Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • 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
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to a radiation-sensitive composition and a method for forming a resist pattern.
• Radiation-sensitive compositions are required to have good sensitivity to radiation such as extreme ultraviolet rays and electron beams, as well as excellent CDU (Critical Dimension Uniformity) performance and development defect suppression.
• the object of the present invention is to provide a radiation-sensitive composition and a method for forming a resist pattern that are excellent in sensitivity, CDU, and suppression of development defects.
• the invention made to solve the above-mentioned problems is a radiation-sensitive composition containing a polymer (hereinafter also referred to as "polymer [A]”) having a first structural unit including a partial structure in which a hydrogen atom of a carboxy group or a phenolic hydroxyl group is substituted with an acid-dissociable group represented by the following formula (1), and a compound (hereinafter also referred to as “compound [Z]”) having an anion moiety including an aromatic ring in which at least one hydrogen atom is substituted with an iodine atom and one type of anion group, and a radiation-sensitive onium cation moiety:
• Ar 1 is a group in which one hydrogen atom has been removed from an aromatic ring in which at least one hydrogen atom has been substituted with an iodine atom.
• R 1 and R 2 are each independently a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or these groups taken together form an alicyclic ring having 3 to 20 ring members together with the carbon atom to which they are bonded. However, R 1 and R 2 cannot both be hydrogen atoms. * indicates the bonding site with the etheric oxygen atom of a carboxy group or the oxygen atom of a phenolic hydroxyl group.) It is.
• Another invention made to solve the above problem is a method for forming a resist pattern, comprising the steps of applying the radiation-sensitive composition directly or indirectly to a substrate, exposing the resist film formed by the application, and developing the exposed resist film.
• the radiation-sensitive composition of the present invention has excellent sensitivity, CDU, and suppression of development defects.
• the resist pattern forming method of the present invention can form a resist pattern with good sensitivity, excellent CDU, and suppression of the occurrence of development defects.
• the radiation-sensitive composition contains the polymer [A] and the compound [Z], and thus has excellent sensitivity, CDU, and development defect suppression properties.
• the reason why the radiation-sensitive composition has the above-mentioned effects due to having the above-mentioned configuration is not necessarily clear, but it is presumed, for example, as follows. That is, by using the polymer [A] having a specific structural unit described below in combination with the compound [Z] having a specific anion structure described below, the absorption efficiency of the exposure light is improved, and the acid generation effect is increased, which is thought to result in excellent sensitivity and CDU. Furthermore, the polymer [A] improves the wettability of the resist film, which is thought to result in excellent development defect suppression properties.
• the radiation-sensitive composition can be prepared, for example, by mixing [A] a polymer and [Z] a compound, and, if necessary, [B] an acid generator, [C] an acid diffusion controller, [D] an organic solvent, [F] a polymer and other optional components, in a predetermined ratio, and filtering the resulting mixture through a membrane filter with a pore size of 0.2 ⁇ m or less.
• the components contained in the radiation-sensitive composition are described below.
• the polymer [A] preferably further has a structural unit containing a phenolic hydroxyl group (hereinafter also referred to as “structural unit (II)").
• the polymer [A] may further have a structural unit containing an acid dissociable group other than the acid dissociable group (a) (hereinafter also referred to as “structural unit (III)”).
• the polymer [A] may further have other structural units (hereinafter also referred to as "other structural units”) other than the structural units (I) to (III).
• the polymer [A] may have one or more types of each structural unit.
• the lower limit of the content of the polymer [A] in the radiation-sensitive composition is preferably 50% by mass, more preferably 70% by mass, and even more preferably 80% by mass, based on all components other than the organic solvent [D] contained in the radiation-sensitive composition.
• the upper limit of the content is preferably 99% by mass, and more preferably 95% by mass.
• the lower limit of the weight average molecular weight (Mw) of the polymer [A] in terms of polystyrene as determined by gel permeation chromatography (GPC) is preferably 1,000, more preferably 2,000, even more preferably 3,000, and even more preferably 5,000.
• the upper limit of the above Mw is preferably 30,000, more preferably 20,000, even more preferably 10,000, and even more preferably 8,000.
• the upper limit of the ratio of Mw to the polystyrene equivalent number average molecular weight (Mn) of the polymer (A) by GPC is preferably 2.5, more preferably 2.0, even more preferably 1.8, and even more preferably 1.7.
• the lower limit of the above ratio is usually 1.0, preferably 1.1, more preferably 1.2, even more preferably 1.3, and even more preferably 1.4.
• Mw and Mn of the polymer in this specification are values measured by gel permeation chromatography (GPC) under the following conditions.
• GPC column 2 "G2000HXL", 1 "G3000HXL” and 1 "G4000HXL” from Tosoh Corporation
• Column temperature 40°C
• Elution solvent tetrahydrofuran
• Flow rate 1.0 mL/min
• Sample concentration 1.0 mass%
• Sample injection volume 100 ⁇ L
• Detector Differential refractometer Standard material: Monodisperse polystyrene
• the polymer can be synthesized, for example, by polymerizing monomers that provide each structural unit using a known method.
• Alicyclic hydrocarbon group refers to a hydrocarbon group that contains only an alicyclic ring as a ring structure and does not contain an aromatic ring, and includes both monocyclic alicyclic hydrocarbon group and polycyclic alicyclic hydrocarbon group. However, it does not have to be composed only of an alicyclic structure, and it may contain a chain structure as part of it.
• “Aromatic hydrocarbon group” refers to a hydrocarbon group that contains an aromatic ring as a ring structure. However, it does not have to be composed only of an aromatic ring, and it may contain a chain structure or an alicyclic ring as part of it.
• Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include monocyclic alicyclic saturated hydrocarbon groups such as cyclopentyl and cyclohexyl groups; polycyclic alicyclic saturated hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl groups; monocyclic alicyclic unsaturated hydrocarbon groups such as cyclopentenyl and cyclohexenyl groups; and polycyclic alicyclic unsaturated hydrocarbon groups such as norbornenyl, tricyclodecenyl, and tetracyclododecenyl groups.
• the alicyclic ring is preferably an aliphatic hydrocarbon ring having 3 to 20 ring members, more preferably a saturated aliphatic hydrocarbon ring having 3 to 20 ring members, even more preferably a monocyclic saturated aliphatic hydrocarbon ring having 3 to 20 ring members, and even more preferably a cyclopentane ring or a cyclohexane ring.
• R 1 and R 2 are not both hydrogen atoms.
• the carbon atom bonded to the etheric oxygen atom of the carboxyl group or the oxygen atom of the phenolic hydroxyl group in the acid dissociable group (a) (the carbon atom bonded to * in the above formula (1)) becomes a primary carbon atom and does not exhibit acid dissociability.
• R 1 and R 2 are not both hydrogen atoms, the carbon atom bonded to * in the above formula (1) becomes a secondary or tertiary carbon atom and exhibits acid dissociability.
• a tertiary carbon atom is preferred as the carbon atom bonded to * in the above formula (1).
• the series number of a carbon atom generally represents the number of carbon atoms directly bonded to that carbon atom. In this specification, the series number of a carbon atom is determined in a state where it is bonded to an oxygen atom.
• the acid dissociable group (a) a group that replaces a hydrogen atom of a carboxy group in the structural unit (I) is preferred.
• the acid dissociable group (a) is preferably bonded to an ether oxygen atom of a carbonyloxy group.
• acids-dissociable group (a) groups represented by the following formulas (1-1) to (1-11) are preferred.
• structural unit (I) examples include structural units represented by the following formula (I-1) or (I-2):
• R 13 is preferably a single bond.
• the number of ring members and the type of the aromatic ring that gives Ar 2 include, for example, those exemplified as the aromatic ring that gives Ar 1 in the above formula (1).
• the aromatic ring that gives Ar 2 is preferably an aromatic hydrocarbon ring having 6 to 30 ring members, more preferably a benzene ring.
• the lower limit of the content of the structural unit (I) in the polymer [A] is preferably 5 mol%, more preferably 10 mol%, even more preferably 15 mol%, and even more preferably 20 mol%, based on the total structural units constituting the polymer [A].
• the upper limit of the above content is preferably 80 mol%, more preferably 70 mol%, and even more preferably 60 mol%.
• the polymer [A] having the structural unit (I) can be synthesized by polymerizing a monomer that gives the structural unit (I) (hereinafter also referred to as "monomer [X]”) by a known method.
• the structural unit (II) is a structural unit containing a phenolic hydroxyl group.
• the polymer (A) may contain one or more types of the structural unit (II).
• the polymer [A] having the structural unit (II) can further increase the sensitivity of the radiation-sensitive composition to the exposure light. Therefore, when the polymer [A] has the structural unit (II), the radiation-sensitive composition can be suitably used as a radiation-sensitive composition for KrF exposure, EUV exposure, or electron beam exposure.
• R P is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• L P is a single bond, -COO-, -O- or -CONH-.
• Ar P is a group in which (p+1) hydrogen atoms have been removed from a substituted or unsubstituted aromatic ring. p is an integer from 1 to 3.
• R 3 P is preferably a hydrogen atom or a methyl group.
• L 3 P is preferably a single bond or —COO—, and more preferably a single bond.
• the number and type of ring members of the aromatic ring that gives Ar P may be, for example, those exemplified as the aromatic ring that gives Ar 1 in the above formula (1).
• the aromatic ring that gives Ar P is preferably an aromatic hydrocarbon ring having 6 to 30 ring members, more preferably a benzene ring.
• At least one hydrogen atom of the aromatic ring giving Ar P may be further substituted with a substituent.
• substituents include those exemplified as the substituent that may be possessed by the aromatic ring giving Ar 2 in the above formula (I-2).
• p 1 or 2 is preferable.
• the CDU of the radiation-sensitive composition tends to be improved more than when p is 2, which is preferable.
• p 2
• the sensitivity and development defect suppression of the radiation-sensitive composition tends to be improved more than when p is 1, which is preferable.
• Examples of the structural unit (II) include structural units represented by the following formulas (II-1) to (II-18).
• R 3 P has the same meaning as in the above formula (II).
• the lower limit of the content of the structural unit (II) in the polymer [A] is preferably 10 mol%, more preferably 20 mol%, and even more preferably 25 mol%, based on the total structural units constituting the polymer [A].
• the upper limit of the above content is preferably 70 mol%, more preferably 60 mol%, and even more preferably 50 mol%.
• the structural unit (III) is a structural unit containing an acid dissociable group other than the acid dissociable group (a) (hereinafter also referred to as "acid dissociable group (b)"). More specifically, the structural unit (III) is a structural unit containing a partial structure in which a hydrogen atom of a carboxy group or a phenolic hydroxyl group is substituted with an acid dissociable group (b). The structural unit (III) is a structural unit different from the structural unit (I).
• the polymer (A) can have one or more types of structural units (III).
• the polymer [A] has a structural unit (III) that allows the process window to be adjusted.
• the acid dissociable group (b) is not particularly limited as long as it is a group other than the acid dissociable group (a), and examples thereof include groups represented by the following formulas (b-1) to (b-3) (hereinafter also referred to as "acid dissociable groups (b-1) to (b-3)").
• Examples of the substituent that the hydrocarbon group represented by R X may have include those exemplified as the substituent that the monovalent hydrocarbon group having 1 to 20 carbon atoms which gives R 1 and R 2 in the above formula (1) may have.
• Examples of the oxygen atom-containing aliphatic heterocycle having 4 to 20 ring members formed by combining R U and R W together with the carbon atom to which R U is bonded and the oxygen atom to which R W is bonded include an oxacyclobutane ring, an oxacyclopentane ring, an oxacyclohexane ring, an oxacyclobutene ring, an oxacyclopentene ring, and an oxacyclohexene ring.
• the saturated alicyclic ring is preferably a monocyclic saturated alicyclic ring, more preferably a cyclopentane ring or a cyclohexane ring.
• R 3 B is preferably a hydrogen atom.
• R 3 C is preferably a chain hydrocarbon group, more preferably an alkyl group, and further preferably a methyl group.
• R 11 has the same meaning as in the above formula (I-1)
• R 12 , R 13 , Ar 2 and R 14 have the same meaning as in the above formula (I-2).
• the polymer [A] may be in an embodiment that does not have the structural unit (III), and therefore the content of the structural unit (I) in the polymer [A] may be 100 mol% based on the structural units containing an acid-dissociable group contained in the polymer [A].
• R L1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R L2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• the lower limit of the content of the structural unit (V) is preferably 5 mol %, more preferably 10 mol %, based on the total structural units constituting the polymer [A].
• the upper limit of the content is preferably 40 mol %, more preferably 30 mol %.
• the [Z] compound has the function of generating an acid in the radiation-sensitive composition upon irradiation with radiation, or the function of controlling the diffusion phenomenon in the resist film of the acid generated by the acid generator [B] or the like upon exposure to light, thereby suppressing undesirable chemical reactions in non-exposed areas (for example, dissociation reactions of acid-dissociable groups).
• the [Z] compound functions as a radiation-sensitive acid generator or an acid diffusion controller (quencher) in the radiation-sensitive composition.
• the acid generated from the [Z] compound upon irradiation with radiation dissociates the acid-dissociable group (a) and the like contained in the structural unit (I) of the [A] polymer, generating a carboxy group or a phenolic hydroxyl group, which creates a difference in the solubility of the resist film in a developer between the exposed and unexposed areas, thereby forming a resist pattern.
• the [Z] compound When the [Z] compound functions as an acid diffusion control agent, it generates acid in the exposed areas to increase the solubility or insolubility of the [A] polymer in the developer, and in the non-exposed areas, it exerts a high acid capture function due to the anion, functions as a quencher, and captures the acid that diffuses from the exposed areas. This improves the roughness at the interface between the exposed and non-exposed areas, and increases the difference in solubility in the developer between the exposed and non-exposed areas, thereby improving the resolution.
• the inclusion of the [Z] compound in the radiation-sensitive composition is believed to be one of the factors that allows the radiation-sensitive composition to exhibit excellent sensitivity and CDU.
• the lower limit of the content of the [Z] compound in the radiation-sensitive composition is preferably 1 part by mass, more preferably 5 parts by mass, and even more preferably 10 parts by mass, relative to 100 parts by mass of the [A] polymer.
• the upper limit of the content is preferably 70 parts by mass, more preferably 60 parts by mass, and even more preferably 50 parts by mass.
• the lower limit of the content of the [Z] compound in the radiation-sensitive composition is preferably 20 mol%, more preferably 30 mol%, and even more preferably 40 mol%, relative to 100 mol% of the anion portion of the radiation-sensitive acid generator (the total of the [Z] compound when functioning as a radiation-sensitive acid generator and the acid generator [B] described below that is used in combination as necessary).
• the upper limit of the content is preferably 80 mol%, more preferably 70 mol%, and even more preferably 60 mol%.
• the ring structure giving R A1 has, for example, 3 to 30 ring members, and preferably 6 to 20 ring members.
• the acid diffusion controller [C] is an acid diffusion controller other than the compound [Z].
• the radiation-sensitive composition preferably contains the acid diffusion controller [C].
• the acid diffusion controller [C] controls the diffusion phenomenon in the resist film of the acid generated from the compound [Z] and the acid generator [B] used in combination as necessary upon exposure, and controls undesirable chemical reactions in the non-exposed areas.
• the radiation-sensitive composition may contain one or more acid diffusion controllers [C].
• the anion portion of the above weak acid may, for example, contain a carboxylate anion group as the anion group.
• the photodegradable base a compound that appropriately combines the above-mentioned radiation-sensitive onium cation moiety and the above-mentioned weak acid anion moiety can be used.
• the lower limit of the content of the acid diffusion controller [C] in the radiation-sensitive composition is preferably 20 mol%, more preferably 30 mol%, and even more preferably 40 mol%, relative to 100 mol% of the anion portion of the radiation-sensitive acid generator (the compound [Z] and/or the acid generator [B] when it functions as a radiation-sensitive acid generator).
• the upper limit of the content is preferably 200 mol%, more preferably 120 mol%, and even more preferably 80 mol%.
• Examples of organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents.
• the radiation-sensitive composition can contain one or more types of [D] organic solvents.
• the lower limit of the content of the organic solvent [D] is preferably 50 mass%, more preferably 60 mass%, even more preferably 70 mass%, and particularly preferably 80 mass%, based on all components contained in the radiation-sensitive composition.
• the upper limit of the content is preferably 99.9 mass%, preferably 99.5 mass%, and even more preferably 99.0 mass%.
• the structural unit containing the anion moiety containing an aromatic ring in which at least one hydrogen atom is replaced with an iodine atom and one type of anion group, and the radiation-sensitive onium cation moiety is a structural unit containing the anion moiety (X) and the cation moiety (Y) described above in the section on [[Z] Compound].
• Such a structural unit is a structural unit that generates an acid corresponding to the anion group possessed by the anion moiety (X) under the action of radiation.
• the [A2] polymer functions as a radiation-sensitive acid generator or an acid diffusion controller (quencher) in the radiation-sensitive resin composition, depending on the type of anion group possessed by the anion moiety (X).
• the method for forming a resist pattern includes a step of directly or indirectly applying a radiation-sensitive composition to a substrate (hereinafter also referred to as a "coating step"), a step of exposing the resist film formed by the coating step (hereinafter also referred to as an "exposure step”), and a step of developing the exposed resist film (hereinafter also referred to as a "development step”).
• the radiation-sensitive composition described above is used as the radiation-sensitive composition. Therefore, according to the resist pattern forming method, a resist pattern can be formed that has good sensitivity, excellent CDU, and suppresses the occurrence of development defects.
• the radiation-sensitive composition is applied directly or indirectly to a substrate, thereby forming a resist film directly or indirectly on the substrate.
• the radiation-sensitive composition described above is used as the radiation-sensitive composition.
• Substrates include conventionally known ones such as silicon wafers, silicon dioxide, and aluminum-coated wafers.
• PB pre-baking
• the PB temperature and time there are no particular limitations on the PB temperature and time, and the PB is performed, for example, at a temperature of 60°C to 150°C for a time of 5 seconds to 300 seconds.
• the average thickness of the resist film formed there are no particular limitations on the average thickness of the resist film formed, and it is, for example, 10 nm to 1,000 nm.
• Mw Weight average molecular weight
• Mn number average molecular weight
• Mw/Mn polydispersity
• NEt 3 is triethylamine.
• the cooled polymerization solution was poured into n-hexane (1,000 parts by mass) to coagulate and purify the polymer.
• propylene glycol monomethyl ether 150 parts by mass
• methanol 150 parts by mass
• triethylamine 1.5 molar equivalents relative to the amount of monomer (M-2) used
• water 1.5 molar equivalents relative to the amount of monomer (M-2) used
• the hydrolysis reaction was carried out for 8 hours while refluxing at the boiling point. After the reaction was completed, the solvent and triethylamine were distilled off under reduced pressure, and the obtained polymer was dissolved in acetone (150 parts by mass).
• R-1 Preparation of Radiation-Sensitive Composition (R-1) [A] 100 parts by mass of polymer (A-1) as a polymer, [F] 3 parts by mass of polymer (F-1) as a polymer, [B] 45 parts by mass of acid generator (B-1) as an acid generator, [C] 50 mol % of acid diffusion controller (C-1) as an acid diffusion controller based on the anion part of acid generator (B-1), and [D] 5,500 parts by mass of (D-1) and 1,500 parts by mass of (D-2) as an organic solvent were mixed. The resulting mixture was filtered through a membrane filter having a pore size of 0.2 ⁇ m to prepare radiation-sensitive composition (R-1).
• the exposure dose required to form a 25 nm contact hole pattern was determined as the optimum exposure dose, and this optimum exposure dose was determined as the sensitivity (mJ/ cm2 ). The smaller the value of the sensitivity, the better it is. Sensitivity was evaluated as "A” (very good) when it was less than 60 mJ/ cm2 , “B” (good) when it was 60 mJ/ cm2 or more and 63 mJ/ cm2 or less, and “C” (poor) when it exceeded 63 mJ/cm2.
• the resist film was exposed and developed at the optimal exposure dose determined in the above [Sensitivity] section to form a 25 nm contact hole pattern.
• the number of defects on the wafer was measured using a defect inspection device (KLA-Tencor's "KLA2810"). The measured defects were classified into those determined to be originating from the resist film and foreign matter originating from the external environment.
• the development defect suppression was evaluated as "A" (very good) when the number of defects determined to be originating from the resist film was less than 30, as "B" (good) when the number was 30 to 50, and as "C” (poor) when the number was more than 50.

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