WO2020203246A1 - Procédé de production de composition de résine sensible à la lumière active ou au rayonnement actif, procédé de formation de motif et procédé de production de dispositif électronique - Google Patents

Procédé de production de composition de résine sensible à la lumière active ou au rayonnement actif, procédé de formation de motif et procédé de production de dispositif électronique Download PDF

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Publication number
WO2020203246A1
WO2020203246A1 PCT/JP2020/011635 JP2020011635W WO2020203246A1 WO 2020203246 A1 WO2020203246 A1 WO 2020203246A1 JP 2020011635 W JP2020011635 W JP 2020011635W WO 2020203246 A1 WO2020203246 A1 WO 2020203246A1
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group
filter
sensitive
polymer solution
radiation
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PCT/JP2020/011635
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English (en)
Japanese (ja)
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聡 上村
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富士フイルム株式会社
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Priority to JP2021511395A priority Critical patent/JP7301123B2/ja
Publication of WO2020203246A1 publication Critical patent/WO2020203246A1/fr

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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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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

Definitions

  • the present invention relates to a method for producing a sensitive light-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device.
  • the resist for KrF excimer laser (248 nm) Since the resist for KrF excimer laser (248 nm), a pattern forming method using chemical amplification has been used to compensate for the decrease in sensitivity due to light absorption.
  • the positive chemical amplification method first, the photoacid generator contained in the exposed portion is decomposed by light irradiation to generate an acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process or the like, the alkali-insoluble group of the resin contained in the sensitive light-sensitive or radiation-sensitive resin composition is alkali-soluble by the catalytic action of the generated acid. The solubility in a developing solution is changed by changing the base. Then, for example, development is carried out using a basic aqueous solution.
  • PEB Post Exposure Bake
  • the exposed portion is removed to obtain a desired pattern.
  • the wavelength of the exposure light source has been shortened and the numerical aperture (NA) of the projection lens has been increased.
  • NA numerical aperture
  • an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. Under these circumstances, various configurations have been proposed as sensitive light-sensitive or radiation-sensitive resin compositions (resist compositions).
  • Patent Document 1 a resist composition containing a resin component, an acid-generating component that generates an acid upon exposure, and an organic solvent is filtered under specific conditions to develop a resist pattern surface after development. It discloses a method for suppressing defects.
  • a method for producing a sensitive light-sensitive or radiation-sensitive resin composition used in a semiconductor device manufacturing process Step A of purifying a polymer solution containing a resin and a solvent which are decomposed by the action of an acid and whose polarity is increased.
  • a step B of preparing a sensitive light-sensitive or radiation-sensitive resin composition by adding a compound that generates an acid by irradiation with active light or radiation to the polymer solution that has undergone the above step A is included.
  • a method for producing a sensitive light-sensitive or radiation-sensitive resin composition wherein the step A comprises a step X in which the polymer solution is passed through a filter X and filtered.
  • the filter X is selected from the group consisting of a nylon film having a pore diameter of 0.03 ⁇ m or less, a polyolefin resin film having a pore diameter of 0.01 ⁇ m or less, and a fluororesin film having a pore diameter of 0.01 ⁇ m or less [1].
  • step A The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the above step X is carried out in a temperature environment of 15 to 25 ° C.
  • step A The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the step A includes the step X twice or more.
  • the above step A is A step X0 in which the polymer solution is passed through the filter X0 and filtered, and a step X1 in which the polymer solution passed through the step X0 is passed through the filter X1 and filtered is included.
  • a step X1 in which the polymer solution is passed through the filter X1 and filtered, and a step X2 in which the polymer solution passed through the step X1 is passed through the filter X2 and filtered is included.
  • the filter X0 and the filter X2 are filters different from the filter X1 and are selected from a polyolefin resin film having a pore diameter of 0.01 ⁇ m or less and a fluororesin film having a pore diameter of 0.01 ⁇ m or less, [1] to [ 4]
  • the above step A is With respect to the polymer solution comprising the step X0 of passing the polymer solution through the filter X0 and filtering, and the step X1 of passing the polymer solution through the step X0 and filtering the filter X1 and passing through the step X1.
  • the step of carrying out the step X0 and the step X1 is included one or more times.
  • the polymer solution comprising the step X1 of passing the polymer solution through the filter X1 and filtering, and the step X2 of passing the polymer solution through the filter X2 and filtering the filter X2, and passing through the step X2.
  • the step of carrying out the step X1 and the step X2 is included once or more, or
  • [6] includes one or more steps of performing the above-mentioned step X0, the above-mentioned step X1 and the above-mentioned X2 on the polymer solution which has been subjected to the above-mentioned step X2 and includes the step X2 for filtering.
  • the method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to the above method.
  • a method for producing a radiation-sensitive resin composition [9] Any of [1] to [8], wherein the resin that is decomposed by the action of the above acid and whose polarity is increased contains a resin containing a repeating unit derived from at least one of an acrylic acid ester and a methacrylic acid ester.
  • the method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to.
  • the present invention it is possible to provide a method for producing a sensitive light-sensitive or radiation-sensitive resin composition capable of forming a pattern in which bridge defects are suppressed.
  • the present invention can also provide a pattern forming method using a sensitive light-sensitive or radiation-sensitive resin composition capable of forming a pattern in which bridge defects are suppressed, and a method for manufacturing an electronic device.
  • the present invention will be described in detail.
  • the description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the notation without substitution and non-substitution 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).
  • the "organic group” in the present specification means a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent.
  • the term “active light” or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB). : Electron Beam) and the like.
  • LED means active light or radiation.
  • the term "exposure” as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beams and It also includes drawing with particle beams such as ion beams.
  • "-" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
  • the bonding direction of the divalent group described in the present specification is not limited unless otherwise specified. For example, when Y is -COO- in the compound represented by the general formula "XYZ", Y may be -CO-O-, and is -O-CO-. You may. Moreover, the said compound may be "X-CO-O-Z" or "X-O-CO-Z".
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acrylic represents acrylic and methacrylic.
  • the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin are determined by a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Toso).
  • the acid dissociation constant (pKa) represents pKa in an aqueous solution
  • the following software package 1 is used to obtain a value based on a database of Hammett's substituent constants and known literature values. , It is a value obtained by calculation. All pKa values described herein indicate values calculated using this software package.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Step A A step of purifying a polymer solution containing a resin (hereinafter, also referred to as “acid-degradable resin”) whose polarity is increased by the action of an acid and a solvent, wherein the polymer solution is filtered through X. Includes step X of passing through and filtering.
  • Step B A compound that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as “photoacid generator”) is added to the polymer solution that has undergone the above step A to form a sensitive light-sensitive or radiation-sensitive resin.
  • photoacid generator A compound that generates an acid by irradiation with active light or radiation
  • filtration purification by filtering is generally carried out at the stage of preparing the resist composition.
  • the present inventor has performed filtration purification by filtering at a stage after preparation of a resist composition, in which impurities mixed with raw material components and brought into the resist composition (hereinafter, also referred to as “raw material-derived impurities”).
  • impurities containing metal atoms hereinafter, also referred to as “metal impurities”
  • by-products derived from acid-degradable resins
  • the resist composition obtained by the production method of the present invention can reduce the number of minute aggregates generated in the resist composition and, by extension, suppress the bridge defects generated on the developed pattern. Be done.
  • the acid-decomposable resin contains one or more of a carbonate structure and a sultone structure, the effect of reducing specific metal impurities in step A is more excellent, and as a result, bridge defects generated on the developed pattern can be further suppressed. Is confirmed.
  • Step A is a step of purifying a polymer solution containing an acid-decomposable resin and a solvent, and is a step X of passing the polymer solution through a filter X and filtering the polymer solution (hereinafter, also referred to as “step X”). including.
  • Step X is preferably carried out in a temperature environment of 15 to 25 ° C.
  • the material of the filter X is not particularly limited, and examples thereof include a polyamide resin, a polyolefin resin, and a fluororesin.
  • a polyamide resin nylon (nylons include nylon 6, nylon 66, nylon 46, and the like) is preferable.
  • nylon resin nylon (nylons include nylon 6, nylon 66, nylon 46, and the like) is preferable.
  • polyolefin resin polyethylene or polypropylene is preferable.
  • fluororesin PTFE (polytetrafluoroethylene) is preferable.
  • a polyamide resin or a polyolefin resin is particularly preferable.
  • the metal impurities contained in the impurities include by-products derived from acid-decomposable resins (examples of by-products include low molecular weight bodies, super molecular weight bodies, and gel components), and chemically and / or. It is presumed that most of them are removed from the polymer solution during filtering by physical adhesion.
  • the pore size of the filter X is not particularly limited, but from the viewpoint of filtration efficiency, for example, it is 0.5 ⁇ m or less, preferably 0.4 ⁇ m or less, and more preferably 0.3 ⁇ m or less.
  • the lower limit of the pore diameter is not particularly limited, but is, for example, 0.001 ⁇ m or more.
  • the "hole diameter" is intended to be the manufacturer's nominal diameter value.
  • a fluororesin film of 01 ⁇ m or less is preferable.
  • the step A may include the step X once, or may include the step X twice or more.
  • the step A may be a one-time liquid passing method in which the polymer solution is passed once in a system in which two or more filters X are connected in series, or a filter.
  • a circulation method may be used in which the polymer solution that has passed through X is further guided to the same filter and circulated in the closed system.
  • the step A may be a method in which the one-time liquid passing method in which the polymer solution is passed once in a system in which two or more filters X are connected in series is repeated a plurality of times.
  • the number of times is not particularly limited, but for example, it is two times or more, preferably three times or more.
  • the upper limit is not particularly limited, but is, for example, 15 times or less, preferably 10 times or less.
  • the number of times of circulation of the polymer solution is, for example, 2 times or more, preferably 3 times or more.
  • the upper limit is not particularly limited, but is, for example, 15 times or less, preferably 10 times or less.
  • the plurality of filters X may be the same or different from each other.
  • "a plurality of filters are different” means that a plurality of filters have different pore diameters and / or materials.
  • the differential pressure of the filter X is preferably 0.3 MPa or less.
  • the lower limit is not particularly limited, but 0 MPa can be mentioned.
  • Step (1) Includes a step X0 in which the polymer solution is passed through the filter X0 and filtered, and a step X1 in which the polymer solution that has passed through the step X0 is passed through the filter X1 and filtered.
  • Step (2) Includes a step X1 in which the polymer solution is passed through the filter X1 and filtered, and a step X2 in which the polymer solution that has passed through the step X1 is passed through the filter X2 and filtered.
  • Step (3) A step X0 in which the polymer solution is passed through the filter X0 and filtered, a step X1 in which the polymer solution through the step X0 is passed through the filter X1 and filtered, and the polymer solution through the step X1 is passed through the filter X2. It includes a step X2 of allowing and filtering.
  • steps (1) to (3) are carried out in a temperature environment of 15 to 25 ° C.
  • steps (1) to (3) will be described in detail.
  • the filter X0 is a filter different from the filter X1 used in the step X1 and is selected from a polyolefin resin film having a pore size of 0.01 ⁇ m or less and a fluororesin film having a pore size of 0.01 ⁇ m or less.
  • the lower limit of the pore size of the polyolefin resin film having a pore size of 0.01 ⁇ m or less is, for example, 0.001 ⁇ m or more.
  • polyethylene or polypropylene is preferable.
  • the lower limit of the pore size of the fluororesin film having a pore size of 0.01 ⁇ m or less is, for example, 0.001 ⁇ m or more. Further, as the fluororesin constituting the fluororesin film, PTFE is preferable.
  • the filter X1 has the same meaning as the filter X used in the above-mentioned step X, and the preferred embodiment is also the same. Further, the procedure of the step X1 is the same as the procedure of the above-mentioned step X.
  • the differential pressure of the filter X0 (intended to be a pressure loss before and after the filter X0) and the differential pressure of the filter X1 are preferably 0.3 MPa or less, respectively.
  • the lower limit is not particularly limited, but 0 MPa can be mentioned.
  • the step A may include the step (1) once, or may include the step (1) twice or more.
  • the case where the step A includes the step (1) twice or more means that the step A includes the step of performing the step X0 and the step X1 again once or more with respect to the polymer solution that has passed through the step X1. Intended.
  • the step A includes the step (1) twice or more the step (1) is a one-time process in which the polymer solution is passed once through a system in which the filter X0 and the filter X1 are connected alternately and in series in this order.
  • a liquid passing method may be used, or a circulation method may be used in which the polymer solution that has passed through the filter X0 and the filter X1 in this order is further guided to the same filter X0 and circulated in the closed system.
  • the number of times is not particularly limited, but for example, it is two times or more, preferably three times or more.
  • the upper limit is not particularly limited, but is, for example, 15 times or less, preferably 10 times or less.
  • the step (1) is performed by the circulation method, for example, when the filter X0 and the filter X1 in the closed system are each one, the number of times of circulation of the polymer solution is, for example, two times or more, and three times or more. Is preferable.
  • the upper limit is not particularly limited, but is, for example, 15 times or less, preferably 10 times or less.
  • the plurality of filters X0 and the plurality of filters X1 may be the same or different from each other.
  • the filter X0 is a polyolefin resin and the filter X1 is a polyamide resin. Further, when the pore diameters of the filter X0 and the filter X1 are different in the step (1), it is preferable that the pore diameter of the filter X0 is larger than the pore diameter of the filter X1.
  • the difference between the pore diameter of the filter X1 and the pore diameter of the filter X0 is preferably, for example, 0.001 to 0.2 ⁇ m.
  • the filter X1 has the same meaning as the filter X used in the above-mentioned step X, and the preferred embodiment is also the same. Further, the procedure of the step X1 is the same as the procedure of the above-mentioned step X.
  • the filter X2 is a filter different from the filter X1 used in the step X1 and is selected from a polyolefin resin film having a pore size of 0.01 ⁇ m or less and a fluororesin film having a pore size of 0.01 ⁇ m or less.
  • the lower limit of the pore size of the polyolefin resin film having a pore size of 0.01 ⁇ m or less is, for example, 0.001 ⁇ m or more.
  • polyethylene or polypropylene is preferable as the polyolefin resin constituting the polyolefin resin film.
  • the lower limit of the pore size of the fluororesin film having a pore size of 0.01 ⁇ m or less is, for example, 0.001 ⁇ m or more. Further, as the fluororesin constituting the fluororesin film, PTFE is preferable.
  • the differential pressure of the filter X1 and the differential pressure of the filter X2 are preferably 0.3 MPa or less, respectively.
  • the lower limit is not particularly limited, but 0 MPa can be mentioned.
  • the step A may include the step (2) once, or may include the step (2) twice or more.
  • the case where the step A includes the step (2) twice or more means that the step A includes a step of performing the step X1 and the step X2 once or more with respect to the polymer solution that has passed through the step X2. Intended.
  • the step A includes the step (2) more than once the step (2) is a one-time process in which the polymer solution is passed once through a system in which the filter X1 and the filter X2 are connected alternately and in series in this order.
  • a liquid passing method may be used, or a circulation method may be used in which the polymer solution that has passed through the filter X1 and the filter X2 in this order is further guided to the same filter X1 and circulated in the closed system.
  • the number of times is not particularly limited, but for example, it is two times or more, preferably three times or more.
  • the upper limit is not particularly limited, but is, for example, 15 times or less, preferably 10 times or less.
  • the step (2) is performed by the circulation method, for example, when the filter X1 and the filter X2 in the closed system are each one, the number of times of circulation of the polymer solution is, for example, two or more, and three or more times. Is preferable.
  • the upper limit is not particularly limited, but is, for example, 15 times or less, preferably 10 times or less.
  • the plurality of filters X1 and the plurality of filters X2 may be the same or different from each other.
  • the filter X1 is a polyamide resin and the filter X2 is a polyolefin resin. Further, when the pore diameters of the filter X1 and the filter X2 are different in the step (2), it is preferable that the pore diameter of the filter X1 is larger than the pore diameter of the filter X2.
  • the difference between the pore diameter of the filter X2 and the pore diameter of the filter X1 is preferably, for example, 0.001 to 0.2 ⁇ m.
  • Step X0 has the same meaning as step X0 in the above-mentioned step (1), and the preferred embodiment is also the same.
  • the filter X1 has the same meaning as the filter X used in the above-mentioned step X, and the preferred embodiment is also the same. Further, the procedure of the step X1 is the same as the procedure of the above-mentioned step X.
  • the step X2 is a step of passing the polymer solution that has undergone the step X1 through the filter X2 and filtering, and is the same as the step X2 in the above-mentioned step (2) except that the target of filtration and purification is the polymer solution that has passed through the step X1.
  • the same is true, and the preferred embodiment is also the same.
  • the differential pressure of the filter X0, the differential pressure of the filter X1, and the differential pressure of the filter X2 are preferably 0.3 MPa or less, respectively.
  • the lower limit is not particularly limited, but 0 MPa can be mentioned.
  • the step A may include the step (3) once, or may include the step (3) twice or more.
  • step A includes the step (3) twice or more, it means that the step X0, the step X1 and the step X2 are performed once or more with respect to the polymer solution that has undergone the step X2. Intended.
  • step (3) passes the polymer solution once in a system in which filter X0, filter X1 and filter X2 are connected alternately and in series in this order. It may be a one-time liquid passing method in which the polymer solution is passed through the filter X0, the filter X1 and the filter X2 in this order, and the polymer solution is further guided to the same filter X0 and circulated in the closed system.
  • the number of times is not particularly limited, but for example, it is two times or more, preferably three times or more.
  • the upper limit is not particularly limited, but is, for example, 15 times or less, preferably 10 times or less.
  • the step (3) is performed by the circulation method, for example, when there is one filter X0, one filter X1 and one filter X2 in the closed system, the number of circulations of the polymer solution is, for example, two or more. It is preferably 3 times or more.
  • the upper limit is not particularly limited, but is, for example, 15 times or less, preferably 10 times or less.
  • the plurality of filters X0, the plurality of filters X1, and the plurality of filters X2 may be the same or different. You may be.
  • the filter X0 is a polyolefin resin or a fluororesin
  • the filter X1 is a polyamide resin.
  • the pore diameters of the filter X0 and the filter X1 are different in the step (3), it is preferable that the pore diameter of the filter X0 is larger than the pore diameter of the filter X1.
  • the difference between the pore diameter of the filter X1 and the pore diameter of the filter X0 is preferably, for example, 0.001 to 0.2 ⁇ m.
  • the filter X1 is a polyamide resin and the filter X2 is a polyolefin resin or a fluororesin.
  • the pore diameters of the filter X1 and the filter X2 are different in the step (3), it is preferable that the pore diameter of the filter X1 is larger than the pore diameter of the filter X2.
  • the difference between the pore diameter of the filter X2 and the pore diameter of the filter X1 is preferably, for example, 0.001 to 0.2 ⁇ m.
  • the filter X0 and the filter X2 are made of different materials. Further, it is preferable that the pore diameter is larger in the order of the filter X2, the filter X1, and the filter 0.
  • the production method of the present invention may optionally include other steps other than step A and step B.
  • steps other than step A and step B examples include step Z (hereinafter, also referred to as “step Z”) for measuring the content of metal impurities (impurities containing metal atoms) that can be contained in the polymer solution obtained through step A. ..
  • step Z for measuring the content of metal impurities (impurities containing metal atoms) that can be contained in the polymer solution obtained through step A. ..
  • the "metal impurities” are intended as metal ions and impurities contained in the polymer solution as solids (including simple metals and particulate metal-containing compounds). In the semiconductor device manufacturing process, it is required to reduce metal impurities in the resist composition.
  • the type of the metal atom in the metal impurity is not particularly limited, but examples of the metal whose content in the resist composition is desired to be small include Na, K, Ca, Fe, Cu, Mg, Mn, and Al.
  • Each metal atom such as Li, Cr, Ni, Sn, Zn, Ag, As, Au, Ba, Cd, Co, Pb, V, W, Zr, and Mo (hereinafter, also referred to as "specific metal atom") is mentioned. Be done.
  • the content of metal impurities in the polymer solution is intended to be the content of metal atoms measured by ICP-MS (inductively coupled plasma mass spectrometry). The method for measuring the content of metal atoms using ICP-MS is as described in Examples described later.
  • each metal atom is preferably 100 mass ppb or less, more preferably 50 mass ppb or less, further preferably 20 mass ppb or less, and particularly preferably 10 mass ppb, based on the total mass of the solution.
  • 5.0 mass ppb or less is most preferable, and 1.0 mass ppb or less is more preferable.
  • the lower limit of the content of each metal atom is preferably not substantially contained (below the detection limit of the measuring device), and more preferably 0.
  • the total content of the specific metal atom in the polymer solution is preferably 100 mass ppb or less, more preferably 50 mass ppb or less, further preferably 20 mass ppb or less, and 10 mass ppb with respect to the total mass of the solution. Particularly preferably, 5.0 mass ppb or less is most preferable, and 1.0 mass ppb or less is more preferable.
  • the lower limit of the total content of the specific metal atom is preferably not substantially contained (below the detection limit of the measuring device), and more preferably 0.
  • step A is schematic views of the apparatus used in step A.
  • the device of FIG. 1 is a device used when the step A is a mode in which the step X is carried out by a one-time liquid passing method only once.
  • the tank 1, the pump 2, and the column 100 on which the filter X is installed are connected by flow paths 5 to 7. Further, a flow meter 3 and a filling port 8 are installed in the flow path 7.
  • the polymer solution filled in the tank 1 passes through the column 100 in which the filter X is installed, and the polymer solution that has passed through the column 100 is filled in the treatment liquid filling container 4.
  • the device of FIG. 2 is a device used when step A is a mode in which step X is performed two or more times in a circulation manner.
  • the tank 1, the pump 2, and the column 100 on which the filter X is installed are connected by flow paths 5 to 7.
  • the flow path 7 is also connected to the tank 1, and by driving the pump 2, the polymer solution contained in the tank 1 is circulated in the system.
  • a filling port 8 is provided in the flow path 7, and the polymer solution that has undergone a predetermined circulation filtration step is filled in the treatment liquid filling container 4.
  • the filling port 8 is often closed at the start of driving the pump so that a predetermined number of circulations can be achieved.
  • the number of circulations can be calculated using the flow meter 3 installed in the flow path 7.
  • the device of FIG. 3 is a device used when the step A is a mode in which the step (3) is carried out by a one-time liquid passing method only once.
  • the tank 1, the pump 2, the column 200 in which the filter X0 is installed, the column 300 in which the filter X1 is installed, and the column 400 in which the filter X2 is installed are the flow paths 5, 6, 7, and 9. , And 10 are connected. Further, a flow meter 3 and a filling port 8 are installed in the flow path 7.
  • the polymer solution filled in the tank 1 passes through the column 200, the column 300, and the column 400, and the polymer solution that has passed through the column 400 is filled in the treatment liquid filling container 4.
  • the device of FIG. 4 is a device used when the step A is an embodiment in which the step (3) is carried out in a circulation manner.
  • the tank 1, the pump 2, the column 500 in which the filter X0 is installed, the column 600 in which the filter X1 is installed, and the column 700 in which the filter X2 is installed are the flow paths 5, 6, 7, and 9. , And 10 are connected.
  • the flow path 7 is also connected to the tank 1, and by driving the pump 2, the polymer solution contained in the tank 1 is circulated in the system.
  • a filling port 8 is provided in the flow path 7, and the polymer solution that has undergone a predetermined circulation filtration step is filled in the treatment liquid filling container 4.
  • the filling port 8 is often closed at the start of driving the pump so that a predetermined number of circulations can be achieved.
  • the number of circulations can be calculated using the flow meter 3 installed in the flow path 7.
  • the polymer solution contains an acid-degradable resin and a solvent. It is preferable that the polymer solution does not substantially contain a compound (photoacid generator) that generates an acid by irradiation with active light or radiation.
  • the polymer solution substantially does not contain the photoacid generator means that the content of the photoacid generator is 3.0% by mass or less with respect to the total mass of the polymer solution. , 2.0% by mass or less is preferable, and 1.0% by mass or less is more preferable.
  • the polymer solution preferably contains substantially no other components other than the acid-decomposable resin and the solvent.
  • the polymer solution substantially does not contain other components other than the acid-degradable resin and the solvent
  • the total content of the acid-decomposable resin and other components other than the solvent is the total content of the polymer solution. It is intended to be 3.0% by mass or less with respect to the total mass, preferably 2.0% by mass or less, and more preferably 1.0% by mass or less.
  • the polymer solution contains a resin (“acid-decomposable resin” or “resin (A)”) that is decomposed by the action of an acid to increase its polarity.
  • the acid-degradable resin usually contains a repeating unit having a group (hereinafter, also referred to as “acid-degradable group”) that decomposes by the action of an acid to increase its polarity.
  • acid-degradable group typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferable. Is formed in.
  • the resin (A) preferably contains a repeating unit having an acid-decomposable group (hereinafter, also referred to as "repeating unit A").
  • the acid-degradable group preferably contains a structure in which a polar group is protected by a group (leaving group) that is decomposed and eliminated by the action of an acid.
  • Polar groups include carboxy group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group. , Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. (A group that dissociates in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), an alcoholic hydroxyl group, and the like.
  • the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group directly bonded on the aromatic ring (phenolic hydroxyl group), and the ⁇ -position of the hydroxyl group is electron attraction such as a fluorine atom. Excludes aliphatic alcohols substituted with sex groups (eg, hexafluoroisopropanol groups, etc.). As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 is preferable.
  • polar group a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.
  • a preferable group as an acid-degradable group is a group in which the hydrogen atom of these groups is replaced with a group (leaving group) that is eliminated by the action of an acid.
  • Examples of the group (leaving group) desorbed by the action of an acid include -C (R 36 ) (R 37 ) (R 38 ), -C (R 36 ) (R 37 ) (OR 39 ), and-. Examples thereof include C (R 01 ) (R 02 ) (OR 39 ).
  • R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
  • R 36 and R 37 may be combined with each other to form a ring.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
  • the alkyl groups of R 36 to R 39 , R 01 and R 02 are preferably alkyl groups having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and hexyl. Groups, octyl groups and the like can be mentioned.
  • the cycloalkyl groups of R 36 to R 39 , R 01 , and R 02 may be monocyclic or polycyclic.
  • the monocyclic ring is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • a cycloalkyl group having 6 to 20 carbon atoms is preferable, and for example, an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinel group, a tricyclodecanyl group and a tetracyclododecyl group , And androstanyl groups and the like.
  • one or more carbon atoms in the cycloalkyl group may be substituted with 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 6 to 10 carbon atoms, 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 7 to 12 carbon atoms, 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 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
  • a cycloalkyl group (monocyclic or polycyclic) is preferable as the ring formed by bonding R 36 and R 37 to each other.
  • the monocyclic cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group
  • the polycyclic cycloalkyl group is preferably a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group or the like.
  • a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or an acetal ester group is preferable, and an acetal group or a tertiary alkyl ester group is more preferable.
  • the resin (A) preferably contains a repeating unit represented by the following general formula (AI) as the repeating unit A.
  • T represents a single bond or a divalent linking group.
  • the divalent linking group of 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 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 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • 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.
  • Rx 1 to Rx 3 independently represent an alkyl group or a cycloalkyl group, respectively. Any two of Rx 1 to Rx 3 may or may not be combined to form a ring structure.
  • the alkyl groups of Rx 1 , Rx 2 , and Rx 3 may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group. , Isobutyl group, t-butyl group and the like are preferable.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • the alkyl groups of Rx 1 , Rx 2 , and Rx 3 may have a part of the carbon-carbon bond as a double bond.
  • the cycloalkyl groups of Rx 1 , Rx 2 , and Rx 3 may be monocyclic or polycyclic. Examples of the monocyclic cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic cycloalkyl group include a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group and the like.
  • the ring formed by combining Rx 1 , Rx 2 , and Rx 3 may be monocyclic or polycyclic.
  • monocyclic rings include monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, and cyclooctane ring.
  • polycycles include polycyclic cycloalkyl rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring. Of these, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is preferable. Further, as the ring formed by combining Rx 1 , Rx 2 , and Rx 3 , the ring shown below is also preferable.
  • the resin (A) has the repeating unit described in paragraphs [0336] to [0369] of US Patent Application Publication No. 2016/0070167A1 as the repeating unit A.
  • the resin (A), as a repeating unit A contains a group that is decomposed by the action of an acid described in paragraphs [0363] to [0364] of US Patent Application Publication No. 2016/0070167A1 to generate an alcoholic hydroxyl group. It may have a repeating unit that includes.
  • the resin (A) may contain the repeating unit A alone or in combination of two or more.
  • the content of the repeating unit A contained in the resin (A) is preferably 10 to 90 mol%, preferably 20 to 90 mol%, based on all the repeating units of the resin (A). 80 mol% is more preferable, 30 to 80 mol% is further preferable, and 35 to 80 mol% is particularly preferable.
  • the repeating unit resin (A) having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure includes a structure selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure. More preferably, it contains a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure (hereinafter, also referred to as “repeating unit B”).
  • the resin (A) preferably contains one or more of a sultone structure and a carbonate structure in that bridge defects of the formed pattern are more suppressed, and the repeating unit B is a repeating unit having a sultone structure. More preferably, it comprises at least one of a unit and a repeating unit having a carbonate structure.
  • the lactone structure or sultone structure may have a lactone ring or a sultone ring, and a lactone structure having a 5- to 7-membered lactone ring or a sultone structure having a 5- to 7-membered sultone ring is preferable.
  • a lactone structure in which a 5- to 7-membered ring lactone ring is fused with another ring to form a bicyclo structure or a spiro structure is also preferable.
  • a sultone structure in which another ring is fused to a 5- to 7-membered sultone ring in the form of forming a bicyclo structure or a spiro structure is also preferable.
  • the resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-22), or any of the following general formulas (SL1-1) to (SL1-3). It is preferable to include a repeating unit having a sultone structure represented by. Further, the lactone structure or the sultone structure may be directly bonded to the main chain.
  • a lactone structure represented by the general formula (LC1-22) or a sultone structure represented by the general formula (SL1-1) is preferable.
  • the lactone structure or sultone structure may or may not have a substituent (Rb 2 ).
  • 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.
  • a halogen atom, a hydroxyl group, a cyano group or the like is preferable, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferable.
  • n 2 represents an integer from 0 to 4. When n 2 is 2 or more, the plurality of substituents (Rb 2 ) may be the same or different. Further, a plurality of existing substituents (Rb 2 ) may be bonded to each other to form a ring.
  • repeating unit having a lactone structure or a sultone structure a repeating unit represented by the following general formula (III) is preferable.
  • A represents -COO- or -CONH-.
  • n is the number of repetitions of the structure represented by ⁇ R 0 ⁇ Z ⁇ , represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0.
  • n is 0, (-R 0- Z-) n is a single bond.
  • R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R 0s , the plurality of R 0s may be the same or different.
  • the alkylene group represented by R 0 may be either linear or branched.
  • the carbon number of the alkylene group represented by R 0 is, for example, 1 to 12, preferably 1 to 10, and more preferably 1 to 6.
  • the cycloalkylene group represented by R 0 may be either monocyclic or polycyclic.
  • the carbon number of the cycloalkylene group represented by R 0 is, for example, 1 to 12, preferably 1 to 10, and more preferably 1 to 6.
  • Examples of the cycloalkane constituting the cycloalkylene group represented by R 0 include a monocyclic cycloalkane ring such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring, and a norbornane ring and a tetracyclodecane ring. , A tetracyclododecane ring, and a polycyclic cycloalkane ring such as an adamantan ring.
  • the alkylene group or cycloalkylene group of R 0 may have a substituent.
  • the substituent is not particularly limited, and for example, an alkyl group having 1 to 8 carbon atoms (either linear or branched chain) and a cycloalkyl group having 4 to 7 carbon atoms (monocyclic or polycyclic) are used. Any of them may be used), and examples thereof include an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxy group, a halogen atom, a hydroxyl group, and a cyano group.
  • Z represents a single bond, -O-, -COO-, -CONH-, -NH-CO-O-, or -NH-CO-NH-.
  • the plurality of Z's may be the same or different.
  • Z is preferably -O- or -COO-, and more preferably -COO-.
  • R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
  • the lactone structure or the sultone It is preferable that the group is formed by removing one hydrogen atom from one carbon atom constituting the structure. It is preferable that the carbon atom from which one hydrogen atom is removed is not a carbon atom constituting a substituent (Rb 2 ).
  • R 7 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
  • Examples of the organic group represented by R 7 include an alkyl group having 1 to 8 carbon atoms (either linear or branched chain), and a methyl group is preferable.
  • a monomer corresponding to a repeating unit having at least one selected from the group consisting of a lactone structure and a sultone structure will be illustrated.
  • the methyl group attached to the vinyl group may be replaced with a hydrogen atom, a halogen atom, or a monovalent organic group.
  • the resin (A) may have a repeating unit having a carbonate structure.
  • a carbonate structure a cyclic carbonate structure is preferable.
  • a repeating unit having a cyclic carbonate structure a repeating unit represented by the following general formula (A-1) is preferable.
  • RA 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • the monovalent organic group represented by RA 1 include an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a methyl group is preferable.
  • the substituent include a halogen atom and a hydroxyl group.
  • n represents an integer greater than or equal to 0.
  • R A 2 represents a substituent. when n is 2 or more, R A 2 existing in plural, may each be the same or different.
  • the substituent is not particularly limited, and for example, an alkyl group having 1 to 8 carbon atoms (either linear or branched chain) and a cycloalkyl group having 4 to 7 carbon atoms (monocyclic or polycyclic) are used. Any of them may be used), and examples thereof include an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxy group, a halogen atom, a hydroxyl group, and a cyano group.
  • A represents a single bond or a divalent linking group.
  • the divalent linking group represented by A is not particularly limited, but for example, -CO-, -O-, -S-, -SO-, -SO 2- , -NH-, and an alkylene group (preferably carbon). Numbers 1 to 6), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group obtained by combining a plurality of these groups can be mentioned. Among these, an alkylene group (preferably having 1 to 6 carbon atoms) which may contain -CO- and -O- is more preferable.
  • Z represents an atomic group forming a monocyclic or polycyclic ring with a group represented by —O—CO—O— in the formula.
  • an atomic group forming a monocycle with a group represented by —O—CO—O— in the formula is preferable, and the number of ring members of the monocycle is preferably 5 to 6, and more preferably 5.
  • the resin (A) has the repeating unit described in paragraphs [0370] to [0414] of US Patent Application Publication No. 2016/0070167A1 as the repeating unit B.
  • the repeating unit B may be contained alone or in combination of two or more.
  • the content of the repeating unit B contained in the resin (A) is preferably 5 to 70 mol% with respect to all the repeating units in the resin (A). From 20 to 65 mol% is more preferable, 20 to 65 mol% is further preferable, and 20 to 60 mol% is particularly preferable. Among them, the content of the repeating unit having a sultone structure and the repeating unit having a carbonate structure contained in the resin (A) (the total of the repeating units if a plurality of them exist) is based on all the repeating units in the resin (A). 10 to 65 mol% is more preferable, 10 to 60 mol% is further preferable, and 10 to 55 mol% is particularly preferable.
  • the resin (A) preferably contains a repeating unit having a polar group (hereinafter, also referred to as "repeating unit C").
  • the polar group include a hydroxyl group, a cyano group, a carboxy group, a fluorinated alcohol group (for example, a hexafluoroisopropanol group) and the like.
  • the repeating unit C a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferable.
  • the alicyclic hydrocarbon structure substituted with a polar group is preferably a cyclohexyl group, an adamantyl group, or a norbornane group.
  • the resin (A) may have one type of repeating unit C alone, or may contain two or more types in combination.
  • the content of the repeating unit C (if there are a plurality of repeating units C, the total thereof) is 5 to 60 mol with respect to all the repeating units in the resin (A). % Is preferred, 5 to 30 mol% is more preferred, and 5 to 15 mol% is even more preferred.
  • the resin (A) is further referred to as a repeating unit having neither an acid-decomposable group nor a polar group (hereinafter, also referred to as "repeating unit D". ) May be included.
  • the repeating unit D preferably has an alicyclic hydrocarbon structure. Examples of the repeating unit D include the repeating unit described in paragraphs [0236] to [0237] of US Patent Application Publication No. 2016/0026083A1. A preferred example of the monomer corresponding to the repeating unit D is shown below.
  • the resin (A) may contain the repeating unit D alone or in combination of two or more.
  • the content of the repeating unit D (if there are a plurality of repeating units D, the total thereof) is 5 to 40 mol with respect to all the repeating units in the resin (A).
  • % Is preferable 5 to 30 mol% is more preferable, 5 to 25 mol% is further preferable, and 5 to 15 mol% is particularly preferable.
  • the resin (A) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or resolution which is a general necessary property of resist. It may have various repeating units for the purpose of adjusting heat resistance, sensitivity and the like. Examples of such a repeating unit include, but are not limited to, a repeating unit corresponding to a predetermined monomer.
  • the predetermined monomer has one addition-polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. Examples include compounds.
  • an addition-polymerizable unsaturated compound that can be copolymerized with the monomers corresponding to the various repeating units may be used.
  • the resin (A) the molar ratio of each repeating unit is appropriately set in order to adjust various performances.
  • the resin (A) preferably contains a repeating unit derived from at least one of an acrylic acid ester and a methacrylic acid ester.
  • the resin (A), which is an acid-degradable resin has a structure containing a repeating unit derived from at least one of an acrylic acid ester and a methacrylic acid ester, a supermolecular weight substance and a gel component are added to the by-products generated in the manufacturing process. Many can be included. Therefore, when the resin (A), which is an acid-degradable resin, has a structure containing a repeating unit derived from at least one of an acrylic acid ester and a methacrylic acid ester, the effect of the production method of the present invention is more excellent. You can enjoy it.
  • the number of repeating units having an aromatic group is preferably 15 mol% or less with respect to all the repeating units in the resin (A) from the viewpoint of the transmission of ArF light. More preferably, it is 10 mol% or less.
  • the resin (A) is preferably a resin composed of repeating units derived from at least one of an acrylic acid ester and a methacrylic acid ester.
  • the repeating units are methacrylate-based repeating units
  • all of the repeating units are acrylate-based repeating units
  • all of the repeating units are either methacrylate-based repeating units or acrylate-based repeating units.
  • the acrylate-based repeating unit is preferably 50 mol% or less based on all the repeating units of the resin (A).
  • the resin (A) preferably has a repeating unit having an aromatic hydrocarbon ring group, and a repeating unit having a phenolic hydroxyl group, or It is more preferable to include a repeating unit having a structure protected by a leaving group (acid-degradable group) in which the phenolic hydroxyl group is decomposed and eliminated by the action of an acid.
  • a leaving group ascid-degradable group
  • the repeating unit containing a phenolic hydroxyl group include a hydroxystyrene repeating unit and a hydroxystyrene (meth) acrylate repeating unit.
  • the content of the repeating unit having an aromatic hydrocarbon ring group contained in the resin (A) is the total repetition in the resin (A). It is preferably 30 mol% or more with respect to the unit.
  • the upper limit is not particularly limited, but is, for example, 100 mol% or less. Among them, 30 to 100 mol% is preferable, 40 to 100 mol% is more preferable, and 50 to 100 mol% is further preferable.
  • the resin (A) for example, the resin (A) described in International Publication No. 2017/20177253 and the like can be appropriately used.
  • the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 20,000.
  • the degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further 1.1 to 2.0. preferable.
  • the polymer solution contains a solvent.
  • a known resist solvent can be appropriately used.
  • paragraphs [0665] to [0670] of U.S. Patent Application Publication No. 2016/0070167A1 paragraphs [0210] to [0235] of U.S. Patent Application Publication No. 2015/0004544A1, U.S. Patent Application Publication No. 2016/0237190A1.
  • Known solvents disclosed in paragraphs [0424] to [0426] of the specification and paragraphs [0357] to [0366] of US Patent Application Publication No. 2016/0274458A1 can be preferably used.
  • the solvent examples include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and a monoketone compound which may have a ring. (Preferably, the number of carbon atoms is 4 to 10), organic solvents such as alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate are mentioned, and alkylene glycol monoalkyl ether carboxylate is preferable, and propylene glycol monomethyl ether acetate is more preferable.
  • organic solvent one type may be used alone or two or more types may be used in combination, but it is preferable to use one type alone.
  • a mixed solvent in which two or more kinds of organic solvents are used in combination is used, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group are mixed is preferable.
  • the solid content concentration of the polymer solution is preferably 1.0 to 50% by mass, more preferably 2.0 to 40% by mass, and even more preferably 5.0 to 30% by mass.
  • the solid content concentration is the mass percentage of the mass of the components excluding the solvent with respect to the total mass of the polymer solution.
  • step B a compound that generates an acid by irradiation with active light or radiation (photoacid generator) is added to the polymer solution that has undergone the above step A, and a sensitive light-sensitive or radiation-sensitive resin composition (hereinafter, “resist”) is added.
  • resist a sensitive light-sensitive or radiation-sensitive resin composition
  • This is a step of adjusting (also referred to as "composition").
  • the actinic light-sensitive or radiation-sensitive resin composition obtained through step B will be described.
  • the resist composition contains an acid-decomposable resin (resin (A)) derived from the above-mentioned polymer solution.
  • the acid-decomposable resin (resin (A)) is as described above.
  • the resin (A) may be used alone or in combination of two or more.
  • the content of the resin (A) in the resist composition is generally 20.0% by mass or more, preferably 40.0% by mass or more, and 60.0% by mass, based on the total solid content.
  • the above is more preferable, and 70.0% by mass or more is further preferable.
  • the upper limit is not particularly limited, but 99.5% by mass or less is preferable, 99.0% by mass or less is more preferable, and 97.0% by mass or less is further preferable.
  • the solid content is intended to be a component in the composition excluding the solvent, and any component other than the solvent is regarded as a solid content even if it is a liquid component.
  • the resist composition contains a compound that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as “photoacid generator (B)”).
  • the photoacid generator (B) referred to here is an acid generator usually used to cause a deprotection reaction of a resin component (a deprotection reaction of an acid-degradable resin) or to cause a cross-linking reaction of a resin component.
  • the agent is applicable.
  • a compound that generates an organic acid by irradiation with active light or radiation is preferable.
  • Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.
  • a known compound that generates an acid by irradiation with active light or radiation can be appropriately selected and used alone or as a mixture thereof.
  • paragraphs [0125]-[0319] of U.S. Patent Application Publication 2016/0070167A1 paragraphs [0086]-[0094] of U.S. Patent Application Publication 2015/0004544A1
  • U.S. Patent Application Publication 2016 / The known compounds disclosed in paragraphs [0323] to [0402] of 0237190A1 can be preferably used as the photoacid generator (B).
  • photoacid generator (B) for example, a compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is preferable.
  • R 201 , R 202 and R 203 each independently represent an organic group.
  • the number of carbon atoms 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 bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • the two of the group formed by bonding of the R 201 ⁇ R 203, an alkylene group (e.g., butylene group, and pentylene group), and -CH 2 -CH 2 -O-CH 2 -CH 2 - is Can be mentioned.
  • Z - represents an anion.
  • Preferable embodiments of the cation in the general formula (ZI) include the corresponding groups in compound (ZI-1), compound (ZI-2), compound (ZI-3), and compound (ZI-4) described below. Be done.
  • the photoacid generator (B) may be a compound having a plurality of structures represented by the 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 aryl sulfonium compound in which at least one of R 201 to R 203 of the above general formula (ZI) is an aryl group, that is, a compound having aryl sulfonium as a cation.
  • all of R 201 to R 203 may be an aryl group, or a part of R 201 to R 203 may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
  • aryl sulfonium compound examples include a triaryl sulfonium compound, a diallyl alkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diallyl cycloalkyl sulfonium compound, and an aryl dicycloalkyl sulfonium compound.
  • aryl group contained in the arylsulfonium compound a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aryl group 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 heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like.
  • the aryl sulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group contained in the arylsulfonium compound as required is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms.
  • Cycloalkyl group is preferable, and examples thereof include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like.
  • the aryl group, alkyl group, and cycloalkyl group represented by R 201 to R 203 are independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group. It may have (for example, 6 to 14 carbon atoms), 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 R 201 to R 203 in the formula (ZI) each independently represent an organic group having no aromatic ring.
  • the aromatic ring also includes an aromatic ring containing a hetero atom.
  • the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
  • R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and are linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxy groups.
  • a carbonyl methyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
  • Examples of the alkyl group and cycloalkyl group of R 201 to R 203 include a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, etc.). Butyl group and pentyl group) or cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) are preferable.
  • R 201 to R 203 may be further substituted with 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 represented by the following general formula (ZI-3) and has a phenacylsulfonium salt structure.
  • R 1c to R 5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group. , Nitro group, alkylthio group or arylthio 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 each independently represent 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 are combined to form a ring structure, respectively.
  • this ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring formed by combining two or more of these rings.
  • the ring structure include 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 combining 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.
  • Examples of the group formed by bonding R 5c and R 6c , and R 5c and R x a single bond or an alkylene group is preferable.
  • Examples of the alkylene group include a methylene group and an ethylene group.
  • Zc - represents an anion.
  • the compound (ZI-4) is represented by the following general formula (ZI-4).
  • l represents an integer of 0 to 2.
  • r represents an integer from 0 to 8.
  • R 13 represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have substituents.
  • R 14 represents 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 group having a cycloalkyl group. These groups may have substituents. When a plurality of R 14 are present, each independently represents the above group such as a hydroxyl group. R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have substituents. Bonded to two R 15 each other may form a ring.
  • ring skeleton When two R 15 are combined to form a ring together, in the ring skeleton may contain a hetero atom such as an oxygen atom, or a nitrogen atom.
  • a hetero atom such as an oxygen atom, or a nitrogen atom.
  • two R 15 is an alkylene group, it is preferable to form a ring structure.
  • Z - represents an anion.
  • the alkyl groups represented by R 13 , R 14 and R 15 are linear or branched chain.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferable.
  • R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
  • aryl group represented by R 204 to R 207 a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aryl group represented by 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.
  • Examples of the alkyl group and cycloalkyl group represented by R 204 to R 207 include a linear alkyl group having 1 to 10 carbon atoms and a branched chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group and an ethyl group).
  • a propyl group, a butyl group, a pentyl group, etc.) or a cycloalkyl group having 3 to 10 carbon atoms is preferable.
  • the aryl group, alkyl group, and cycloalkyl group represented by R 204 to R 207 may each independently have a substituent.
  • substituents which the aryl group represented by R 204 to R 207 , the alkyl group, and the cycloalkyl group may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, carbon). Numbers 3 to 15), aryl groups (for example, 6 to 15 carbon atoms), alkoxy groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.
  • Z - represents an anion.
  • the represented anion is preferred.
  • o represents an integer of 1 to 3.
  • p represents an integer from 0 to 10.
  • q represents an integer from 0 to 10.
  • Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • the number of carbon atoms 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 Xfs are fluorine atoms.
  • R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If R 4 and R 5 there are a plurality, R 4 and R 5 may each be the same or different.
  • the alkyl group represented by R 4 and R 5 may have a substituent, and 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 the specific examples and preferred embodiments of Xf in the general formula (3).
  • L represents a divalent linking group.
  • -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.
  • the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
  • the alicyclic group may be a monocyclic type or a polycyclic type.
  • Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • polycyclic alicyclic group examples include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • alicyclic groups 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, are preferable.
  • the aryl group may be monocyclic or polycyclic.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
  • the heterocyclic group may be monocyclic or polycyclic.
  • the polycyclic type can suppress the diffusion of acid more.
  • the heterocyclic group may or may not have aromaticity.
  • Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • non-aromatic heterocycle examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
  • lactone ring and the sultone ring examples include the lactone structure and the sultone structure exemplified in the above-mentioned resin.
  • the heterocycle in the heterocyclic 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.
  • substituents include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms) and a cycloalkyl group (monocyclic, polycyclic, and spiroring). Any of them may be used, preferably 3 to 20 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group and a sulfonamide. Examples include groups and sulfonic acid ester groups.
  • the carbon constituting the cyclic organic group may be carbonyl carbon.
  • X B1 and X B2 each independently represent a monovalent organic group having no hydrogen atom or fluorine atom. It is preferable that X B1 and X B2 are hydrogen atoms. X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of X B3 and X B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and both X B3 and X B4 are monovalent organic groups having a fluorine atom or a fluorine atom. Is more preferable. It is even more preferred that both X B3 and X B4 are fluorine-substituted alkyl groups. L, q and W are the same as those in the general formula (3).
  • the represented anion is preferred.
  • Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • Xb independently represents an organic group having no hydrogen atom or fluorine atom.
  • 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 Often, it is preferably a benzenesulfonic acid anion substituted with a branched chain alkyl group or a cycloalkyl group.
  • Ar represents an aryl group and may further have a substituent other than the sulfonic acid anion and the- (DB) group. Further, examples of the substituent which may be possessed 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 further 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 an isopropyl group or a cyclohexyl group.
  • anion Z in formula (ZI) - the anion in the general formula (ZII) Z -, Zc in formula (ZI-3) -, and the general formula Z in (ZI-4) - shows the preferred embodiment below.
  • the photoacid generator (B) may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Further, the form of the low molecular weight compound and the form incorporated in a part of the polymer may be used in combination.
  • the photoacid generator (B) is preferably in the form of a low molecular weight compound.
  • the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
  • the photoacid generator (B) When the photoacid generator (B) is incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above, and is incorporated in a resin different from the resin (A). You may.
  • the photoacid generator (B) may be used alone or in combination of two or more.
  • the content of the photoacid generator (B) in the resist composition (if a plurality of types are present, the total thereof) is preferably 0.1 to 35.0% by mass, preferably 0, based on the total solid content of the composition. .5 to 25.0% by mass is more preferable, and 3.0 to 20.0% by mass is further preferable.
  • the photoacid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the photoacid generator contained in the resist composition (when a plurality of types are present).
  • the total is preferably 5 to 35% by mass, more preferably 7 to 30% by mass, based on the total solid content of the composition.
  • the acid dissociation constant pKa of the acid generated by decomposition of the photoacid generator (B) by irradiation with active light or radiation is, for example, ⁇ 0.01 or less, preferably ⁇ 1.00 or less. It is more preferably ⁇ 1.50 or less, and further preferably ⁇ 2.00 or less.
  • the lower limit of pKa is not particularly limited, but is, for example, ⁇ 5.00 or higher. pKa can be measured by the method described above.
  • the resist composition preferably contains an acid diffusion control agent as long as it does not interfere with the effects of the present invention.
  • the acid diffusion control agent (C) acts as a citric acid that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-degradable resin in the unexposed portion due to the excess generated acid. ..
  • Examples of the acid diffusion control agent (C) include a basic compound (CA), a basic compound (CB) whose basicity is reduced or eliminated by irradiation with active light or radiation, and a weak acid relative to an acid generator.
  • Acid diffusion control of onium salt (CC), low molecular weight compound (CD) having a nitrogen atom and a group desorbed by the action of acid, or onium salt compound (CE) having a nitrogen atom in the cation part, etc. can be used as an agent.
  • a known acid diffusion control agent can be appropriately used.
  • Known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 are suitable as the acid diffusion control agent (C). Can be used for.
  • R 200 , R 201 and R 202 may be the same or different, and each independently has a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl. Represents a group (6 to 20 carbon atoms).
  • R 201 and R 202 may be combined with each other to form a ring.
  • R 203 , R 204 , R 205 and R 206 may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl groups in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
  • 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. It is more preferable that the alkyl groups in the general formulas (A) and (E) are unsubstituted.
  • CA basic compound
  • guanidine aminopyrrolidin, pyrazole, pyrazoline, piperazine, aminomorpholin, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc.
  • a compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like are more preferable.
  • a basic compound (CB) whose basicity is reduced or eliminated by irradiation with active light or radiation (hereinafter, also referred to as “compound (CB)”) has a proton acceptor functional group and is active light or It is a compound that is decomposed by irradiation with radiation to reduce or disappear its proton accepting property, or to change from proton accepting property to acidic.
  • a proton-accepting functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a ⁇ -conjugated group. It means a functional group having a nitrogen atom having an unshared electron pair that does not contribute to.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.
  • Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.
  • the compound (CB) is decomposed by irradiation with active light or radiation to reduce or eliminate the proton acceptor property, or generate a compound in which the proton acceptor property is changed to acidic.
  • the decrease 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 due to the addition of a proton to the proton acceptor property functional group, and is specific.
  • the acid dissociation constant pKa of the compound generated by decomposition of the compound (CB) by irradiation with active light or radiation preferably satisfies pKa ⁇ -1, more preferably -13 ⁇ pKa ⁇ -1, and-. It is more preferable to satisfy 13 ⁇ pKa ⁇ -3.
  • the acid dissociation constant pKa can be obtained by the method described above.
  • an onium salt which is a weak acid relative to the acid generator
  • the acid generator is generated by active light or irradiation with radiation.
  • salt exchange releases the weak acid to produce an onium salt with a strong acid anion.
  • the strong acid is exchanged for the weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.
  • 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, carbon adjacent to S).
  • R 52 is an organic group
  • Y 3 is a linear, branched or cyclic alkylene group or arylene group
  • Rf is a fluorine atom. It is a hydrocarbon group containing, and M + is independently an ammonium cation, a sulfonium cation, or an iodonium cation.
  • Preferred examples of the sulfonium cation or iodonium cation represented by M + include the sulfonium cation exemplified by the general formula (ZI) and the iodonium cation exemplified by the general formula (ZII).
  • the compound (CCA) is preferably a compound represented by any of the following general 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 that links the cation site and the anion site.
  • -X - is, -COO -, -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, and -N.
  • R 1 , R 2 , R 3 , R 4 , and L 1 may be combined with each other to form a ring structure. Further, in the general formula (C-3), two of R 1 to R 3 are combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.
  • Substituents having 1 or more carbon atoms in R 1 to R 3 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. Of these, an alkyl group, a cycloalkyl group, or an aryl group is preferable.
  • L 1 as a divalent linking group includes 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, and two kinds thereof. Examples thereof include groups formed by combining the above.
  • L 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
  • a low molecular weight compound (CD) having a nitrogen atom and having a group desorbed by the action of an acid has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.
  • an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminol ether group is preferable, and a carbamate group or a hemiaminol ether group is more preferable. ..
  • the molecular weight of the compound (CD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
  • Compound (CD) may have a carbamate group having a protecting group on the nitrogen atom.
  • the protecting group constituting the carbamate group is represented by the following general formula (d-1).
  • Rb is independently 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), and an aralkyl group (preferably 3 to 30 carbon atoms). It preferably represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be connected to each other to form a ring.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are independently hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, or halogens. It may be replaced with an atom. The same applies to the alkoxyalkyl group indicated by Rb.
  • Rb 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.
  • the ring formed by connecting the two Rbs to each other include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon, and a derivative thereof.
  • Specific structures of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph [0466] of US Patent Publication US2012 / 0135348A1.
  • the compound (CD) 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
  • Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • the two Ras may be the same or different, and the two Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
  • Rb has the same meaning as Rb in the above general formula (d-1), and the same applies to preferred examples.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are independently substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb, respectively.
  • it may be substituted with a group similar to the group described above.
  • alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra include groups similar to the above-mentioned specific examples for Rb. Be done.
  • particularly preferred compounds (CDs) in the present invention include, but are not limited to, the compounds disclosed in paragraph [0475] of U.S. Patent Application Publication 2012 / 0135348A1.
  • the onium salt compound (CE) having a nitrogen atom in the cation portion (hereinafter, also referred to as “compound (CE)”) is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion.
  • the basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is more preferable that all the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-attracting functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom.
  • Preferred specific examples of the compound (CE) include, but are not limited to, the compound disclosed in paragraph [0203] of US Patent Application Publication 2015/0309408A1.
  • a preferable example of the acid diffusion control agent (C) is shown below.
  • the acid diffusion control agent (C) may be used alone or in combination of two or more.
  • the content of the acid diffusion control agent (C) (if a plurality of types are present, the total thereof) is determined to be 0, based on the total solid content of the composition. It is preferably 01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass.
  • the resist composition may contain a hydrophobic resin (D).
  • the hydrophobic resin (D) is preferably a resin different from the resin (A).
  • the hydrophobic resin (D) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and a polar / non-polar substance is used. It does not have to contribute to uniform mixing.
  • Hydrophobic resin (D) from the viewpoint of uneven distribution in the film surface layer, "fluorine atom”, “silicon atom”, and is selected from the group consisting of "CH 3 partial structure contained in the side chain portion of the resin” It is preferable that the resin has a repeating unit having at least one kind.
  • the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom
  • the fluorine atom and / or the silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin, and the side It may be contained in the chain.
  • the partial structure having a fluorine atom may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. preferable.
  • the hydrophobic resin (D) preferably has at least one group selected from the following groups (x) to (z).
  • Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonyl group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkyl).
  • Carbonyl) imide group bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) ) Methylene groups and the like can be mentioned.
  • the acid group a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis (alkylcarbonyl) methylene group is preferable.
  • Examples of the group (y) that decomposes due to the action of the alkaline developing solution and increases the solubility in the alkaline developing solution include a lactone group, a carboxylic acid ester group (-COO-), and an acid anhydride group (-C (O) OC). (O)-), acidimide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC (O) O-), sulfate ester group (-OSO 2 O-), and Examples thereof include a sulfonic acid ester group (-SO 2 O-), and a lactone group or a carboxylic acid ester group (-COO-) is preferable.
  • the repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of a resin, and examples thereof include a repeating unit made of an acrylic acid ester and a methacrylic acid ester.
  • these groups may be bonded to the main chain of the resin via a linking group.
  • the repeating unit may be introduced into the end of the resin by using a polymerization initiator or chain transfer agent having these groups at the time of polymerization.
  • Examples of the repeating unit having a lactone group include the same repeating units having the lactone structure described above in the section of resin (A).
  • the content of the repeating unit having a group (y) that decomposes by the action of the alkaline developer and increases the solubility in the alkaline developer is 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin (D). Is preferable, 3 to 98 mol% is more preferable, and 5 to 95 mol% is further preferable.
  • the repeating unit having a group (z) that decomposes by the action of an acid may be the same as the repeating unit having an acid-degradable group mentioned in the resin (A).
  • the repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having the group (z) decomposed by the action of the acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all the repeating units in the hydrophobic resin (D). , 20-60 mol% is more preferred.
  • the hydrophobic resin (D) may further have a repeating unit different from the repeating unit described above.
  • the repeating unit having a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all the repeating units in the hydrophobic resin (D).
  • the repeating unit having a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all the repeating units in the hydrophobic resin (D).
  • a hydrophobic resin (D) is also preferable that is substantially free of fluorine atom and a silicon atom. Further, it is preferable that the hydrophobic resin (D) is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.
  • the weight average molecular weight of the hydrophobic resin (D) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
  • the total content of the residual monomer and / or oligomer component contained in the hydrophobic resin (D) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
  • the degree of dispersion (Mw / Mn) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.
  • hydrophobic resin (D) a known resin can be appropriately selected and used alone or as a mixture thereof.
  • known resins disclosed in paragraphs [0451]-[0704] of U.S. Patent Application Publication 2015 / 0168830A1 and paragraphs [0340]-[0356] of U.S. Patent Application Publication 2016 / 0274458A1. Can be suitably used as the hydrophobic resin (D).
  • the repeating unit disclosed in paragraphs [0177] to [0258] of US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin (D).
  • a preferable example of the monomer corresponding to the repeating unit constituting the hydrophobic resin (D) is shown below.
  • the hydrophobic resin (D) may be used alone or in combination of two or more. It is preferable to mix and use two or more kinds of hydrophobic resins (D) having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
  • the content of the hydrophobic resin (D) in the resist composition is preferably 0.01 to 20.0% by mass, more preferably 0.05 to 8.0% by mass, based on the total solid content in the composition. ..
  • the resist composition contains a solvent.
  • the solvent contained in the resist composition may include not only the solvent brought in by the polymer solution but also the solvent separately added in the step B.
  • a known resist solvent can be appropriately used.
  • paragraphs [0665] to [0670] of U.S. Patent Application Publication No. 2016/0070167A1 paragraphs [0210] to [0235] of U.S. Patent Application Publication No. 2015/0004544A1
  • U.S. Patent Application Publication No. 2016/0237190A1 U.S. Patent Application Publication No.
  • 2016/0274458A1 can be preferably used.
  • the solvent that can be used when preparing the resist composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, and cyclic lactone (preferably having 4 to 10 carbon atoms).
  • organic solvents such as alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
  • a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used may be used.
  • the solvent having a hydroxyl group and the solvent having 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 (propylene glycol monomethyl ether).
  • PGME propylene glycol monoethyl ether
  • methyl 2-hydroxyisobutyrate or ethyl lactate
  • alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, 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 ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, ethyl ethoxypropionate, Cyclohexanone, cyclopentanone or 2-heptanone is more preferred.
  • PMEA propylene Glycol monomethyl ether acetate
  • ethyl ethoxypropionate 2-heptanone
  • ⁇ -butyrolactone cyclohexanone
  • Propylene carbonate is also preferable as the solvent having no hydroxyl group.
  • the mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable.
  • a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.
  • the solvent preferably contains propylene glycol monomethyl ether acetate, and may be a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.
  • the resist composition may contain a surfactant.
  • a surfactant a fluorine-based and / or a silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) Is preferable.
  • the resist composition contains a surfactant
  • a pattern having good sensitivity and resolution and few adhesions and development defects can be obtained when an exposure light source of 250 nm or less, particularly 220 nm or less is used.
  • Fluorine-based and / or silicon-based surfactants include those described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
  • other surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 can also be used.
  • surfactants may be used alone or in combination of two or more.
  • the content of the surfactant is, for example, 0.0001 to 20% by mass and 0.0001 to 2.0% by mass with respect to the total solid content of the composition. Is preferable, and 0.0005 to 1.0% by mass is more preferable.
  • the content of the surfactant is 10 ppm or more with respect to the total solid content of the composition, the uneven distribution of the surface of the hydrophobic resin (D) is increased. As a result, the surface of the resist film formed from the resist composition can be made more hydrophobic, and the water followability during immersion exposure is improved.
  • the resist composition may further contain other additives such as acid growth agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and dissolution accelerators. ..
  • the solid content concentration of the resist composition is usually preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass. It is more preferably 0 to 5.3% by mass.
  • the light source wavelength used in the exposure step is KrF line, it is usually preferably 1.0 to 50% by mass, more preferably 2.0 to 30% by mass.
  • the solid content concentration is the mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.
  • the film thickness of the resist film formed from the resist composition is preferably 90 nm or less, more preferably 85 nm or less, and more preferably 85 nm or less, when the light source wavelength used in the exposure step is other than KrF line.
  • the light source wavelength used for is KrF line, it is preferably 1000 nm or less, more preferably 800 nm or less.
  • Such a film thickness can be obtained by setting the solid content concentration in the resist composition in an appropriate range to give an appropriate viscosity and improving the coatability or the film forming property.
  • the resist composition is used by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, filtering the mixture, and then applying the resist composition onto a predetermined support (substrate).
  • the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
  • the pore size of the filter used for filter filtration is preferably 3 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.3 ⁇ m or less. ..
  • the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • filter filtration for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Laid-Open No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be arranged in series or in parallel. It may be connected to and filtered. Moreover, you may filter the resist composition a plurality of times. Further, the resist composition may be degassed before and after the filter filtration.
  • the resist composition obtained by the production method of the present invention corresponds to a resist composition whose properties change in response to irradiation with active light or radiation. More specifically, the resist composition obtained by the production method of the present invention includes a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, a molding structure for imprinting, and the like.
  • the present invention relates to a resist composition used for a photofabrication process, a slab printing plate, or a production of an acid curable composition.
  • the pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems), and the like.
  • the pattern forming method of the present invention (I) A step of forming a resist film (sensitive light-sensitive or radiation-sensitive film) on the support by the resist composition obtained by the above-mentioned production method of the present invention (resist film forming step). (Ii) A step (exposure step) of exposing the resist film (irradiating active light rays or radiation), (Iii) A step of developing the exposed resist film with a developing solution (development step), and Have.
  • the pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) above, and may further include the following steps.
  • the exposure method in the (ii) exposure step may be immersion exposure.
  • the pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.
  • the pattern forming method of the present invention preferably includes (v) post-exposure heating (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) development step.
  • the pattern forming method of the present invention may include (ii) exposure steps a plurality of times.
  • the pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
  • the pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.
  • the above-mentioned (i) film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.
  • a resist underlayer film for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film
  • SOG Spin On Glass
  • SOC Spin On Carbon
  • antireflection film As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
  • a protective film (top coat) may be formed on the upper layer of the resist film.
  • a known material can be appropriately used.
  • composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used.
  • the composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.
  • a protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.
  • the support is not particularly limited, and is generally used in a semiconductor manufacturing process such as an IC, a circuit board manufacturing process such as a liquid crystal or a thermal head, and other photolithography lithography processes.
  • a substrate can be used.
  • Specific examples of the support include an inorganic substrate such as silicon, SiO 2 , and SiN.
  • the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 130 ° C., still more preferably 80 to 120 ° C. in both the (iv) preheating step and the (v) post-exposure heating step.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, still more preferably 30 to 90 seconds in both the (iv) preheating step and the (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 by using a hot plate or the like.
  • the wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, polar ultraviolet light (EUV), X-ray, and electron beam.
  • far-ultraviolet light is preferable, and the wavelength thereof is preferably 250 nm or less, more preferably 220 nm or less, further 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), or an electron beam or the like, KrF excimer laser, ArF excimer laser, EUV or electron beam is preferable.
  • (Iii) In the developing step it may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).
  • alkaline developer a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition to this, alkaline aqueous solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines, and cyclic amines are also available. It can be used. Further, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant.
  • the alkali concentration of the alkaline developer is usually 0.1 to 20% by mass.
  • the pH of the alkaline developer is usually 10 to 15.
  • the time for developing with an alkaline developer is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkaline 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 a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. Is preferable.
  • ketone solvent examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl ketone.
  • Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like can be mentioned.
  • ester solvent examples include 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, and diethylene glycol monoethyl.
  • examples thereof include butyl acid acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate and the like.
  • the solvents disclosed in paragraphs [0715] to [0718] of US Patent Application Publication No. 2016/0070167A1 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 mass, more preferably less than 20% by mass, further preferably less than 10% by mass, most preferably less than 0 to 5% by mass, and substantially free of water. Is particularly preferable.
  • the content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferable.
  • the organic developer may contain an appropriate amount of a known surfactant, if necessary.
  • the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developing solution.
  • the organic developer may contain the acid diffusion control agent described above.
  • Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method), and a substrate.
  • Examples include a method of spraying the developer on the surface (spray method) or a method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic discharge method). Be done.
  • a step of developing with an alkaline aqueous solution (alkaline developing step) and a step of developing with a developer containing an organic solvent (organic solvent developing step) may be combined.
  • the pattern can be formed without dissolving only the region of the intermediate exposure intensity, so that a finer pattern can be formed.
  • pure water can be used as the rinsing solution used in the rinsing step after the developing step using the alkaline developer.
  • Pure water may contain an appropriate amount of a surfactant.
  • a process of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be added.
  • a heat treatment may be performed to remove the water remaining in the pattern.
  • the rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a general solution containing an organic solvent can be used.
  • a rinsing solution use a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. Is preferable.
  • Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent include the same as those described for the developing solution containing the organic solvent.
  • a rinsing solution containing a monohydric alcohol is more preferable.
  • Examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. 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 methylisobutylcarbinol can be mentioned.
  • Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, methyl isobutyl carbinol and the like. ..
  • a plurality of each component may be mixed, or may be mixed and used with an organic solvent other than the above.
  • the water content in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Good development characteristics can be obtained by setting the water content to 10% by mass or less.
  • the rinse solution may contain an appropriate amount of a surfactant.
  • the substrate developed with an organic developer is washed with a rinsing solution containing an organic solvent.
  • the cleaning treatment method is not particularly limited, and for example, a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotary coating method), or a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the substrate surface (spray method).
  • the cleaning treatment by the rotary coating method, and after cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate.
  • 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 resist composition obtained by the production method of the present invention, and various materials used in the pattern forming method of the present invention preferably do not contain impurities such as metal components, isomers, and residual monomers.
  • the content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and substantially not contained (below the detection limit of the measuring device). Is particularly preferable.
  • Examples of the method for removing impurities such as metals from the above-mentioned various materials include filtration using a filter.
  • the filter pore size is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less.
  • a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • the filter may be one that has been pre-cleaned with an organic solvent.
  • Filter In the filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step.
  • the filter it is preferable that the eluate is reduced as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426).
  • impurities may be removed by an adsorbent, and filter filtration and an adsorbent may be used in combination.
  • the adsorbent a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
  • Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500). Further, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Alternatively, a method such as lining the inside of the apparatus with Teflon (registered trademark) or the like to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned.
  • Teflon registered trademark
  • glass lining treatment it is also preferable to apply glass lining treatment to all processes of the manufacturing equipment for synthesizing various materials (resin, photoacid generator, etc.) of the resist component in order to reduce impurities such as metals to the order of ppt.
  • the preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
  • a method for 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 for improving the surface roughness of the pattern for example, a method of treating the pattern with a 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 as described in 8328 83280N-1 “EUV Resist Curing Technology for LWR Reduction and Etch Sensitivity Enhancement” may be applied.
  • the pattern formed by the above method is a spacer process disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/209941. Can be used as a core material (Core).
  • the present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern forming method.
  • the electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electrical and electronic device (for example, home appliances, OA (Office Automation) related devices, media related devices, optical devices, communication devices, etc.). Will be done.
  • an electrical and electronic device for example, home appliances, OA (Office Automation) related devices, media related devices, optical devices, communication devices, etc.
  • the monomers corresponding to each repeating unit of the resin P-AP1 shown below were mixed in a mixed solvent of 6/4 (mass ratio) of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether at a molar ratio of 40/60, respectively. It was dissolved and a monomer solution was prepared. Further, a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the dissolved solution was added dropwise to the solvent 1 over 6 hours. After completion of the dropping, the reaction was further carried out at 80 ° C. for 2 hours.
  • the reaction solution was allowed to cool, poured into hexane / ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain a resin (P-AP1).
  • the weight average molecular weight of the obtained resin (P-AP1) was 8,000, and the dispersity (Mw / Mn) was 1.5. Further, the resin (P-AP1) was dissolved in propylene glycol monomethyl ether acetate to obtain a polymer solution (P-AP1-0) of 15% by mass.
  • Step A Polymer solution filtration step
  • Step A filtering step of the polymer solution
  • ⁇ Purification Example 1 Preparation of Polymer Solution (P-AP1-1)> First, a filtration facility composed of a first filter of a nylon film (Pall-made Ultipleats / P-nylon, pore diameter 0.02 ⁇ m) was prepared. Next, the prepared polymer solution (P-AP1-0) was passed through the first filter under the condition of a linear velocity of 132 L / (hr ⁇ m 2 ) in an environment of 22 ° C. to obtain a polymer solution (P-AP1-0). P-AP1-1) was obtained. In addition, purification example 1 corresponds to the form in which step A includes the above-mentioned step X once.
  • ⁇ Purification Example 2 Preparation of Polymer Solution (P-AP1-2)> First, the first filter of nylon film (Pall's Ultipleated P-nylon, pore diameter 0.02 ⁇ m) and the second filter of polyethylene film (Microgard Plus made by Entegris, pore diameter 0.005 ⁇ m) are connected in series. I prepared a filtration facility. Next, the prepared polymer solution (P-AP1-0) is passed through the first filter to the second filter in this order under the condition of a linear velocity of 132 L / (hr ⁇ m 2 ) in an environment of 22 ° C. As a result, a polymer solution (P-AP1-2) was obtained.
  • the purification example 2 corresponds to the form in which the step A includes the above-mentioned step X twice or more, and specifically corresponds to the above-mentioned step (2).
  • the first filter corresponds to the above-mentioned filter X1
  • the second filter corresponds to the above-mentioned filter X2.
  • ⁇ Purification Example 3 Preparation of Polymer Solution (P-AP1-3)> First, the first filter of nylon film (Pall's Ultipleated P-nylon, pore diameter 0.02 ⁇ m) and the second filter of polyethylene film (Microgard Plus made by Entegris, pore diameter 0.005 ⁇ m) are connected in series. I prepared a filtration facility. Next, the prepared polymer solution (P-AP1-0) was applied 5 times in the order of the first filter to the second filter under the condition of a linear velocity of 132 L / (hr ⁇ m 2 ) in an environment of 22 ° C. The polymer solution (P-AP1-3) was obtained by repeating the liquid passing.
  • purification example 3 corresponds to the form in which step A includes the above-mentioned step X twice or more, and specifically corresponds to the above-mentioned step (2).
  • the first filter corresponds to the above-mentioned filter X1
  • the second filter corresponds to the above-mentioned filter X2.
  • Step B Preparation of resist composition
  • a first filter of nylon membrane pore diameter; 0.01 ⁇ m
  • a second filter of polyethylene membrane pore diameter; 0.002 ⁇ m
  • a third filter of polyethylene membrane pore diameter; 0.002 ⁇ m
  • Filtering equipment connected in series in this order was prepared.
  • each component is mixed according to the formulation shown in Table 4 below, and the obtained mixed solution is passed through the filtration equipment, whereby the resist composition (R-1 to R-) having a total solid content concentration shown in Table 4 is passed. 21, RC-1 to RC-3) were obtained.
  • A-3 Megafuck R-41 (manufactured by DIC Corporation) (fluorine-based)
  • Example AP-1 to AP-9, Comparative Example AP-1 The composition for forming an organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 95 nm.
  • the resist compositions R-1 to R-9 and RC-1 were each applied thereto, and the mixture was baked at 90 ° C. for 60 seconds to form a resist film having a film thickness of 85 nm.
  • Example AN-1 to AN-6, Comparative Example AN-1 The composition for forming an organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 95 nm.
  • the resist compositions R-10 to R-15 and RC-2 were applied thereto and baked at 90 ° C. for 60 seconds to form a resist film having a film thickness of 85 nm.
  • Examples KP-1 to KP-6, Comparative Example KP-1 An organic antireflection film forming composition DUV42 (manufactured by Brewer Science Co., Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 64 nm.
  • the resist compositions R-16 to 21 and RC-3 were applied thereto and baked at 130 ° C. for 60 seconds to form a resist film having a film thickness of 600 nm.

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  • General Physics & Mathematics (AREA)
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Abstract

Le premier problème abordé par la présente invention est de fournir un procédé de production d'une composition de résine sensible à la lumière active ou au rayonnement actif qui est capable de former un motif qui est exempt de défauts de pont. Le second problème abordé par la présente invention est de fournir : un procédé de formation de motif qui utilise une composition de résine sensible à la lumière active ou au rayonnement actif capable de former un motif qui est exempt de défauts de pont ; et un procédé de production d'un dispositif électronique.　Un procédé de production d'une composition de résine sensible à la lumière active ou au rayonnement actif selon la présente invention produit une composition de résine sensible à la lumière active ou au rayonnement actif qui est utilisée dans un procédé de production de dispositifs à semi-conducteur, et comprend : une étape A consistant à purifier une solution de polymère qui contient un solvant et une résine qui est décomposée par l'action d'un acide, ce qui augmente la polarité ; et une étape B consistant à préparer une composition de résine sensible à la lumière active ou au rayonnement actif par l'ajout d'un composé qui génère un acide lors de l'irradiation de la solution de polymère avec une lumière active ou un rayonnement actif après l'étape A. L'étape A comprend une étape X dans laquelle la solution de polymère est filtrée par passage à travers un filtre X.
PCT/JP2020/011635 2019-03-29 2020-03-17 Procédé de production de composition de résine sensible à la lumière active ou au rayonnement actif, procédé de formation de motif et procédé de production de dispositif électronique WO2020203246A1 (fr)

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JP2016089064A (ja) * 2014-11-06 2016-05-23 三菱レイヨン株式会社 半導体リソグラフィー用重合体の精製方法および製造方法、レジスト組成物の製造方法、ならびにパターンが形成された基板の製造方法
JP2016206500A (ja) * 2015-04-24 2016-12-08 信越化学工業株式会社 リソグラフィー用塗布膜形成用組成物の製造方法及びパターン形成方法
WO2018084302A1 (fr) * 2016-11-07 2018-05-11 富士フイルム株式会社 Liquide de préparation et procédé de formation de motifs

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JP2017169626A (ja) 2016-03-18 2017-09-28 有限会社Ｍｅｄｉｃａｌ・Ｌｉｎｋ 枕
WO2017169626A1 (fr) * 2016-03-30 2017-10-05 富士フイルム株式会社 Composition de résine active photosensible ou sensible aux rayonnements, procédé de formation de motif et procédé de fabrication de dispositif électronique

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WO2015151765A1 (fr) * 2014-03-31 2015-10-08 富士フイルム株式会社 Procédé de fabrication d'une composition de résine sensible à la lumière actinique ou sensible au rayonnement, et composition de résine sensible à la lumière actinique ou sensible au rayonnement
JP2016089064A (ja) * 2014-11-06 2016-05-23 三菱レイヨン株式会社 半導体リソグラフィー用重合体の精製方法および製造方法、レジスト組成物の製造方法、ならびにパターンが形成された基板の製造方法
JP2016206500A (ja) * 2015-04-24 2016-12-08 信越化学工業株式会社 リソグラフィー用塗布膜形成用組成物の製造方法及びパターン形成方法
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