファニル基及びp-トリルスルファニル基等のアリールスルファニル基;アルキル基;シクロアルキル基;アリール基;ヘテロアリール基;水酸基;カルボキシ基;ホルミル基;スルホ基;シアノ基;アルキルアミノカルボニル基;アリールアミノカルボニル基;スルホンアミド基;シリル基;アミノ基;モノアルキルアミノ基;ジアルキルアミノ基;アリールアミノ基;並びにこれらの組み合わせが挙げられる。
本発明の感活性光線性又は感放射線性樹脂組成物の特徴点としては、特定添加剤を組成物中の全固形分に対して所定量含む点が挙げられる。
本発明の組成物は、典型的には、化学増幅型のレジスト組成物である。
本発明の組成物は、酸分解性基を有する繰り返し単位を含む樹脂(以下、「樹脂(A)」ともいう。)を含む。
この場合、本発明のパターン形成方法において、典型的には、現像液としてアルカリ現像液を採用した場合には、ポジ型パターンが好適に形成され、現像液として有機系現像液を採用した場合には、ネガ型パターンが好適に形成される。
なお、樹脂(A)のガラス転移温度は、カタログ値又は文献値がある場合はその値を採り、無い場合には、示差走査熱量測定(DSC:Differential scanning calorimetry)法によって測定できる。
式(1) 1/(273+Tg)=Σ(Wi/(273+Tgi))
Tg:樹脂(A)のガラス転移温度(℃)
Tgi:単量体iの単独重合体のガラス転移温度(℃)
Wi:単量体iの質量比率。なお、ΣWi=1である。
樹脂(A)は、酸分解性基を有する繰り返し単位(以下、「繰り返し単位X1」ともいう。)を含む。
酸分解性基としては、酸の作用により分解して、極性基を生じる基が好ましい。
極性基としては、カルボキシ基、フェノール性水酸基、フッ素化アルコール基、スルホン酸基、スルホンアミド基、スルホニルイミド基、(アルキルスルホニル)(アルキルカルボニル)メチレン基、(アルキルスルホニル)(アルキルカルボニル)イミド基、ビス(アルキルカルボニル)メチレン基、ビス(アルキルカルボニル)イミド基、ビス(アルキルスルホニル)メチレン基、ビス(アルキルスルホニル)イミド基、トリス(アルキルカルボニル)メチレン基、及びトリス(アルキルスルホニル)メチレン基等の酸性基(2.38質量%テトラメチルアンモニウムヒドロキシド水溶液中で解離する基)、並びにアルコール性水酸基等が挙げられる。
酸の作用により脱離する基(脱離基)としては、例えば、-C(R36)(R37)(R38)、-C(R36)(R37)(OR39)、及び-C(R01)(R02)(OR39)等が挙げられる。
式中、R36~R39は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基、又はアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。
R01及びR02は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、又はアルケニル基を表す。
R36~R39、R01及びR02のシクロアルキル基は、単環でも、多環でもよい。単環のシクロアルキル基としては、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、シクロブチル基、シクロペンチル基、シクロへキシル基、及びシクロオクチル基等が挙げられる。多環のシクロアルキル基としては、炭素数6~20のシクロアルキル基が好ましく、例えば、アダマンチル基、ノルボルニル基、イソボルニル基、カンファニル基、ジシクロペンチル基、α-ピネル基、トリシクロデカニル基、テトラシクロドデシル基、及びアンドロスタニル基等が挙げられる。なお、シクロアルキル基中の少なくとも1つの炭素原子が酸素原子等のヘテロ原子によって置換されていてもよい。
R36~R39、R01及びR02のアリール基は、炭素数6~10のアリール基が好ましく、例えば、フェニル基、ナフチル基、及びアントリル基等が挙げられる。
R36~R39、R01及びR02のアラルキル基は、炭素数7~12のアラルキル基が好ましく、例えば、ベンジル基、フェネチル基、及びナフチルメチル基等が挙げられる。
R36~R39、R01及びR02のアルケニル基は、炭素数2~8のアルケニル基が好ましく、例えば、ビニル基、アリル基、ブテニル基、及びシクロへキセニル基等が挙げられる。
R36とR37とが互いに結合して形成される環としては、シクロアルキル基(単環又は多環)であることが好ましい。シクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、又はノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
樹脂(A)は、繰り返し単位X1として、下記一般式(AI)で表される繰り返し単位を有することが好ましい。
Xa1は、水素原子、ハロゲン原子、又は1価の有機基を表す。
Tは、単結合又は2価の連結基を表す。
Rx1~Rx3は、各々独立に、アルキル基又はシクロアルキル基を表す。
Rx1~Rx3のいずれか2つが結合して環構造を形成してもよく、形成しなくてもよい。
Tは、単結合又は-COO-Rt-が好ましい。Rtは、炭素数1~5の鎖状アルキレン基が好ましく、-CH2-、-(CH2)2-、又は-(CH2)3-がより好ましい。Tは、単結合であることがより好ましい。
Xa1のアルキル基は、置換基を有していてもよく、置換基としては、例えば、水酸基、及びハロゲン原子(好ましくは、フッ素原子)が挙げられる。
Xa1のアルキル基は、炭素数1~4が好ましく、メチル基、エチル基、プロピル基、ヒドロキシメチル基及びトリフルオロメチル基等が挙げられる。Xa1のアルキル基は、メチル基であることが好ましい。
Rx1、Rx2及びRx3のシクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、又はノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
樹脂(A)は、繰り返し単位X1として、フェノール性水酸基が脱離基で保護された構造を有する繰り返し単位を有することも好ましい。なお、本明細書において、フェノール性水酸基とは、芳香族炭化水素基の水素原子をヒドロキシル基で置換してなる基である。芳香族炭化水素基の芳香環は単環又は多環の芳香環であり、ベンゼン環及びナフタレン環等が挙げられる。
式(Y1):-C(Rx1)(Rx2)(Rx3)
式(Y2):-C(=O)OC(Rx1)(Rx2)(Rx3)
式(Y3):-C(R36)(R37)(OR38)
式(Y4):-C(Rn)(H)(Ar)
なかでも、Rx1~Rx3は、各々独立に、直鎖状又は分岐鎖状のアルキル基を表す繰り返し単位であることがより好ましく、Rx1~Rx3が、各々独立に、直鎖状のアルキル基を表す繰り返し単位であることが更に好ましい。
Rx1~Rx3の2つが結合して、単環若しくは多環を形成してもよい。
Rx1~Rx3のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、及びt-ブチル基等の炭素数1~4のアルキル基が好ましい。
Rx1~Rx3のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。なかでも、炭素数5~6の単環のシクロアルキル基がより好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
式(Y1)及び(Y2)で表される基は、例えば、Rx1がメチル基又はエチル基であり、Rx2とRx3とが結合して上述のシクロアルキル基を形成している態様が好ましい。
R61、R62及びR63は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。但し、R62はAr6と結合して環を形成していてもよく、その場合のR62は単結合又はアルキレン基を表す。
X6は、単結合、-COO-、又は-CONR64-を表す。R64は、水素原子又はアルキル基を表す。
L6は、単結合又はアルキレン基を表す。
Ar6は、(n+1)価の芳香族炭化水素基を表し、R62と結合して環を形成する場合には(n+2)価の芳香族炭化水素基を表す。
Y2は、n≧2の場合には各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Y2の少なくとも1つは、酸の作用により脱離する基を表す。Y2としての酸の作用により脱離する基は、式(Y1)~(Y4)であることが好ましい。
nは、1~4の整数を表す。
以下に一般式(AII)で表される繰り返し単位の具体例を示すが、本発明は、これらに制限されない。
樹脂(A)は、繰り返し単位X1以外に、その他の繰り返し単位を含んでいてもよい。
以下に、樹脂(A)が含み得る他の繰り返し単位について詳述する。
・フェノール性水酸基を有する繰り返し単位
樹脂(A)は、上述した繰り返し単位X1以外に、フェノール性水酸基を有する繰り返し単位(以下、「繰り返し単位X2」ともいう。)を含むことが好ましい。なお、繰り返し単位X2は、酸分解性基を有さない。樹脂(A)は、繰り返し単位X2を含むことにより、アルカリ現像時の溶解速度により優れる。
繰り返し単位X2としては、ヒドロキシスチレン繰り返し単位、又は、ヒドロキシスチレン(メタ)アクリレート繰り返し単位が挙げられる。繰り返し単位X2としては、なかでも、下記一般式(I)で表される繰り返し単位が好ましい。
R41、R42及びR43は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。但し、R42はAr4と結合して環を形成していてもよく、その場合のR42は単結合又はアルキレン基を表す。
X4は、単結合、-COO-、又は-CONR64-を表し、R64は、水素原子又はアルキル基を表す。
L4は、単結合又は2価の連結基を表す。
Ar4は、(n+1)価の芳香族炭化水素基を表し、R42と結合して環を形成する場合には(n+2)価の芳香族炭化水素基を表す。
nは、1~5の整数を表す。
一般式(I)で表される繰り返し単位を高極性化する目的では、nが2以上の整数、又はX4が-COO-、又は-CONR64-であることも好ましい。
一般式(I)におけるR41、R42、及びR43で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が挙げられ、フッ素原子が好ましい。
一般式(I)におけるR41、R42、及びR43で表されるアルコキシカルボニル基に含まれるアルキル基としては、上記R41、R42、及びR43におけるアルキル基と同様のものが好ましい。
(n+1)価の芳香族炭化水素基は、更に置換基を有していてもよい。
X4により表される-CONR64-(R64は、水素原子又はアルキル基を表す)におけるR64のアルキル基としては、置換基を有していてもよい、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、ヘキシル基、2-エチルヘキシル基、オクチル基、及びドデシル基等の炭素数20以下のアルキル基が好ましく、炭素数8以下のアルキル基がより好ましい。
X4としては、単結合、-COO-、又は-CONH-が好ましく、単結合、又は-COO-がより好ましい。
Ar4としては、置換基を有していてもよい炭素数6~18の芳香族炭化水素基が好ましく、ベンゼン環基、ナフタレン環基、又はビフェニレン環基がより好ましい。なかでも、一般式(I)で表される繰り返し単位は、ヒドロキシスチレンに由来する繰り返し単位であることが好ましい。即ち、Ar4は、ベンゼン環基であることが好ましい。
樹脂(A)は、残留溶剤をより揮発しやすくできる点で、ヘテロ原子を含んでいてもよい、炭素数が2以上の非酸分解性鎖状アルキル基を有する繰り返し単位(以下、「繰り返し単位X3」ともいう。)を含むことが好ましい。なお、「非酸分解性」とは、光酸発生剤が発生する酸により、脱離/分解反応が起こらない性質を有することを意味する。つまり、「非酸分解性鎖状アルキル基」とは、より具体的には、光酸発生剤が発生する酸の作用により樹脂(A)から脱離しない鎖状アルキル基、又は、光酸発生剤が発生する酸の作用により分解しない鎖状アルキル基が挙げられる。
繰り返し単位X3としては、ホモポリマーとしたときのガラス転移温度(Tg(℃))が50℃以下(好ましくは30℃以下)であるモノマーを由来とする繰り返し単位であることが好ましい。なお、下限値は特に制限されないが、-80℃以上の場合が多い。
以下、繰り返し単位X3について説明する。なお、上記ガラス転移温度は、カタログ値又は文献値がある場合はその値を採り、無い場合には、示差走査熱量測定(DSC)法によって測定することができる。
ヘテロ原子を含む炭素数2~20の鎖状アルキル基としては、例えば、1つ又は2つ以上の-CH2-が、-O-、-S-、-CO-、-NR6-、又はこれらを2以上組み合わせた2価の有機基で置換された鎖状アルキル基が挙げられる。上記R6は、水素原子、又は炭素数が1~6のアルキル基を表す。
ヘテロ原子を含んでいてもよい、炭素数が2以上の非酸分解性鎖状アルキル基としては、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、イソブチル基、sec-ブチル基、1-エチルペンチル基、及び2-エチルヘキシル基、並びに、これらの1つ又は2つ以上の-CH2-が-O-又は-O-CO-で置換された1価のアルキル基が挙げられる。
なお、炭素数が2以上の非酸分解性鎖状アルキル基は、置換基(例えば置換基Tで例示する置換基が挙げられる。)を有していてもよい。
R1で表されるアルキル基(直鎖状、分岐鎖状、及び環状のいずれであってもよい。)としては、特に制限されないが、例えば、炭素数1~10のアルキル基が挙げられ、具体的には、メチル基、エチル基、及びtert-ブチル基等が挙げられる。なかでも、炭素数1~3のアルキル基が好ましく、メチル基がより好ましい。
R1としては、なかでも、水素原子又はメチル基が好ましい。
樹脂(A)において、繰り返し単位X3の含有量(繰り返し単位X3が複数存在する場合はその合計)は、樹脂(A)の全繰り返し単位に対して、5モル%以上が好ましく、5~30モル%がより好ましく、5~20モル%が更に好ましい。
樹脂(A)は、ラクトン構造、スルトン構造、及びカーボネート構造からなる群から選択される少なくとも1種を有する繰り返し単位(以下、「繰り返し単位X4」ともいう。)を含むことが好ましい。
樹脂(A)は、下記一般式(LC1-1)~(LC1-21)のいずれかで表されるラクトン構造、又は、下記一般式(SL1-1)~(SL1-3)のいずれかで表されるスルトン構造を有する繰り返し単位を含んでいることが更に好ましい。また、ラクトン構造又はスルトン構造が主鎖に直接結合していてもよい。好ましい構造としては、一般式(LC1-1)、一般式(LC1-4)、一般式(LC1-5)、一般式(LC1-8)、一般式(LC1-16)、若しくは一般式(LC1-21)で表されるラクトン構造、又は、一般式(SL1-1)で表されるスルトン構造が挙げられる。
Aは、エステル結合(-COO-で表される基)又はアミド結合(-CONH-で表される基)を表す。
nは、-R0-Z-で表される構造の繰り返し数であり、0~5の整数を表し、0又は1であることが好ましく、0であることがより好ましい。nが0である場合、-R0-Z-は存在せず、単結合となる。
R0は、アルキレン基、シクロアルキレン基、又はその組み合わせを表す。R0が複数個ある場合、R0は、各々独立に、アルキレン基、シクロアルキレン基、又はその組み合わせを表す。
Zは、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表す。Zが複数個ある場合には、Zは、各々独立に、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表す。
R8は、ラクトン構造又はスルトン構造を有する1価の有機基を表す。
R7は、水素原子、ハロゲン原子又は1価の有機基(好ましくはメチル基)を表す。
Zとしては、エーテル結合、又はエステル結合が好ましく、エステル結合がより好ましい。
環状炭酸エステル構造を有する繰り返し単位は、下記一般式(A-1)で表される繰り返し単位であることが好ましい。
nは0以上の整数を表す。
RA 2は、置換基を表す。nが2以上の場合、RA 2は、各々独立して、置換基を表す。
Aは、単結合、又は2価の連結基を表す。
Zは、式中の-O-C(=O)-O-で表される基と共に単環構造又は多環構造を形成する原子団を表す。
樹脂(A)は、繰り返し単位X1及び繰り返し単位X2以外の芳香族環を有する繰り返し単位(以下、「繰り返し単位X5」ともいう。)を含んでいることが好ましい。
繰り返し単位X5としては、例えば、下記一般式(III)で表される繰り返し単位が好ましい。
一般式(III)で表される繰り返し単位の原料モノマーとしては、具体的に、ベンジル(メタ)アクリレート、及びスチレン等が挙げられる。
樹脂(A)において、繰り返し単位X5の含有量(繰り返し単位X5が複数存在する場合はその合計)は、樹脂(A)の全繰り返し単位に対して、5モル%以上が好ましく、5~30モル%がより好ましく、5~20モル%が更に好ましい。
このような繰り返し構造単位としては、所定の単量体に相当する繰り返し構造単位が挙げられるが、これらに制限されない。
その他にも、上記種々の繰り返し構造単位に相当する単量体と共重合可能である付加重合性の不飽和化合物を用いてもよい。
樹脂(A)において、各繰り返し構造単位の含有モル比は、種々の性能を調節するために適宜設定される。
本発明の組成物中、樹脂(A)の含有量は、組成物の全固形分に対して、一般的に20質量%以上の場合が多く、40質量%以上が好ましく、60質量%以上がより好ましく、80質量%以上が更に好ましい。上限は特に制限されないが、99.5質量%以下が好ましく、99質量%以下がより好ましく、98質量%以下が更に好ましい。
本発明の組成物は、特定添加剤(以下、「特定添加剤(B)」ともいう。)を含む。
特定添加剤(B)は、融点又はガラス転移温度が25℃未満であり、且つ、分子量が180以上である。なお、特定添加剤(B)は、融点及びガラス転移温度の少なくとも一方が25℃未満であればよい。特定添加剤(B)が上記所定特性を有することで、形成されるレジスト膜の可塑性が向上し、結果として、例えば、露光前加熱(PB(PreBake))時等において膜中の溶剤が揮発しやすくなる。
特定添加剤(B)の融点及びガラス転移温度(Tg(℃))は、形成されるパターンの膜密度がより優れる点で、25℃以下が好ましく、0℃以下がより好ましい。なお、その下限値は、例えば、-100℃以上である。なお、上記融点及びガラス転移温度は、カタログ値又は文献値がある場合はその値を採り、無い場合には、示差走査熱量測定(DSC)法によって測定できる。
また、特定添加剤(B)の分子量は、形成されるパターンの膜密度がより優れる点で、200以上が好ましい。また、その上限値は、例えば、400以下である。なお、特定添加剤(B)が分子量分布を有する場合、その重量平均分子量は、形成されるパターンの膜密度がより優れる点で、200以上が好ましい。なお、その上限値は、例えば、400以下である。
特定添加剤(B)としては上記条件を満たせば特に制限されないが、現像時にアルカリ現像液に溶解しやすい点で、水溶性であることが好ましい。なお、水溶性とは、水に対する溶解度(25℃)が300g/L以上であることを意図する。
特定添加剤(B)が水溶性である場合、現像の際に現像液に溶解しやすいことからパターンに残存しにくく、結果として、形成されるパターンの膜密度がより優れる。
上記反応基としては特に制限されないが、水酸基、カルボキシル基、及びアミノ基等が挙げられる。特定添加剤(B)が上記反応基を有することにより、レジスト膜を露光及び現像した後、上記特定添加剤(B)が上記反応基により樹脂と結合して膜中に取り込まれるため、形成されるパターンの膜密度がより優れる。
ポリ(オキシアルキレン)構造を有する化合物において、オキシアルキレン単位中の炭素数としては、2~6が好ましく、2~3がより好ましい。また、オキシアルキレン単位の平均付加数としては、2~10が好ましく、2~6がより好ましい。
特定添加剤(B)として具体的には、例えば下記のものが挙げられる。
本発明の組成物中、特定添加剤(B)の含有量は、組成物の全固形分に対して、1質量%以上であり、3質量%以上が好ましく、5質量%以上が更に好ましい。また、その上限は、例えば30質量%以下であり、25質量%以下が好ましい。
本発明の組成物は、光酸発生剤(以下、「光酸発生剤(C)」ともいう。)を含む。
光酸発生剤は、活性光線又は放射線の照射により酸を発生する化合物である。
光酸発生剤としては、活性光線又は放射線の照射により有機酸を発生する化合物が好ましい。例えば、スルホニウム塩化合物、ヨードニウム塩化合物、ジアゾニウム塩化合物、ホスホニウム塩化合物、イミドスルホネート化合物、オキシムスルホネート化合物、ジアゾジスルホン化合物、ジスルホン化合物、及びo-ニトロベンジルスルホネート化合物が挙げられる。
R201、R202及びR203は、各々独立に、有機基を表す。
R201、R202及びR203としての有機基の炭素数は、一般的に1~30であり、1~20が好ましい。
また、R201~R203のうち2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合、又はカルボニル基を含んでいてもよい。R201~R203の内の2つが結合して形成する基としては、アルキレン基(例えば、ブチレン基、ペンチレン基)及び-CH2-CH2-O-CH2-CH2-が挙げられる。
Z-は、アニオンを表す。
なお、光酸発生剤(C)は、一般式(ZI)で表される構造を複数有する化合物であってもよい。例えば、一般式(ZI)で表される化合物のR201~R203の少なくとも1つと、一般式(ZI)で表されるもうひとつの化合物のR201~R203の少なくとも一つとが、単結合又は連結基を介して結合した構造を有する化合物であってもよい。
化合物(ZI-1)は、上記一般式(ZI)のR201~R203の少なくとも1つがアリール基である、アリールスルホニウム化合物、すなわち、アリールスルホニウムをカチオンとする化合物である。
アリールスルホニウム化合物は、R201~R203の全てがアリール基でもよいし、R201~R203の一部がアリール基であり、残りがアルキル基又はシクロアルキル基であってもよい。
アリールスルホニウム化合物としては、例えば、トリアリールスルホニウム化合物、ジアリールアルキルスルホニウム化合物、アリールジアルキルスルホニウム化合物、ジアリールシクロアルキルスルホニウム化合物、及びアリールジシクロアルキルスルホニウム化合物が挙げられる。
アリールスルホニウム化合物が必要に応じて有しているアルキル基又はシクロアルキル基は、炭素数1~15の直鎖状アルキル基、炭素数3~15の分岐鎖状アルキル基、又は炭素数3~15のシクロアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、n-ブチル基、sec-ブチル基、t-ブチル基、シクロプロピル基、シクロブチル基、及びシクロヘキシル基等が挙げられる。
化合物(ZI-2)は、式(ZI)におけるR201~R203が、各々独立に、芳香環を有さない有機基を表す化合物である。ここで芳香環とは、ヘテロ原子を含む芳香族環も包含する。
R201~R203としての芳香環を有さない有機基の炭素数は、一般的に1~30であり、1~20が好ましい。
R201~R203は、各々独立に、好ましくはアルキル基、シクロアルキル基、アリル基、又はビニル基であり、より好ましくは直鎖状又は分岐鎖状の2-オキソアルキル基、2-オキソシクロアルキル基、又はアルコキシカルボニルメチル基、さらに好ましくは直鎖状又は分岐鎖状の2-オキソアルキル基である。
R201~R203は、ハロゲン原子、アルコキシ基(例えば炭素数1~5)、水酸基、シアノ基、又はニトロ基によって更に置換されていてもよい。
化合物(ZI-3)は、下記一般式(ZI-3)で表され、フェナシルスルフォニウム塩構造を有する化合物である。
R1c~R5cは、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アルキルカルボニルオキシ基、シクロアルキルカルボニルオキシ基、ハロゲン原子、水酸基、ニトロ基、アルキルチオ基又はアリールチオ基を表す。
R6c及びR7cは、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアリール基を表す。
Rx及びRyは、各々独立に、アルキル基、シクロアルキル基、2-オキソアルキル基、2-オキソシクロアルキル基、アルコキシカルボニルアルキル基、アリル基又はビニル基を表す。
上記環構造としては、芳香族又は非芳香族の炭化水素環、芳香族又は非芳香族の複素環、及びこれらの環が2つ以上組み合わされてなる多環縮合環が挙げられる。環構造としては、3~10員環が挙げられ、4~8員環が好ましく、5又は6員環がより好ましい。
R5cとR6c、及びR5cとRxが結合して形成する基としては、単結合又はアルキレン基が好ましい。アルキレン基としては、メチレン基、及びエチレン基等が挙げられる。
Zc-は、アニオンを表す。
化合物(ZI-4)は、下記一般式(ZI-4)で表される。
lは0~2の整数を表す。
rは0~8の整数を表す。
R13は、水素原子、フッ素原子、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、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。
R14は、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。R14は、複数存在する場合は各々独立して、水酸基等の上記基を表す。
R15は、各々独立して、アルキル基、シクロアルキル基又はナフチル基を表す。これらの基は置換基を有してもよい。2つのR15が互いに結合して環を形成してもよい。2つのR15が互いに結合して環を形成するとき、環骨格内に、酸素原子、又は窒素原子等のヘテロ原子を含んでもよい。一態様において、2つのR15がアルキレン基であり、互いに結合して環構造を形成することが好ましい。
Z-は、アニオンを表す。
一般式(ZII)、及び(ZIII)中、R204~R207は、各々独立に、アリール基、アルキル基又はシクロアルキル基を表す。
R204~R207のアリール基としてはフェニル基、又はナフチル基が好ましく、フェニル基がより好ましい。R204~R207のアリール基は、酸素原子、窒素原子、又は硫黄原子等を有する複素環構造を有するアリール基であってもよい。複素環構造を有するアリール基の骨格としては、例えば、ピロール、フラン、チオフェン、インドール、ベンゾフラン、及びベンゾチオフェン等が挙げられる。
R204~R207のアルキル基及びシクロアルキル基としては、炭素数1~10の直鎖状アルキル基又は炭素数3~10の分岐鎖状アルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基、及びペンチル基)、又は、炭素数3~10のシクロアルキル基(例えばシクロペンチル基、シクロヘキシル基、及びノルボルニル基)が好ましい。
Z-は、アニオンを表す。
oは、1~3の整数を表す。pは、0~10の整数を表す。qは、0~10の整数を表す。
Xfは、フッ素原子又は炭素数1~4のパーフルオロアルキル基であることが好ましく、フッ素原子又はCF3であることがより好ましい。特に、双方のXfがフッ素原子であることが更に好ましい。
R4及びR5で表されるアルキル基は、置換基を有していてもよく、炭素数1~4が好ましい。R4及びR5は、好ましくは水素原子である。
少なくとも一つのフッ素原子で置換されたアルキル基の具体例及び好適な態様は一般式(3)中のXfの具体例及び好適な態様と同じである。
2価の連結基としては、例えば、-COO-(-C(=O)-O-)、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-S-、-SO-、-SO2-、アルキレン基(好ましくは炭素数1~6)、シクロアルキレン基(好ましくは炭素数3~15)、アルケニレン基(好ましくは炭素数2~6)及びこれらの複数を組み合わせた2価の連結基等が挙げられる。これらの中でも、-COO-、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-SO2-、-COO-アルキレン基-、-OCO-アルキレン基-、-CONH-アルキレン基-又は-NHCO-アルキレン基-が好ましく、-COO-、-OCO-、-CONH-、-SO2-、-COO-アルキレン基-又は-OCO-アルキレン基-がより好ましい。
環状の有機基としては、例えば、脂環基、アリール基、及び複素環基が挙げられる。
脂環基は、単環式であってもよく、多環式であってもよい。単環式の脂環基としては、例えば、シクロペンチル基、シクロヘキシル基、及びシクロオクチル基等の単環のシクロアルキル基が挙げられる。多環式の脂環基としては、例えば、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が挙げられる。中でも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の炭素数7以上の嵩高い構造を有する脂環基が好ましい。
複素環基は、単環式であってもよく、多環式であってもよい。多環式の方がより酸の拡散を抑制可能である。また、複素環基は、芳香族性を有していてもよいし、芳香族性を有していなくてもよい。芳香族性を有している複素環としては、例えば、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、及びピリジン環が挙げられる。芳香族性を有していない複素環としては、例えば、テトラヒドロピラン環、ラクトン環、スルトン環及びデカヒドロイソキノリン環が挙げられる。ラクトン環及びスルトン環の例としては、前述の樹脂において例示したラクトン構造及びスルトン構造が挙げられる。複素環基における複素環としては、フラン環、チオフェン環、ピリジン環、又はデカヒドロイソキノリン環が特に好ましい。
XB1及びXB2は、各々独立に、水素原子、又はフッ素原子を有さない1価の有機基を表す。XB1及びXB2は、水素原子であることが好ましい。
XB3及びXB4は、各々独立に、水素原子、又は1価の有機基を表す。XB3及びXB4の少なくとも一方がフッ素原子又はフッ素原子を有する1価の有機基であることが好ましく、XB3及びXB4の両方がフッ素原子又はフッ素原子を有する1価の有機基であることがより好ましい。XB3及びXB4の両方が、フッ素原子で置換されたアルキル基であることが更に好ましい。
L、q及びWは、一般式(3)と同様である。
Arは、アリール基を表し、スルホン酸アニオン及び-(D-B)基以外の置換基を更に有していてもよい。更に有してもよい置換基としては、フッ素原子及び水酸基等が挙げられる。
光酸発生剤は、低分子化合物の形態であることが好ましい。
光酸発生剤が、低分子化合物の形態である場合、分子量は3,000以下が好ましく、2,000以下がより好ましく、1,000以下が更に好ましい。
光酸発生剤が、重合体の一部に組み込まれた形態である場合、前述した樹脂(A)の一部に組み込まれてもよく、樹脂(A)とは異なる樹脂に組み込まれてもよい。
光酸発生剤は、1種単独で使用してもよいし、2種以上を併用してもよい。
本発明の組成物中、光酸発生剤の含有量(複数種存在する場合はその合計)は、組成物の全固形分に対して、0.1~35質量%が好ましく、0.5~25質量%がより好ましく、1~20質量%が更に好ましく、1~15質量%が特に好ましい。
本発明の組成物は、酸拡散制御剤(D)を含むことが好ましい。
酸拡散制御剤(D)は、露光時に光酸発生剤等から発生する酸をトラップし、余分な発生酸による、未露光部における酸分解性樹脂の反応を抑制するクエンチャーとして作用する。例えば、塩基性化合物(DA)、活性光線又は放射線の照射により塩基性が低下又は消失する塩基性化合物(DB)、酸発生剤に対して相対的に弱酸となるオニウム塩(DC)、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物(DD)、又はカチオン部に窒素原子を有するオニウム塩化合物(DE)等を酸拡散制御剤として使用できる。本発明の組成物においては、公知の酸拡散制御剤を適宜使用できる。例えば、米国特許出願公開2016/0070167A1号明細書の段落<0627>~<0664>、米国特許出願公開2015/0004544A1号明細書の段落<0095>~<0187>、米国特許出願公開2016/0237190A1号明細書の段落<0403>~<0423>、及び、米国特許出願公開2016/0274458A1号明細書の段落<0259>~<0328>に開示された公知の化合物を酸拡散制御剤(D)として好適に使用できる。
R200、R201及びR202は、同一でも異なってもよく、各々独立に、水素原子、アルキル基(好ましくは炭素数1~20)、シクロアルキル基(好ましくは炭素数3~20)又はアリール基(炭素数6~20)を表す。R201とR202は、互いに結合して環を形成してもよい。
R203、R204、R205及びR206は、同一でも異なってもよく、各々独立に、炭素数1~20のアルキル基を表す。
上記アルキル基について、置換基を有するアルキル基としては、炭素数1~20のアミノアルキル基、炭素数1~20のヒドロキシアルキル基、又は炭素数1~20のシアノアルキル基が好ましい。
一般式(A)及び(E)中のアルキル基は、無置換であることがより好ましい。
プロトンアクセプター性は、pH測定を行うことによって確認できる。
光酸発生剤と、光酸発生剤から生じた酸に対して相対的に弱酸である酸を発生するオニウム塩とを混合して用いた場合、活性光線性又は放射線の照射により光酸発生剤から生じた酸が未反応の弱酸アニオンを有するオニウム塩と衝突すると、塩交換により弱酸を放出して強酸アニオンを有するオニウム塩を生じる。この過程で強酸がより触媒能の低い弱酸に交換されるため、見かけ上、酸が失活して酸拡散が制御される。
化合物(DCA)としては、下記一般式(C-1)~(C-3)のいずれかで表される化合物が好ましい。
R1、R2、及びR3は、各々独立に炭素数1以上の置換基を表す。
L1は、カチオン部位とアニオン部位とを連結する2価の連結基又は単結合を表す。
-X-は、-COO-、-SO3 -、-SO2 -、及び-N--R4から選択されるアニオン部位を表す。R4は、隣接するN原子との連結部位に、カルボニル基(-C(=O)-)、スルホニル基(-S(=O)2-)、及びスルフィニル基(-S(=O)-)のうち少なくとも1つを有する1価の置換基を表す。
R1、R2、R3、R4、及びL1は、互いに結合して環構造を形成してもよい。また、一般式(C-3)において、R1~R3のうち2つを合わせて1つの2価の置換基を表し、N原子と2重結合により結合していてもよい。
酸の作用により脱離する基としては、アセタール基、カルボネート基、カルバメート基、3級エステル基、3級水酸基、又はヘミアミナールエーテル基が好ましく、カルバメート基、又はヘミアミナールエーテル基がより好ましい。
化合物(DD)の分子量は、100~1000が好ましく、100~700がより好ましく、100~500が更に好ましい。
化合物(DD)は、窒素原子上に保護基を有するカルバメート基を有してもよい。カルバメート基を構成する保護基としては、下記一般式(d-1)で表される。
Rbは、各々独立に、水素原子、アルキル基(好ましくは炭素数1~10)、シクロアルキル基(好ましくは炭素数3~30)、アリール基(好ましくは炭素数3~30)、アラルキル基(好ましくは炭素数1~10)、又はアルコキシアルキル基(好ましくは炭素数1~10)を表す。Rbは相互に連結して環を形成していてもよい。
Rbが示すアルキル基、シクロアルキル基、アリール基、及びアラルキル基は、各々独立にヒドロキシル基、シアノ基、アミノ基、ピロリジノ基、ピペリジノ基、モルホリノ基、オキソ基等の官能基、アルコキシ基、又はハロゲン原子で置換されていてもよい。Rbが示すアルコキシアルキル基についても同様である。
2つのRbが相互に連結して形成する環としては、脂環式炭化水素、芳香族炭化水素、複素環式炭化水素及びその誘導体等が挙げられる。
一般式(d-1)で表される基の具体的な構造としては、米国特許公報US2012/0135348A1号明細書の段落<0466>に開示された構造が挙げられるが、これに制限されない。
lは0~2の整数を表し、mは1~3の整数を表し、l+m=3を満たす。
Raは、水素原子、アルキル基、シクロアルキル基、アリール基又はアラルキル基を表す。lが2のとき、2つのRaは同じでも異なっていてもよく、2つのRaは相互に連結して式中の窒素原子と共に複素環を形成していてもよい。この複素環には式中の窒素原子以外のヘテロ原子を含んでいてもよい。
Rbは、上記一般式(d-1)におけるRbと同義であり、好ましい例も同様である。
一般式(6)において、Raとしてのアルキル基、シクロアルキル基、アリール基、及びアラルキル基は、各々独立にRbとしてのアルキル基、シクロアルキル基、アリール基、及びアラルキル基が置換されていてもよい基として前述した基と同様な基で置換されていてもよい。
本発明における特に好ましい化合物(DD)の具体例としては、米国特許出願公開2012/0135348A1号明細書の段落<0475>に開示された化合物が挙げられるが、これに制限されない。
化合物(DE)の好ましい具体例としては、米国特許出願公開2015/0309408A1号明細書の段落<0203>に開示された化合物が挙げられるが、これに制限されない。
酸拡散制御剤(D)の組成物中の含有量(複数種存在する場合はその合計)は、組成物の全固形分に対して、0.01~10質量%が好ましく、0.01~5質量%がより好ましい。
本発明の組成物は、溶剤を含むことが好ましい。
本発明の組成物においては、公知のレジスト溶剤を適宜使用できる。例えば、米国特許出願公開2016/0070167A1号明細書の段落<0665>~<0670>、米国特許出願公開2015/0004544A1号明細書の段落<0210>~<0235>、米国特許出願公開2016/0237190A1号明細書の段落<0424>~<0426>、及び、米国特許出願公開2016/0274458A1号明細書の段落<0357>~<0366>に開示された公知の溶剤を好適に使用できる。
組成物を調製する際に使用できる溶剤としては、例えば、アルキレングリコールモノアルキルエーテルカルボキシレート、アルキレングリコールモノアルキルエーテル、乳酸アルキルエステル、アルコキシプロピオン酸アルキル、環状ラクトン(好ましくは炭素数4~10)、環を有してもよいモノケトン化合物(好ましくは炭素数4~10)、アルキレンカーボネート、アルコキシ酢酸アルキル、及びピルビン酸アルキル等の有機溶剤が挙げられる。
水酸基を含む溶剤、及び水酸基を含まない溶剤としては、前述の例示化合物を適宜選択できるが、水酸基を含む溶剤としては、アルキレングリコールモノアルキルエーテル、又は乳酸アルキル等が好ましく、プロピレングリコールモノメチルエーテル(PGME)、プロピレングリコールモノエチルエーテル(PGEE)、2-ヒドロキシイソ酪酸メチル、又は乳酸エチルがより好ましい。また、水酸基を含まない溶剤としては、アルキレングリコールモノアルキルエーテルアセテート、アルキルアルコキシプロピオネート、環を有していてもよいモノケトン化合物、環状ラクトン、又は酢酸アルキル等が好ましく、これらの中でも、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)、エチルエトキシプロピオネート、2-ヘプタノン、γ-ブチロラクトン、シクロヘキサノン、シクロペンタノン又は酢酸ブチルがより好ましく、プロピレングリコールモノメチルエーテルアセテート、γ-ブチロラクトン、エチルエトキシプロピオネート、シクロヘキサノン、シクロペンタノン又は2-ヘプタノンが更に好ましい。水酸基を含まない溶剤としては、プロピレンカーボネートも好ましい。
水酸基を含む溶剤と水酸基を含まない溶剤との混合比(質量比)は、1/99~99/1であり、10/90~90/10が好ましく、20/80~60/40がより好ましい。水酸基を有さない溶剤を50質量%以上含む混合溶剤が、塗布均一性の点で好ましい。
溶剤は、プロピレングリコールモノメチルエーテルアセテートを含むことが好ましく、プロピレングリコールモノメチルエーテルアセテート単独溶剤でもよいし、プロピレングリコールモノメチルエーテルアセテートを含む2種類以上の混合溶剤でもよい。
本発明の組成物は、酸の作用により樹脂を架橋する化合物(以下、「架橋剤(F)」ともいう。)を含んでもよい。架橋剤(F)としては、公知の化合物を適宜に使用できる。例えば、米国特許出願公開2016/0147154A1号明細書の段落<0379>~<0431>、及び、米国特許出願公開2016/0282720A1号明細書の段落<0064>~<0141>に開示された公知の化合物を架橋剤(F)として好適に使用できる。
架橋剤(F)は、樹脂を架橋しうる架橋性基を有している化合物であり、架橋性基としては、ヒドロキシメチル基、アルコキシメチル基、アシルオキシメチル基、アルコキシメチルエーテル基、オキシラン環、及びオキセタン環等が挙げられる。
架橋性基は、ヒドロキシメチル基、アルコキシメチル基、オキシラン環又はオキセタン環であることが好ましい。
架橋剤(F)は、架橋性基を2個以上有する化合物(樹脂も含む)であることが好ましい。
架橋剤(F)は、ヒドロキシメチル基又はアルコキシメチル基を有する、フェノール誘導体、ウレア系化合物(ウレア構造を有する化合物)又はメラミン系化合物(メラミン構造を有する化合物)であることがより好ましい。
架橋剤は1種単独で用いてもよく、2種以上を併用してもよい。
架橋剤(F)の含有量は、レジスト組成物の全固形分に対して、1~50質量%が好ましく、3~40質量%が好ましく、5~30質量%が更に好ましい。
本発明の組成物は、界面活性剤を含むことが好ましい。界面活性剤を含む場合、フッ素系及び/又はシリコン系界面活性剤(具体的には、フッ素系界面活性剤、シリコン系界面活性剤、又はフッ素原子とケイ素原子との両方を有する界面活性剤)が好ましい。
フッ素系及び/又はシリコン系界面活性剤として、米国特許出願公開第2008/0248425号明細書の段落<0276>に記載の界面活性剤が挙げられる。
また、米国特許出願公開第2008/0248425号明細書の段落<0280>に記載の、フッ素系及び/又はシリコン系界面活性剤以外の他の界面活性剤を使用することもできる。
本発明の組成物が界面活性剤を含む場合、界面活性剤の含有量は、組成物の全固形分に対して、0.0001~2質量%が好ましく、0.0005~1質量%がより好ましい。
本発明の組成物は、更に、酸増殖剤、染料、可塑剤、光増感剤、光吸収剤、アルカリ可溶性樹脂、溶解阻止剤、及び溶解促進剤等を含んでいてもよい。
本発明の組成物の固形分濃度は、通常1.0質量%以上であり、より厚膜のパターンを形成できる点で、10質量%以上が好ましく、20質量%がより好ましく、30質量%が更に好ましい。その上限は特に制限されないが、例えば、50質量%以下である。なお、固形分濃度とは、組成物の総質量に対する、溶剤を除く他のレジスト成分の質量の質量百分率である。
なお、粘度は、E型粘度計により測定できる。
なお、後述するように、本発明の組成物からパターンを形成できる。
また、形成されるパターンの膜密度は、イオンインプランテーション工程でのイオン漏れがより抑制できる点で、1.05g/cm3以上が好ましく、1.10g/cm3以上がより好ましい。
なお、上記膜密度は、基板上に本発明の組成物を塗布して塗膜を形成した後、上記塗膜を150℃にて90秒間ベークして得られる膜厚9μmの膜の膜密度を意図する。
本発明の組成物は、活性光線又は放射線の照射により反応して性質が変化する感活性光線性又は感放射線性樹脂組成物に関する。更に詳しくは、本発明の組成物は、IC(Integrated Circuit)等の半導体製造工程、液晶若しくはサーマルヘッド等の回路基板の製造、インプリント用モールド構造体の作製、その他のフォトファブリケーション工程、又は平版印刷版、若しくは酸硬化性組成物の製造に使用される感活性光線性又は感放射線性樹脂組成物に関する。本発明において形成されるパターンは、イオンインプランテーション工程、エッチング工程、バンプ電極形成工程、再配線形成工程、及びMEMS(Micro Electro Mechanical Systems)等においても使用できる。
なかでも、本発明の組成物は、赤外光成分を選択的に透過する赤外光透過フィルタを含む固体撮像素子の製造における、上記赤外光透過フィルタ用の受光部(言い換えると、赤外光を感知する受光部)を形成するためのイオンインプランテーション工程に用いられることが好ましい。
本発明は上記感活性光線性又は感放射線性樹脂組成物を用いたパターン形成方法にも関する。以下、本発明のパターン形成方法について説明する。また、パターン形成方法の説明と併せて、本発明のレジスト膜(言い換えると、感活性光線性又は感放射線性樹脂組成物の塗膜)についても説明する。
(i)上述した感活性光線性又は感放射線性樹脂組成物を用いてレジスト膜を支持体上に形成する工程(レジスト膜形成工程)と、
(ii)上記レジスト膜を露光する(活性光線又は放射線を照射する)工程(露光工程)と、
(iii)上記露光されたレジスト膜を、現像液を用いて現像する工程(現像工程)と、を含む。
本発明のパターン形成方法は、(ii)露光工程における露光方法が、液浸露光であってもよい。
本発明のパターン形成方法は、(ii)露光工程の前に、(iv)前加熱(PB:PreBake)工程を含むことが好ましい。
本発明のパターン形成方法は、(ii)露光工程の後、かつ、(iii)現像工程の前に、(v)露光後加熱(PEB:Post Exposure Bake)工程を含むことが好ましい。
本発明のパターン形成方法は、(ii)露光工程を、複数回含んでいてもよい。
本発明のパターン形成方法は、(iv)前加熱工程を、複数回含んでいてもよい。
本発明のパターン形成方法は、(v)露光後加熱工程を、複数回含んでいてもよい。
また、必要に応じて、レジスト膜と支持体との間にレジスト下層膜(例えば、SOG(Spin On Glass)、SOC(Spin On Carbon)、及び、反射防止膜)を形成してもよい。レジスト下層膜を構成する材料としては、公知の有機系又は無機系の材料を適宜使用できる。
レジスト膜の上層に、保護膜(トップコート)を形成してもよい。保護膜としては、公知の材料を適宜使用できる。例えば、米国特許出願公開第2007/0178407号明細書、米国特許出願公開第2008/0085466号明細書、米国特許出願公開第2007/0275326号明細書、米国特許出願公開第2016/0299432号明細書、米国特許出願公開第2013/0244438号明細書、及び国際特許出願公開第2016/157988A号明細書に開示された保護膜形成用組成物を好適に使用できる。保護膜形成用組成物としては、上述した酸拡散制御剤を含むものが好ましい。
加熱時間は、(iv)前加熱工程及び(v)露光後加熱工程のいずれにおいても、30~300秒が好ましく、30~180秒がより好ましく、30~90秒が更に好ましい。
加熱は、露光装置及び現像装置に備わっている手段で行うことができ、ホットプレート等を用いて行ってもよい。
更に、上記アルカリ現像液は、アルコール類、及び/又は界面活性剤を適当量含んでいてもよい。アルカリ現像液のアルカリ濃度は、通常0.1~20質量%である。アルカリ現像液のpHは、通常10~15である。
アルカリ現像液を用いて現像を行う時間は、通常10~300秒である。
アルカリ現像液のアルカリ濃度、pH、及び現像時間は、形成するパターンに応じて、適宜調整できる。
有機系現像液に対する有機溶剤の含有量は、現像液の全量に対して、50~100質量%が好ましく、80~100質量%がより好ましく、90~100質量%が更に好ましく、95~100質量%が特に好ましい。
炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤、及びエーテル系溶剤の具体例としては、有機溶剤を含む現像液において説明したものと同様のものが挙げられる。
この場合のリンス工程に用いるリンス液としては、1価アルコールを含むリンス液がより好ましい。
リンス液中の含水率は、10質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下が更に好ましい。含水率を10質量%以下とすることで、良好な現像特性が得られる。
洗浄処理の方法は特に制限されないが、例えば、一定速度で回転している基板上にリンス液を吐出しつづける方法(回転塗布法)、リンス液が満たされた槽中に基板を一定時間浸漬する方法(ディップ法)、又は基板表面にリンス液を噴霧する方法(スプレー法)等が挙げられる。中でも、回転塗布法で洗浄処理を行い、洗浄後に基板を2,000~4,000rpm(revolution per minute)の回転数で回転させ、リンス液を基板上から除去することが好ましい。また、リンス工程の後に加熱工程(Post Bake)を含むことも好ましい。この加熱工程によりパターン間及びパターン内部に残留した現像液及びリンス液が除去される。リンス工程の後の加熱工程において、加熱温度は通常40~160℃であり、70~95℃が好ましく、加熱時間は通常10秒~3分であり、30秒~90秒が好ましい。
フィルタ濾過のほか、吸着材による不純物の除去を行ってもよく、フィルタ濾過と吸着材を組み合わせて使用してもよい。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル若しくはゼオライト等の無機系吸着材、又は活性炭等の有機系吸着材を使用できる。金属吸着剤としては、例えば、日本国特許出願公開第2016-206500号明細書(特開2016-206500)に開示されるものが挙げられる。
また、上記各種材料に含まれる金属等の不純物を低減する方法としては、各種材料を構成する原料として金属含有量が少ない原料を選択する、各種材料を構成する原料に対してフィルタ濾過を行う、又は装置内をテフロン(登録商標)でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法が挙げられる。各種材料を構成する原料に対して行うフィルタ濾過における好ましい条件は、上記した条件と同様である。
本発明の固体撮像素子の製造方法は、上述したパターン形成方法を含む、固体撮像素子の製造方法であって、
(i)基板上に形成されたパターンをマスクとして上記基板の非マスク領域にイオンを注入することにより、赤外光を感知する受光部を形成するイオンインプランテーション工程(イオンインプランテーション工程)と、
(ii)上記パターンを基板上から除去する工程(マスク除去工程)と、
(iii)上記基板のイオン注入された領域の上に赤外光透過フィルタ層を配置する、赤外光透過フィルタ層配置工程(赤外光透過フィルタ層配置工程)と、を含む。
また、(ii)マスク除去工程、及び(iii)赤外光透過フィルタ層配置工程については、公知の方法を使用できる。例えば、特開2015-063593号公報等を参照できる。
以下に、表1に示す感活性光線性又は感放射線性樹脂組成物に含まれる各種成分を示す。
表1に示した各成分を、表1に記載される固形分濃度となるように混合した。次いで、得られた混合液を、3μmのポアサイズを有するポリエチレンフィルタで濾過することにより、感活性光線性又は感放射線性樹脂組成物(以下、「レジスト組成物」ともいう。)を調製した。なお、レジスト組成物において、固形分とは、溶剤以外の全ての成分を意味する。また、レジスト組成物の固形分濃度は、溶剤の含有量で調整し、表2に記載の膜厚になるように調整した。
得られたレジスト組成物を、実施例及び比較例で使用した。
表1に示される樹脂A~Eの構造を以下に示す。なお、表1に、樹脂A~Eの重量平均分子量(Mw)、分散度(Mw/Mn)及びガラス転移温度(Tg(℃))を示す。
なお、樹脂A~Eの重量平均分子量(Mw)及び分散度(Mw/Mn)はGPC(キャリア:テトラヒドロフラン(THF))により測定した(ポリスチレン換算値である)。また、樹脂A~Eの組成比(モル%比)は、13C-NMR(nuclear magnetic resonance)により測定した。
また、樹脂A~Eのガラス転移温度(Tg(℃))は、DSC法により測定した。DSC装置としては、ティー・エイ・インスツルメント・ジャパン(株)社製「熱分析DSC示差走査熱量計Q1000型」を用い、昇温速度は10℃/minとして測定した。
PHS:パラヒドロキシスチレン
TBm:t-ブチルメタクリレート
St:スチレン
Bzm:ベンジルメタクリレート
Bza:ベンジルアクリレート
2EtHx:2-エチルヘキシルメタクリレート
TBa:t-ブチルアクリレート
表1に示される特定添加剤の構造を以下に示す。なお、下記に示す特定添加剤はいずれも水溶性である。
・テトラエチレングリコールジメチルエーテル
表1に示される光酸発生剤の構造を以下に示す。
表1に示される酸拡散制御剤の構造を以下に示す。
表1に示される界面活性剤の構造を以下に示す。
・メガファックR-41、DIC(株)製
<溶剤>
表1に示される溶剤を以下に示す。
・PGME:プロピレングリコールモノメチルエーテル
・PGMEA:プロピレングリコールモノメチルエーテルアセテート
実施例及び比較例の各レジスト組成物を用いて、下記に示す測定を実施した。
東京エレクトロン製スピンコーター「ACT-8」を用いて、ヘキサメチルジシラザン処理を施した8インチのSi基板(Advanced Materials Technology社製(以下、「基板」ともいう。))上に、反射防止層を設けることなく、レジスト組成物を基板が静止した状態で滴下した。滴下した後、基板を回転し、その回転数を、3秒間500rpmで維持し、その後2秒間100rpmで維持し、更に3秒間500rpmで維持し、再び2秒間100rpmで維持した後、膜厚設定回転数(9μmの膜厚となるような回転数)に上げて60秒間維持した。その後、ホットプレート上で150℃にて90秒間加熱乾燥を行い、膜厚9μmの膜を形成した。
次いで、得られた膜厚9μmの膜に対し、下記の測定を実施することにより膜密度を算出した。
(2)基板と膜との合計質量W1(g)を測定する。
(3)メタノールを用いて基板上の膜を除去(溶解及び/又は剥離)し、膜除去後の基板の質量W2(g)を測定する。
(4)W1からW2を差し引くことにより、膜の質量W(g)を求める(W(g)=W1(g)-W2(g))。
(5)WをVで除することにより、膜厚9μmでの膜密度Tを求める(T(g/cm3)=W(g)/V(cm3))。
結果を表2に示す。
東京エレクトロン製スピンコーター「ACT-8」を用いて、8インチのSi基板(Advanced Materials Technology社製(以下、「基板」ともいう。))上に、反射防止層を設けることなく、レジスト組成物を基板が静止した状態で滴下した。滴下した後、基板を回転し、その回転数を、3秒間500rpmで維持し、その後2秒間100rpmで維持し、更に3秒間500rpmで維持し、再び2秒間100rpmで維持した後、膜厚設定回転数(9μmの膜厚となるような回転数)に上げて60秒間維持した。その後、ホットプレート上で150℃にて90秒間加熱乾燥を行い、膜厚9μmの膜を形成した。
次いで、得られた膜厚9μmの膜を一定量のメタノールで基板から剥離し且つ溶解させたサンプル液をガスクロマトグラフィー装置にて測定し、膜中の残留溶剤量(%)を算出した。
結果を表2に示す。
東京エレクトロン製スピンコーター「ACT-8」を用いて、ヘキサメチルジシラザン処理を施した8インチのSi基板(Advanced Materials Technology社製(以下、「基板」ともいう。))上に、反射防止層を設けることなく、上記で調製したレジスト組成物を基板が静止した状態で滴下した。滴下した後、基板を回転し、その回転数を、3秒間500rpmで維持し、その後2秒間100rpmで維持し、更に3秒間500rpmで維持し、再び2秒間100rpmで維持した後、膜厚設定回転数(表2に記載の膜厚となるような回転数)に上げて60秒間維持した。その後、ホットプレート上で150℃にて90秒間加熱乾燥を行い、表2に示す膜厚(μm)のレジスト膜を形成した。
上記手順により、基板と、基板上に形成されたレジスト膜のべた膜とを有するレジスト膜付きウェハを得た。このレジスト膜付きウェハを、露光及び現像処理をせずに、評価用ウェハとして用いた。
具体的には、イオン注入法により、リンを、ドーズ量2×1013cm-2、エネルギー80KeVの条件で注入した後、上記マスクを剥離除去した。この後、基板に対するリンの注入量をダイナミックSIMS(Secondary Ion Mass Spectrometry)分析により定量化した。なお、実施例及び比較例の各値は、実施例1の値を1(基準)として規格化して示した。
結果を表2に示す。
また、実施例1~6の対比から、膜密度が1.10以上の場合、イオン注入の際にイオン漏れがより抑制されることが確認された。
また、実施例1~6の対比から、特定添加剤が分子中に樹脂と反応可能な反応基(例えばOH基)を含むことにより、形成されるパターンの膜密度がより向上することが確認された。
東京エレクトロン製スピンコーター「ACT-8」を用いて、ヘキサメチルジシラザン処理を施した8インチのSi基板(Advanced Materials Technology社製(以下、「基板」ともいう。))上に、反射防止層を設けることなく、上記で調製した樹脂組成物を基板が静止した状態で滴下した。滴下した後、基板を回転し、その回転数を、3秒間500rpmで維持し、その後2秒間100rpmで維持し、更に3秒間500rpmで維持し、再び2秒間100rpmで維持した後、膜厚設定回転数(表2に記載の膜厚となるような回転数)に上げて60秒間維持した。その後、ホットプレート上で150℃にて90秒間加熱乾燥を行い、表2に示す膜厚(μm)のレジスト膜を形成した。
このレジスト膜に対し、縮小投影露光及び現像後に形成されるパターンのスペース幅が5μm、ピッチ幅が25μmとなるような、ラインアンドスペースパターンを有するマスクを介して、KrFエキシマレーザースキャナー(ASML製、PAS5500/850C波長248nm)を用いて、NA=0.60、σ=0.75の露光条件でパターン露光した。照射後に120℃にて60秒間ベークし、2.38質量%テトラメチルアンモニウムハイドロオキサイド(TMAH)水溶液を用いて60秒間浸漬した後、30秒間、純水でリンスして乾燥した後、110℃にて60秒ベークして、スペース幅が5μm、ピッチ幅が25μmの孤立スペースパターンを形成した。
実施例1~6のレジスト組成物によれば、いずれも直線性に優れたパターンが形成可能であることが確認された。
Claims (12)
- イオンインプランテーション工程においてマスクとして用いられるパターンを形成するための感活性光線性又は感放射線性樹脂組成物であり、
酸分解性基を有する繰り返し単位を含む樹脂と、
光酸発生剤と、
融点又はガラス転移温度が25℃未満であり、且つ、分子量が180以上の添加剤と、を含み、
前記添加剤の含有量が、組成物中の全固形分に対して1質量%以上である、感活性光線性又は感放射線性樹脂組成物。 - 前記パターンの膜厚が、5μm以上である、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。
- 前記パターンの膜厚が、7μm以上である、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。
- 組成物中の固形分濃度が20質量%以上である、請求項1~3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。
- 基板上に前記感活性光線性又は感放射線性樹脂組成物を塗布して塗膜を形成した後、上記塗膜を150℃にて90秒間ベークして得られる膜厚9μmの膜の膜密度が、1.05g/cm3以上である、請求項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。
- 前記膜密度が、1.10g/cm3以上である、請求項5に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂のガラス転移温度が、170℃以下である、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。
- 前記添加剤が、水溶性である、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。
- 前記イオンインプランテーション工程が、赤外光成分を選択的に透過する赤外光透過フィルタを含む固体撮像素子の製造における、前記赤外光透過フィルタ用の受光部を形成するためのイオンインプランテーション工程である、請求項1~8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1~9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により形成されたレジスト膜。
- 請求項1~9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レジスト膜を形成するレジスト膜形成工程と、
前記レジスト膜を露光する露光工程と、
露光された前記レジスト膜を、現像液を用いて現像する現像工程と、を含むパターン形成方法。 - 請求項11に記載のパターン形成方法を含む、固体撮像素子の製造方法であって、
基板上に形成された前記パターンをマスクとして前記基板の非マスク領域にイオンを注入することにより、赤外光を感知する受光部を形成するイオンインプランテーション工程と、
前記パターンを前記基板上から除去する工程と、
前記基板のイオン注入された領域の上に赤外光透過フィルタ層を配置する、赤外光透過フィルタ層配置工程と、を含む固体撮像素子の製造方法。
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