WO2016088785A1 - Procédé de formation de film auto-assemblé, procédé de formation de motif et composition pour la formation dudit film auto-assemblé - Google Patents

Procédé de formation de film auto-assemblé, procédé de formation de motif et composition pour la formation dudit film auto-assemblé Download PDF

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WO2016088785A1
WO2016088785A1 PCT/JP2015/083826 JP2015083826W WO2016088785A1 WO 2016088785 A1 WO2016088785 A1 WO 2016088785A1 JP 2015083826 W JP2015083826 W JP 2015083826W WO 2016088785 A1 WO2016088785 A1 WO 2016088785A1
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self
solvent
forming
polymer
assembled film
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Japanese (ja)
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裕之 小松
信也 峯岸
岳彦 成岡
永井　智樹
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Jsr株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention relates to a method for forming a self-assembled film, a pattern forming method, and a composition for forming a self-assembled film.
  • pattern miniaturization is required in the pattern formation process.
  • a method of forming a self-organized pattern using a so-called self-organized phase separation (microdomain) structure that spontaneously forms an ordered pattern has been proposed.
  • an ultrafine pattern is formed by self-assembly using a block copolymer obtained by copolymerizing a monomer compound having one property and a monomer compound having a different property.
  • There are known methods for forming see JP 2008-149447 A, JP 2002-519728 A and JP 2003-218383 A).
  • a structure can be formed in a self-aligned manner in order to arrange the structures having the same properties so as to gather together.
  • a method of forming a fine pattern by self-organizing a composition containing a plurality of polymers having different properties See the publication.
  • phase separation structure formed by self-assembly is not sufficiently good, and as a result, defects in the pattern formed from the self-assembled film cannot be suppressed.
  • a method of forming a lower layer film under the self-assembled film and a method of forming a pre-pattern as a guide in advance in the self-assembled film formation region have been studied.
  • the occurrence of defects in the regular arrangement structure of the self-assembled film cannot be sufficiently suppressed.
  • the present invention has been made based on the above circumstances, and an object of the present invention is to provide a method for forming a self-assembled film that can form a self-assembled film with few defects in a regular arrangement structure. It is in.
  • the invention made in order to solve the above problems includes one or more first polymers (hereinafter also referred to as “[A] polymers”) and a solvent (hereinafter referred to as “a polymer”) that can form a phase separation structure by self-assembly.
  • a process for forming a liquid film on a substrate hereinafter referred to as “a solvent”) (hereinafter also referred to as “composition (I)”).
  • a solvent hereinafter also referred to as “composition (I)”.
  • Liquid solvent forming step) is a first solvent having a boiling point at 1 atm of 150 ° C. to 300 ° C. and a surface tension at 25 ° C. of 29 mN / m to 60 mN / m (hereinafter “ [B1] Solvent ”), and the content of the first solvent in the solvent is a method for forming a self-assembled film of 50% by mass or more.
  • Another invention made in order to solve the above problems includes a method of forming the self-assembled film and a step of removing a part of the phase of the self-assembled film (hereinafter also referred to as “removing step”). It is the pattern formation method provided.
  • Still another invention made in order to solve the above-mentioned problem includes one or more kinds of first polymers capable of forming a phase separation structure by self-assembly and a solvent, and the solvent is 1 atm.
  • This is a composition for forming an organized film.
  • Directed Self Assembly refers to a phenomenon in which an organization or structure is spontaneously constructed without being caused only by control from an external factor.
  • the method for forming a self-assembled film and the composition for forming a self-assembled film of the present invention it is possible to form a self-assembled film having a regular arrangement structure with few defects.
  • the pattern forming method of the present invention it is possible to form a pattern with a good shape using the self-assembled film with few defects of the regular arrangement structure. Therefore, they can be suitably used in pattern formation processes in the manufacture of various electronic devices such as semiconductor devices and liquid crystal devices that are required to be further miniaturized.
  • the formation method of the self-organization film of the present invention it is a mimetic diagram showing an example of the state after forming the self-assembly film.
  • the pattern formation method of this invention it is a schematic diagram which shows an example of the state after forming a lower layer film
  • the pattern formation method of this invention it is a schematic diagram which shows an example of the state after forming a pre pattern on a lower layer film.
  • the pattern formation method of this invention it is a schematic diagram which shows an example of the state after forming a liquid film in the area
  • the pattern formation method of this invention it is a schematic diagram which shows an example of the state after forming a self-organization film
  • the method for forming a self-assembled film includes a liquid film forming step, and the liquid film in the liquid film forming step is formed from the composition (I).
  • Composition (I) contains [A] a polymer that can form a phase-separated structure by self-organization, and [B1] a solvent that contains a specific amount of [B1] solvent that has a specific range of boiling point and surface tension. .
  • the method for forming a self-assembled film it is possible to form a self-assembled film having a regular array structure with few defects.
  • the [B] solvent contains a [B1] solvent having a specific property. For example, the separation can be performed better.
  • the method of forming the self-assembled film further includes a step of standing the liquid film (hereinafter also referred to as “stationary step”) and a step of heating the liquid film (hereinafter also referred to as “heating step”). It is preferable to provide.
  • phase separation structure formed by the method for forming a self-assembled film examples include a sea-island structure, a cylinder structure, a co-continuous structure, and a lamella structure.
  • the phase separation structure formed by the method for forming the self-assembled film may be partial.
  • it demonstrates, referring drawings for the order of each process and composition (I).
  • This step is a step of forming a liquid film 102 on the substrate 101 as shown in FIG.
  • the liquid film 102 is formed from the composition (I) described later.
  • the substrate 101 include conventionally known ones such as a silicon wafer, silicon dioxide, and a wafer coated with aluminum. Further, as will be described later, a lower layer film and / or a pre-pattern may be formed on the substrate before this step.
  • the method for forming the liquid film 102 include spin coating, cast coating, and roll coating.
  • the lower limit of the average thickness of the liquid film 102 to be formed is not particularly limited, but is preferably 0.2 nm, more preferably 1 nm, and even more preferably 2 nm.
  • the upper limit of the average thickness of the liquid film 102 is not particularly limited, but is preferably 1,000 nm, more preferably 200 nm, and still more preferably 120 nm.
  • the formation method of the self-assembled film may further include a step of removing the solvent from the liquid film 102 (hereinafter also referred to as “solvent removing step”) after the liquid film forming step.
  • solvent removing step a step of removing the solvent from the liquid film 102
  • Examples of the method for performing the solvent removal step include a method for heating the liquid film 102.
  • This step is a step of allowing the liquid film 102 formed in the liquid film forming step to stand. “Leave the liquid film” means that the liquid film is maintained and is not moved.
  • the method for forming the self-assembled film can form a better phase separation structure by including this step. In this step, as long as the liquid film 102 maintains a liquid film state, a part or all of the [B] solvent may be evaporated from the liquid film 102.
  • the lower limit of the standing time is preferably 1 minute, more preferably 3 minutes, and even more preferably 5 minutes.
  • the upper limit of the time is preferably 120 minutes, more preferably 60 minutes, further preferably 30 minutes, and particularly preferably 20 minutes from the viewpoint of productivity.
  • This step is a step of heating the liquid film 102.
  • This step may be performed in any of the liquid film forming step, the standing step, and the solvent removing step, but is preferably performed in the standing step.
  • a better phase separation structure can be formed by performing this step in the stationary step.
  • Examples of the heating method in the heating step include a method of heating with an oven, a hot plate, or the like.
  • the lower limit of the temperature of the heating step is preferably 40 ° C, more preferably 100 ° C, further preferably 150 ° C, and particularly preferably 200 ° C.
  • 300 degreeC is preferable, 280 degreeC is more preferable, 260 degreeC is further more preferable, 240 degreeC is especially preferable.
  • the lower limit of the heating step time is preferably 1 minute, more preferably 3 minutes, and even more preferably 5 minutes.
  • the upper limit of the time is preferably 120 minutes, more preferably 60 minutes, still more preferably 30 minutes, and particularly preferably 20 minutes.
  • a phase separation structure is formed from the liquid film 102 by performing the liquid film forming step and, if necessary, the solvent removing step, the standing step and / or the heating step, and as a result, a self-assembled film 103 is formed.
  • the composition (I) contains a [C] polymer, which will be described later, as shown in FIG. 2, for example, the [C] polymer is unevenly distributed above the self-assembled film 103 to form the region 104, A] The polymer is phase-separated in a substantially vertical direction to form a self-assembled film 103.
  • the lower limit of the average thickness of the self-assembled film 103 is not particularly limited, but is preferably 0.1 nm, more preferably 0.5 nm, and even more preferably 1 nm.
  • the upper limit of the average thickness of the self-assembled film 103 is not particularly limited, but is preferably 500 nm, more preferably 100 nm, and still more preferably 60 nm.
  • the method for forming the self-assembled film may include a step of annealing the formed self-assembled film 103 in order to improve the phase separation structure of the self-assembled film 103.
  • the annealing method include a method of heating with an oven, a hot plate, or the like.
  • 80 ° C is preferred, 100 ° C is more preferred, and 150 ° C is still more preferred.
  • 400 degreeC is preferable, 350 degreeC is more preferable, and 300 degreeC is further more preferable.
  • 1 minute is preferred, 2 minutes are more preferred, and 3 minutes are still more preferred.
  • the upper limit of the heating time is preferably 120 minutes, more preferably 90 minutes, and even more preferably 60 minutes.
  • composition (I) contains the [A] polymer and the [B] solvent.
  • the composition (I) is a second polymer having a surface free energy smaller than that of the [A] polymer (hereinafter also referred to as “[C] polymer”).
  • Other components such as a surfactant may be contained.
  • each component of the composition (I) will be described.
  • the polymer is one or more types of first polymers that can form a phase separation structure by self-assembly.
  • the polymer is preferably composed of only one type of block copolymer (hereinafter also referred to as “[A1] block copolymer”).
  • the polymer is preferably composed of a plurality of types of polymers (hereinafter also referred to as “[A2] polymer”).
  • the block copolymer is a polymer having a structure in which a plurality of blocks are bonded. Each of the blocks is composed of a chain structure of structural units derived from one type of monomer.
  • the same type of blocks are aggregated together by standing or heating to form a phase composed of the same type of blocks. At this time, since phases formed from different types of blocks do not mix with each other, it is presumed that a phase separation structure having an ordered pattern in which different types of phases are periodically and alternately repeated can be formed.
  • the block copolymer for example, a diblock copolymer having a structure in which two blocks are bonded, a triblock copolymer having a structure in which three blocks are bonded, and four blocks are bonded.
  • examples thereof include a tetrablock copolymer having a structure.
  • diblock copolymers and triblock copolymers are preferable, and diblock copolymers are more preferable.
  • Examples of the block include a polystyrene block, a poly (meth) acrylate block, a polyvinyl acetal block, a polyurethane block, a polyurea block, a polyimide block, a polyamide block, an epoxy block, a novolac type phenol block, and a polyester block.
  • the [A1] block copolymer is preferably a polymer comprising a polystyrene block and a poly (meth) acrylate block.
  • the mass ratio ((A) / (B)) of the content ratio of the two types of structural units (A) and (B) constituting the block copolymer is as follows:
  • the line / space width ratio of the desired line space pattern, the size of the contact hole, and the like can be selected as appropriate.
  • the lower limit of the above (A) / (B) is preferably 35/65, more preferably 40/60, from the viewpoint of forming a fine and good phase separation structure.
  • the upper limit of the above (A) / (B) is preferably 65/35, more preferably 60/40.
  • the upper limit of the above (A) / (B) is preferably 85/15, more preferably 75/25.
  • the block copolymer can be synthesized by forming the blocks in a desired order by living anion polymerization, living radical polymerization, or the like. Specifically, for example, a polystyrene block, a poly (meth) acrylic acid ester block, and other blocks other than these are linked while polymerizing in the desired order, and then synthesized by adding methanol or the like to stop the polymerization. can do.
  • styrene is first used in an appropriate solvent using an anionic polymerization initiator.
  • a polystyrene block is synthesized by polymerizing.
  • the polymerization is stopped by adding methanol or the like.
  • combining method of each block it can synthesize
  • Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, 2-heptanone; Ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes; Examples thereof include alcohols
  • the reaction temperature in the above polymerization may be appropriately determined according to the type of anionic polymerization initiator.
  • the lower limit of the reaction temperature in the polymerization is usually ⁇ 150 ° C., preferably ⁇ 80 ° C.
  • polymerization it is 50 degreeC normally and 40 degreeC is preferable.
  • the lower limit of the reaction time in the polymerization is usually 5 minutes, and preferably 20 minutes.
  • the upper limit of the reaction time in the polymerization is usually 24 hours and preferably 12 hours.
  • anionic polymerization initiator used for the polymerization examples include alkyl lithium, alkyl magnesium halide, sodium naphthalene, alkylated lanthanoid compounds, and the like.
  • alkyl lithium when the polymerization is performed using styrene or (meth) acrylic acid ester as a monomer, it is preferable to use an alkyl lithium compound.
  • the polymerization terminal is treated with, for example, a terminal treating agent containing a hetero atom, so that a hetero atom is contained at the terminal of the block copolymer.
  • a terminal treating agent containing a hetero atom so that a hetero atom is contained at the terminal of the block copolymer.
  • Groups can also be introduced. [A1] By introducing a group containing a hetero atom at the terminal of the block copolymer, the phase separation in the composition (I) can be controlled to be better.
  • Examples of the terminal treating agent containing a hetero atom include epoxy compounds such as 1,2-butylene oxide, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, propylene oxide, ethylene oxide, and epoxyamine; Isocyanate compound, thioisocyanate compound, imidazolidinone, imidazole, aminoketone, pyrrolidone, diethylaminobenzophenone, nitrile compound, aziridine, formamide, epoxyamine, benzylamine, oxime compound, azine, pyrazone, imine, azocarboxylic acid ester, aminostyrene, vinyl Nitrogen-containing compounds such as pyridine, aminoacrylate, aminodiphenylethylene, and imide compounds; Silane compounds such as alkoxy silane, amino silane, ketino silane, isocyanate silane, siloxane, glycidyl silane, mercapto silane, vinyl
  • the block copolymer synthesized by the above polymerization is preferably recovered by a reprecipitation method. That is, after the polymerization reaction, the target copolymer is recovered as a powder by introducing the reaction solution into a reprecipitation solvent.
  • a reprecipitation solvent alcohols or alkanes can be used alone or in admixture of two or more.
  • the polymer can be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.
  • the lower limit of the weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the block copolymer is preferably 1,000, more preferably 8,000, still more preferably 20,000, 000 is particularly preferred.
  • the upper limit of the Mw of the block copolymer is preferably 150,000, more preferably 100,000, still more preferably 80,000, and particularly preferably 70,000.
  • GPC gel permeation chromatography
  • the lower limit of the ratio (Mw / Mn) between the Mw and the number average molecular weight (Mn) of the block copolymer is usually 1.
  • the upper limit of Mw / Mn of the block copolymer is usually 5, preferably 3, more preferably 2, more preferably 1.5, and particularly preferably 1.2.
  • Mw / Mn of the block copolymer By setting Mw / Mn of the block copolymer in the above range, a better phase separation structure can be formed.
  • the polymer comprises a plurality of types of polymers.
  • the [A2] polymer having such a plurality of types of polymers is dissolved in an appropriate solvent, the same types of polymers aggregate to form a phase composed of the same types of polymers.
  • the layers formed from different types of polymers do not mix with each other, so it is presumed that a phase-separated structure having an ordered pattern in which different phases are periodically repeated alternately can be formed. .
  • the polymer can contain two or more kinds of polymers depending on the desired phase separation structure, but two kinds are preferred.
  • a polymer constituting the polymer for example, an acrylic polymer, a styrene polymer, a vinyl acetal polymer, a urethane polymer, a urea polymer, an imide polymer, an amide polymer, Examples thereof include novolak type phenol polymers and ester polymers.
  • the polymer may be a homopolymer synthesized from one type of monomer or a copolymer synthesized from a plurality of types of monomers.
  • the polymer preferably includes a styrene polymer and an acrylic polymer, and more preferably includes only a styrene polymer and an acrylic polymer.
  • the lower limit of the mass ratio of each polymer in the [A2] polymer is preferably 10/90, more preferably 20/80, and further 30/70 preferable.
  • the upper limit of the mass ratio of each polymer in the polymer is preferably 90/10, more preferably 80/20, and even more preferably 70/30.
  • Each polymer in the polymer is obtained by polymerizing, for example, a monomer corresponding to each predetermined structural unit in a suitable polymerization reaction solvent using a polymerization initiator such as a radical polymerization initiator. Can be manufactured.
  • a polymerization initiator such as a radical polymerization initiator.
  • Examples of the polymer synthesis method include a method in which a solution containing a monomer and a polymerization initiator is dropped into a polymerization reaction solvent or a solution containing a monomer to cause a polymerization reaction, a solution containing the monomer and a polymerization A method in which a solution containing an initiator is dropped into a polymerization reaction solvent or a solution containing a monomer separately to cause a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a polymerization initiator And a method in which a polymerization reaction is carried out by dropping them into a solution containing a polymerization reaction solvent or a monomer.
  • radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropylene). Pionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo radical polymerization initiators such as dimethyl 2,2′-azobisisobutyrate; benzoyl peroxide, t-butyl hydroperoxide And peroxide radical polymerization initiators such as cumene hydroperoxide. Of these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred. These radical polymerization initiators can be used alone or in combination of two or more.
  • the same solvents as mentioned in the above-mentioned method for synthesizing the [A1] block copolymer can be used.
  • the lower limit of the reaction temperature in the polymerization is usually 40 ° C., and preferably 50 ° C.
  • polymerization it is 150 degreeC normally and 120 degreeC is preferable.
  • the lower limit of the reaction time in the polymerization is usually 1 hour.
  • the upper limit of the reaction time in the polymerization is usually 48 hours, preferably 24 hours.
  • the polymer obtained by the above polymerization reaction is preferably recovered by a reprecipitation method in the same manner as in the method for synthesizing the above [A1] block copolymer.
  • the lower limit of Mw of each polymer in the [A2] polymer is not particularly limited, but is preferably 3,000, more preferably 5,000, still more preferably 7,000, and particularly preferably 8,000.
  • the upper limit of the Mw of the polymer is not particularly limited, but is preferably 50,000, more preferably 30,000, still more preferably 20,000, and particularly preferably 15,000.
  • the lower limit of Mw / Mn of each polymer in the polymer is usually 1.
  • the upper limit of Mw / Mn of the polymer is usually 5, preferably 3 and more preferably 2.
  • the lower limit of the content of the polymer is preferably 70% by mass, more preferably 80% by mass, still more preferably 90% by mass, and 95% by mass with respect to the total solid content of the composition (I). Particularly preferred.
  • the solvent includes [B1] solvent.
  • the solvent may contain a solvent other than the [B1] solvent as long as the effects of the present invention are not impaired.
  • the solvent is a solvent having a boiling point at 1 atm of 150 ° C. to 300 ° C. and a surface tension at 25 ° C. of 29 mN / m to 60 mN / m.
  • the content of the [B1] solvent in the [B] solvent is 50% by mass or more.
  • the [B] solvent contains the [B1] solvent, whereby a self-assembled film with few defects in the ordered arrangement structure can be formed.
  • the lower limit of the boiling point of the solvent at 1 atm is preferably 155 ° C, more preferably 160 ° C, further preferably 165 ° C, and particularly preferably 170 ° C.
  • the upper limit of the boiling point of the solvent at 1 atm is preferably 260 ° C, more preferably 240 ° C, further preferably 230 ° C, and particularly preferably 220 ° C.
  • the lower limit of the surface tension of the solvent at 25 ° C is preferably 29.5 mN / m, more preferably 30.0 mN / m, and even more preferably 30.5 mN / m.
  • the upper limit of the surface tension of the solvent at 25 ° C is preferably 55 mN / m, more preferably 50 mN / m, and even more preferably 45 mN / m.
  • the “surface tension” refers to the static surface tension when the liquid surface is stationary, and is a value measured by the Wilhelmy method.
  • Examples of the solvent include ketone solvents, ester solvents, amide solvents, aprotic polar solvents, alcohol solvents, and the like.
  • ketone solvent examples include cyclohexanone (boiling point: 155 ° C., surface tension: 35.2 mN / m), cycloheptanone (boiling point 180 ° C., surface tension: 34 mN / m), and the like.
  • ester solvent examples include lactones such as ⁇ -butyrolactone (boiling point: 204 ° C., surface tension: 43 mN / m); Propylene glycol diacetate (boiling point: 190 ° C., surface tension: 31.2 mN / m), 1,4-butanediol diacetate (boiling point: 232 ° C., surface tension: 34.2 mN / m), 1,3-butylene glycol Alkylene glycol diacetates such as diacetate (boiling point: 232 ° C., surface tension: 31.4 mN / m), 1,6-hexanediol diacetate (boiling point: 260 ° C., surface tension: 34.1 mN / m); Diethylene glycol monomethyl ether acetate (boiling point: 217 ° C., surface tension: 30.9 mN / m), diethylene glycol monoe
  • amide solvent examples include N, N-dimethylformamide (boiling point: 153 ° C., surface tension: 35.2 mN / m).
  • aprotic polar solvent examples include sulfoxide such as dimethyl sulfoxide (boiling point: 189 ° C., surface tension: 43.5 mN / m).
  • Examples of the alcohol solvent include 1,3-butylene glycol (boiling point: 208 ° C., surface tension: 36.1 mN / m), diethylene glycol monoethyl ether (boiling point: 202 ° C., surface tension: 31.3 mN / m), And tripropylene glycol methyl ether (boiling point: 242 ° C., surface tension: 30 mN / m), tripropylene glycol n-butyl ether (boiling point: 274 ° C., surface tension: 29.7 mN / m), and the like.
  • ester solvents Among these solvents, ester solvents, ketone solvents and combinations thereof are preferable, ester solvents are more preferable, alkylene glycol diacetate, dialkylene glycol monoalkyl ether acetate and combinations thereof are preferable. Further preferred.
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • the lower limit of the solubility parameter (SP value) of the solvent is preferably 8 (cal / cm 3 ) 1/2, more preferably 8.3 (cal / cm 3 ) 1/2 , and 8.5 (cal / Cm 3 ) 1/2 is more preferable.
  • the upper limit of the SP value of the [B1] solvent is preferably 15 (cal / cm 3 ) 1/2, more preferably 13 (cal / cm 3 ) 1/2 , and 12.5 (cal / cm 3 ). 1/2 is more preferable.
  • SP value is calculated by the method proposed by Fedors et al. Specifically, it can be calculated by the method described in “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 147 to 154)”.
  • the lower limit of the viscosity of the solvent at 25 ° C is preferably 1 mPa ⁇ s, more preferably 1.3 mPa ⁇ s, and even more preferably 1.5 mPa ⁇ s.
  • the upper limit of the viscosity is preferably 20 mPa ⁇ s, more preferably 10 mPa ⁇ s, further preferably 5 mPa ⁇ s, and particularly preferably 3 mPa ⁇ s.
  • a more favorable phase-separation structure can be formed by making the said viscosity into the said range.
  • the lower limit of the content of the solvent [B1] in the solvent is preferably 70% by mass, more preferably 80% by mass, still more preferably 90% by mass, particularly preferably 99% by mass, and 99.9% by mass. Further particularly preferred.
  • the [C] polymer is a polymer having a surface free energy smaller than that of the [A] polymer. As shown in FIG. 1, when the liquid film 102 is formed from the composition (I) containing the [C] polymer, the surface free energy of the [C] polymer is smaller than that of the [A] polymer.
  • the [C] polymer is considered to be unevenly distributed in the upper region in the liquid film 102 during the self-assembly process. Moreover, it is thought that the [B1] solvent in the liquid film 102 promotes uneven distribution of the [C] polymer in the upper region.
  • the phase separation of the [A] polymer proceeds better.
  • a self-assembled film 103 having a better phase separation structure can be formed, and as a result, a self-assembled film with fewer defects in a regular arrangement structure can be obtained.
  • the reason why the [C] polymer provides better phase separation is not necessarily clear, but may be considered as follows, for example. That is, when the [C] polymer is not applied, the surface free energy difference between the atmosphere and the [A] polymer is large, so that phase separation in a substantially horizontal direction tends to be promoted.
  • the difference in surface free energy from the [A] polymer becomes smaller than that in the atmosphere, and phase separation in a substantially horizontal direction is suppressed. It is conceivable that the phase separation is effectively carried out.
  • the [C] polymer is unevenly distributed in the region 104 above the self-assembled film 103.
  • the surface free energy of each polymer is determined by, for example, forming a thin film of each polymer by, for example, spin-coating a solution of each polymer and then heating, and the document “JOURNAL OF APPLIED POLYMER SCIENCE VOL.13, PP.1741- 1747 (1969) ". K.
  • the contact angle of liquid such as pure water and methylene iodide on the thin film is measured, and can be obtained from the measured value using the relationship of the following formula (X) and the following formula (Y). .
  • the lower limit of the value obtained by subtracting the surface free energy of the polymer [C] from the surface free energy of the polymer is preferably 1 mN / m, more preferably 3 mN / m, still more preferably 5 mN / m, and 7 mN / m. m is particularly preferable, and 9 mN / m is further particularly preferable.
  • the upper limit of the value obtained by subtracting the surface free energy of the [C] polymer from the surface free energy of the polymer is preferably 20 mN / m, more preferably 18 mN / m, still more preferably 15 mN / m, and 13 mN / m.
  • the [C] polymer is more effectively unevenly distributed in the standing step, and the interaction between the [C] polymer and the [A] polymer is more effective. As a result, it is possible to obtain a self-assembled film with fewer regular arrangement defects.
  • the polymer is not particularly limited as long as the surface free energy is smaller than that of the [A] polymer, but is a structural unit containing a fluorine atom and / or a silicon atom (hereinafter also referred to as “structural unit (I)”). It is preferable to have.
  • the lower limit of the content of the structural unit (I) in the polymer is preferably 10 mol%, more preferably 14 mol%, and more preferably 18 mol% with respect to all structural units constituting the [C] polymer. % Is more preferable, and 22 mol% is particularly preferable.
  • the content rate of the said structural unit (I) 50 mol% is preferable with respect to all the structural units which comprise a [C] polymer, 45 mol% is more preferable, 40 mol% is further more preferable, 36 Mole% is particularly preferred.
  • the polymer may have a structural unit other than the structural unit (I) (hereinafter also referred to as “structural unit (II)”).
  • structural unit (II) include structural units derived from (meth) acrylic acid esters, structural units derived from styrene compounds, and the like.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, and (meth) acrylic.
  • Examples include acid adamantyl, tetrahydrofurfuryl (meth) acrylate, and the like.
  • styrene compound examples include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 4-hydroxystyrene, 4- (t-butoxy) styrene, and the like.
  • the structural unit possessed by the [C] polymer from the viewpoint of forming a better phase separation structure by appropriately increasing the interaction with the [A] polymer, the structural unit possessed by the [A] polymer It is preferable to include at least a part, and it is more preferable to include all the structural units of the [A] polymer.
  • the [A] polymer is a diblock copolymer of polystyrene block-poly (meth) acrylic acid tetrahydrofurfuryl block
  • the [C] polymer is derived from styrene in addition to the structural unit (I).
  • a structural unit derived from tetrahydrofurfuryl (meth) acrylate and a structural unit derived from styrene and tetrahydrofurfuryl (meth) acrylate More preferably.
  • the [C] polymer is preferably a random copolymer from the viewpoint of forming a better phase separation structure by more effectively exhibiting the interaction with the [A] polymer.
  • a monomer that gives each structural unit such as the structural unit (I) and the structural unit (II) is used to initiate radical polymerization in the same manner as the above-described method for synthesizing the polymer [A]. It can synthesize
  • the lower limit of the Mw of the [C] polymer is preferably 1,000, more preferably 5,000, still more preferably 8,000, and particularly preferably 10,000.
  • the upper limit of the Mw of the polymer is preferably 100,000, more preferably 60,000, still more preferably 40,000, and particularly preferably 30,000.
  • the lower limit of Mw / Mn of the polymer is usually 1 and preferably 1.1.
  • the upper limit of Mw / Mn of the polymer is usually 5, preferably 3, more preferably 2.5, still more preferably 1.8, and particularly preferably 1.5.
  • Mw / Mn of the polymer By setting Mw / Mn of the polymer within the above range, a self-assembled film with fewer defects in the ordered structure can be formed.
  • composition (I) may further contain a surfactant.
  • substrate etc. can be improved because composition (I) contains surfactant.
  • composition (I) can be prepared, for example, by mixing the [A] polymer, the [B] solvent, and other components as necessary, and filtering through a membrane filter having a pore diameter of about 200 nm.
  • a minimum of solid content concentration of composition (I) 0.01 mass% is preferred, 0.1 mass% is more preferred, 0.3 mass% is still more preferred, and 0.5 mass% is especially preferred.
  • the pattern forming method includes a forming method and a removing step of the self-assembled film.
  • the pattern forming method includes a step of forming a lower layer film on the upper surface side of the substrate (hereinafter also referred to as a “lower layer film forming step”) and / or a liquid film forming step in the method for forming the self-assembled film described above. Or you may further provide the process (henceforth a "pre-pattern formation process") which forms a pre pattern in the upper surface side of the said board
  • the pattern forming method may further include a step of removing a pre-pattern (hereinafter, also referred to as “pre-pattern removing step”) after the method of forming the self-assembled film. It is preferable to further include a step of etching the substrate using the pattern as a mask (hereinafter also referred to as “substrate pattern forming step”).
  • pre-pattern removing step a step of removing a pre-pattern
  • substrate pattern forming step etching the substrate using the pattern as a mask
  • This step is a step of forming the lower layer film 105 on the upper surface side of the substrate 101.
  • a substrate with a lower layer film in which the lower layer film 105 is formed on the substrate 101 can be obtained.
  • a self-assembled film 103 described later is formed on the lower layer film 105.
  • the phase separation structure of the self-assembled film 103 is changed by the interaction with the lower layer film 105 in addition to the interaction between the blocks of the [A1] block copolymer contained in the composition (I).
  • the structure control may be easier.
  • the transfer process can be improved by having the lower layer film 105.
  • composition for forming an underlayer film used for forming the underlayer film 105 a conventionally known organic underlayer film forming material or the like can be used.
  • a composition for forming an underlayer film containing a crosslinking agent, a thermal acid generator, and the like Is mentioned.
  • the formation method of the lower layer film 105 is not particularly limited.
  • the lower layer film 105 is formed by applying a composition for forming the lower layer film on the substrate 101 by a known method such as a spin coat method, and then curing by exposure and / or heating. Methods and the like. Examples of radiation used for this exposure include visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, ⁇ -rays, molecular beams, and ion beams.
  • the lower limit of the heating temperature is not particularly limited, but 90 ° C. is preferable. Although it does not specifically limit as an upper limit of the said heating temperature, 550 degreeC is preferable, 450 degreeC is more preferable, and 300 degreeC is further more preferable.
  • the upper limit of the heating time is preferably 1,200 seconds, more preferably 600 seconds, and even more preferably 300 seconds.
  • the lower limit of the average thickness of the lower layer film 105 is not particularly limited, but is preferably 1 nm, more preferably 2 nm, and even more preferably 3 nm.
  • the upper limit of the average thickness of the lower layer film 105 is not particularly limited, but is preferably 20,000 nm, more preferably 1,000 nm, and still more preferably 100 nm.
  • This step is a step of forming a pre-pattern.
  • This pre-pattern may be formed on the substrate, or may be formed on the lower layer film 105 formed in the lower layer film forming step as shown in FIG.
  • the shape of the phase separation structure is controlled by the pre-pattern 106, and a finer pattern can be formed. That is, among the blocks of the [A1] block copolymer contained in the composition (I), blocks having high affinity with the side surface of the prepattern (referred to as “block (II)”) are blocked along the prepattern.
  • the phase (II) 103b is formed, and the block having low affinity (referred to as “block (I)”) forms the block phase (I) 103a at a position away from the pre-pattern.
  • the pattern to be formed becomes finer and better.
  • the phase separation structure of the self-assembled film 103 can be finely controlled by the material, size, shape, etc. of the pre-pattern.
  • the pre-pattern 106 can be appropriately selected according to the pattern to be finally formed. For example, a line and space pattern, a hole pattern, a cylinder pattern, or the like can be used.
  • a method for forming the pre-pattern 106 a method similar to a known resist pattern forming method may be used.
  • a composition used for formation of this pre-pattern 106 it is using conventional resist compositions, such as a composition containing the polymer which has an acid dissociable group, a radiation sensitive acid generator, and an organic solvent. it can.
  • a commercially available chemically amplified resist composition is applied onto the substrate 101 or the lower layer film 105 to form a resist film.
  • exposure is performed by irradiating a desired region of the resist film with radiation through a mask having a specific pattern.
  • the radiation examples include electromagnetic waves such as ultraviolet rays, far ultraviolet rays, and X-rays; and charged particle beams such as electron beams and ⁇ rays.
  • far ultraviolet rays are preferable
  • ArF excimer laser light and KrF excimer laser are preferable
  • ArF excimer laser light is more preferable.
  • immersion exposure can also be performed as an exposure method.
  • post-exposure baking PEB is performed, and development is performed using a developer such as an alkali developer or an organic solvent, so that a desired pre-pattern 106 can be formed.
  • the obtained pre-pattern 106 is further accelerated by a process of, for example, irradiating UV light of 254 nm, and then heating.
  • the lower limit of the heating temperature is, for example, 100 ° C.
  • the upper limit of the heating temperature is usually 200 ° C.
  • the lower limit of the heating time is, for example, 1 minute.
  • the upper limit of the heating time is, for example, 30 minutes.
  • the pre-pattern 106 As a method for forming the pre-pattern 106, a method similar to a known resist pattern forming method can be used. Further, as the pre-pattern forming composition, a conventional resist film-forming composition can be used.
  • the surface of the pre-pattern 106 may be subjected to a hydrophobic treatment or a hydrophilic treatment.
  • a hydrogenation treatment by exposing to hydrogen plasma for a certain period of time can be cited.
  • self-assembly can be further promoted.
  • the formation of the self-assembled film is as described in the section of the method for forming the self-assembled film.
  • the composition (I) is applied to the region on the lower layer film 105 sandwiched between the prepatterns 106 to form the liquid film 102.
  • a self-assembled film 103 having a phase separation structure having an interface substantially perpendicular to the substrate 101 is formed on the lower layer film 105 formed on the substrate 101.
  • the phase separation structure of the self-assembled film 103 is preferably formed along the pre-pattern 106, and the interface formed by the phase separation is substantially parallel to the side surface of the pre-pattern 106.
  • the block copolymer [A1] is composed of a styrene block and a poly (meth) acrylic acid block and the affinity between the prepattern and the styrene block is high, the phase of the styrene block is linear along the prepattern.
  • a lamellar phase separation structure in which a poly (meth) acrylic acid block phase and a styrene block phase are alternately arranged in this order is formed.
  • the phase separation structure to be formed is composed of a plurality of phases, and the interface formed from these phases is usually substantially vertical, but the interface itself is not necessarily clear.
  • the ratio of the length of each block chain in the block copolymer molecule, the length of the block copolymer molecule, the pre-pattern, the lower layer film, etc. are precisely controlled to obtain the desired fine structure. A pattern can be obtained.
  • This step is a step of removing a part of the phase separation structure of the self-assembled film 103.
  • the pre-pattern 106 can also be removed simultaneously with or separately from the partial phase. As shown in FIGS. 6 and 7, the block phase (I) 103a and the pre-pattern 106 of the self-assembled film 103 are removed by etching using the difference in the etching rate of each block phase phase-separated by self-assembly. can do.
  • the phase to be removed by etching is a polymethyl methacrylate block phase
  • radiation of 254 nm can be used. Since the polymethyl methacrylate block phase is decomposed by the radiation irradiation, etching becomes easier.
  • Examples of a method for removing a part of the block phase in the phase separation structure of the self-assembled film 103 include reactive ion etching (RIE) such as chemical dry etching and chemical wet etching; sputter etching and ion beam etching.
  • RIE reactive ion etching
  • a known method such as physical etching is used.
  • reactive ion etching (RIE) is preferable.
  • chemical dry etching using CF 4 , O 2 gas or the like, and chemical wet etching (wet development) using a liquid etching solution such as an organic solvent or hydrofluoric acid are preferable. More preferred.
  • organic solvent examples include alkanes such as n-pentane, n-hexane and n-heptane, cycloalkanes such as cyclohexane, cycloheptane and cyclooctane, ethyl acetate, n-butyl acetate, i-butyl acetate and propionic acid.
  • Saturated carboxylic acid esters such as methyl, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol And the like.
  • these solvents may be used independently and may use 2 or more types together.
  • Pre-pattern removal process This step is a step of removing the pre-pattern 106 as shown in FIGS. By removing the pre-pattern 106, a finer and more complicated pattern can be formed. As a method for removing the pre-pattern 106, a method for removing a part of the phase separation structure described above can be applied. Moreover, this process may be performed simultaneously with the said removal process, and may be performed before or after a removal process.
  • This step is a step of patterning by etching the lower layer film and the substrate using the pattern formed of a part of the remaining self-assembled film as a mask after the removing step. After the patterning on the substrate is completed, the phase used as a mask is removed from the substrate by a dissolution process or the like, and a finally patterned substrate can be obtained.
  • the etching method a method similar to the method in the removing step can be used, and the etching gas and the etching solution can be appropriately selected depending on the material of the lower layer film and the substrate.
  • the substrate is made of a silicon material
  • a mixed gas of chlorofluorocarbon gas and SF 4 or the like can be used.
  • the substrate is a metal film
  • a mixed gas of BCl 3 and Cl 2 or the like can be used.
  • the pattern obtained by the said pattern formation method is used suitably for a semiconductor element etc.
  • the said semiconductor element is used also for LED, a solar cell, etc.
  • the pattern can be similarly formed by the above method.
  • composition for forming a self-assembled film of the present invention contains one or more first polymers capable of forming a phase separation structure by self-assembly and a solvent, and the solvent has a boiling point at 1 atm. Includes a first solvent having a surface tension at 25 ° C. of 29 mN / m or more and 60 mN / m or less, and the content of the first solvent in the solvent is 50% by mass or more. Since the composition for forming a self-assembled film has been described in the section of the composition (I) of the method for forming the self-assembled film, the description thereof is omitted here.
  • Mw and Mn Mw and Mn of the polymer were measured by GPC using Tosoh's GPC columns (two G2000HXL, one G3000HXL and one G4000HXL) under the following conditions.
  • Eluent Tetrahydrofuran (Wako Pure Chemical Industries)
  • Flow rate 1.0 mL / min
  • Sample concentration 1.0% by mass
  • Sample injection volume 100 ⁇ L
  • Detector Differential refractometer Standard material: Monodisperse polystyrene
  • the block copolymer (A1-1) had Mw of 56,000 and Mw / Mn of 1.09. As a result of 13 C-NMR analysis, the ratio of the content ratio of styrene units to the content ratio of methyl methacrylate units in the block copolymer (A1-1) was 69.9 (mol%): 30.1 (mol%) )Met.
  • the block copolymer (A1-1) is a diblock copolymer.
  • the block copolymer (A1-2) had Mw of 56,000 and Mw / Mn of 1.08. As a result of 13 C-NMR analysis, the ratio of the content ratio of styrene units to the content ratio of methyl methacrylate units in the block copolymer (A1-2) was 50.1 (mol%): 49.9 (mol%). )Met.
  • the block copolymer (A1-2) is a diblock copolymer.
  • composition (I) ⁇ Preparation of composition (I)>
  • the [B] solvent used for the preparation of the composition (I) is shown below. Note that (B-1) to (B-8) are [B1] solvents.
  • B-1 cyclohexanone (boiling point: 155 ° C., surface tension: 35.2 mN / m, SP value: 9.9 (cal / cm 3 ) 1/2 )
  • B-2 Cycloheptanone (boiling point: 180 ° C., surface tension: 34 mN / m, SP value: 8.7 (cal / cm 3 ) 1/2 )
  • B-3 ⁇ -butyrolactone (boiling point: 204 ° C., surface tension: 43 mN / m, SP value: 12.0 (cal / cm 3 ) 1/2 )
  • B-4 Cyclohexanol acetate (boiling point: 173 ° C., surface tension: 30.5 mN / m, SP value: 9.2 (cal / cm 3 ) 1/2 )
  • B-5 Propylene glycol diacetate (boiling point: 190 ° C., surface tension: 31.2 mN / m
  • composition (I-1) 1 g of the block copolymer (A1-1) was dissolved in 99 g of cyclohexanone (B-1) as a solvent to obtain a 1% by mass solution. This solution was filtered through a membrane filter having a pore size of 200 nm to prepare a composition (I-1).
  • composition for forming lower layer film A flask equipped with a condenser and a stirrer was charged with 100 g (1.39 mol) of methyl ethyl ketone and purged with nitrogen, then heated to 85 ° C., and at the same temperature, 100 g (1.39 mol) of methyl ethyl ketone and 51.0 g of styrene (0.
  • this resin was diluted with propylene glycol monomethyl ether acetate to obtain a 10% by mass resin solution.
  • 100 g of a resin solution, 5.00 g of a compound represented by the following formula as a thermal acid generator, and 9,895 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dissolved to obtain a mixed solution.
  • the obtained mixed solution was filtered through a membrane filter having a pore size of 0.1 ⁇ m to prepare a composition for forming a lower layer film.
  • the composition for forming the lower layer film is applied using a spin coater (“CLEAN TRACK ACT8 SOD” manufactured by Tokyo Electron Co., Ltd.) to form a coating film having a thickness of 20 nm on the surface of a 12-inch silicon wafer. Baked for 60 seconds. Next, after developing with propylene glycol monomethyl ether acetate to peel off the unreacted resin solution, the substrate was dried at 100 ° C. for 120 seconds to form a lower layer film.
  • a spin coater (“CLEAN TRACK ACT8 SOD” manufactured by Tokyo Electron Co., Ltd.) to form a coating film having a thickness of 20 nm on the surface of a 12-inch silicon wafer. Baked for 60 seconds. Next, after developing with propylene glycol monomethyl ether acetate to peel off the unreacted resin solution, the substrate was dried at 100 ° C. for 120 seconds to form a lower layer film.
  • each of the prepared compositions (I) was applied using the spin coater so that the thickness of the formed self-assembled film was 20 nm. Thereafter, the film was allowed to stand while heating at 220 ° C. for 10 minutes to cause phase separation to form a self-assembled film having a microdomain structure. Thereafter, this self-assembled film was dry-etched with oxygen plasma using a plasma etching apparatus (“UNITY Me” manufactured by Tokyo Electron Ltd.) to form a pattern.
  • a plasma etching apparatus (“UNITY Me” manufactured by Tokyo Electron Ltd.)
  • the obtained pattern is a hole pattern with a pitch of 35 nm when the compositions (I-1) to (I-14) are used, and a pitch of 32 nm when the compositions (CI-1) to (CI-4) are used.
  • a line and space pattern having a pitch of 32 nm was obtained.
  • a self-assembled film having a microdomain structure was formed in the same manner as the pattern formation by dry etching, and then irradiated with 193 nm ArF light using the ArF exposure apparatus. Further, wet etching was performed using isopropyl alcohol to form a pattern.
  • the obtained pattern is a hole pattern with a pitch of 35 nm when the compositions (I-1) to (I-14) are used, and a pitch of 32 nm when the compositions (CI-1) to (CI-4) are used.
  • a line and space pattern having a pitch of 32 nm was obtained.
  • the method for forming a self-assembled film and the composition for forming a self-assembled film of the present invention it is possible to form a self-assembled film having a regular arrangement structure with few defects.
  • the pattern forming method of the present invention it is possible to form a pattern with a good shape using the self-assembled film with few defects of the regular arrangement structure. Therefore, they can be suitably used in pattern formation processes in the manufacture of various electronic devices such as semiconductor devices and liquid crystal devices that are required to be further miniaturized.

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Abstract

La présente invention concerne un procédé permettant la formation d'un film auto-assemblé, le procédé comprenant une étape consistant à former un film liquide sur un substrat en faisant appel à une composition pour la formation d'un film auto-assemblé qui contient un solvant et un ou plusieurs premiers polymères pouvant former une structure de séparation de phase par auto-assemblage, le solvant comprenant un premier solvant qui possède un point d'ébullition à 1 atm de 150 à 300 °C et une tension superficielle à 25 °C de 29 à 60 mN/m, et la teneur en ledit premier solvant dans le solvant étant supérieure ou égale à 50 % en masse. Ce procédé comprend également une étape consistant à laisser reposer ledit film liquide et une étape consistant à chauffer le film liquide. L'étape de chauffage peut être mise en œuvre au cours de l'étape de mise au repos. La teneur en ledit premier solvant dans le solvant est de préférence supérieure ou égale à 70 % en masse. La composition pour la formation d'un film auto-assemblé peut également contenir un second polymère possédant une tension superficielle inférieure à celle du premier polymère, et le second polymère peut être réparti de manière irrégulière sur le côté supérieur du film auto-assemblé. Le paramètre de solubilité du premier solvant est de préférence de 8 (cal/cm3)1/2 à 15 (cal/cm3)1/2.
PCT/JP2015/083826 2014-12-05 2015-12-01 Procédé de formation de film auto-assemblé, procédé de formation de motif et composition pour la formation dudit film auto-assemblé WO2016088785A1 (fr)

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WO2018043729A1 (fr) * 2016-09-02 2018-03-08 Jsr株式会社 Composition, procédé de modification et procédé de modification sélective de surfaces de substrat, procédé de formation de motif et polymère
WO2022049968A1 (fr) * 2020-09-01 2022-03-10 Jsr株式会社 Composition filmogène à auto-organisation, et procédé de formation de motif

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JP7008403B2 (ja) 2016-12-21 2022-01-25 東京応化工業株式会社 相分離構造形成用樹脂組成物、及び、相分離構造を含む構造体の製造方法
US20210009827A1 (en) * 2019-07-09 2021-01-14 Seiko Epson Corporation Solvent-based ink composition

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