WO2011065207A1 - Composition sensible aux rayonnements et procédés de formation d'un motif de photorésine - Google Patents

Composition sensible aux rayonnements et procédés de formation d'un motif de photorésine Download PDF

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Publication number
WO2011065207A1
WO2011065207A1 PCT/JP2010/069732 JP2010069732W WO2011065207A1 WO 2011065207 A1 WO2011065207 A1 WO 2011065207A1 JP 2010069732 W JP2010069732 W JP 2010069732W WO 2011065207 A1 WO2011065207 A1 WO 2011065207A1
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Prior art keywords
group
resist pattern
radiation
repeating unit
sensitive composition
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PCT/JP2010/069732
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English (en)
Japanese (ja)
Inventor
祐亮 庵野
剛史 若松
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Jsr株式会社
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Priority to JP2011543196A priority Critical patent/JP5652404B2/ja
Publication of WO2011065207A1 publication Critical patent/WO2011065207A1/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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a radiation-sensitive composition and a resist pattern forming method. More particularly, the present invention relates to a radiation-sensitive composition that can be used in a double patterning process and can be used in an immersion exposure process such as water without separately forming an upper layer film, and a resist pattern forming method using the same. .
  • DP is a technique in which a resist film is separately formed on a first resist pattern formed by exposing and developing a resist layer, and a second resist pattern is formed by exposing and developing.
  • DE refers to a technique for forming a resist pattern by exposing a resist layer to the same resist layer continuously without developing it and then developing the resist layer.
  • Non-Patent Document 2 discloses forming a 32 nm line with a 1: 1 pitch. Specifically, first, a 32 nm line having a pitch of 1: 3 is formed, and a hard mask (hereinafter also referred to as “HM”) such as SiO 2 is processed by etching. Thereafter, a 32 nm line having a pitch of 1: 3 is similarly formed at a position shifted from the first resist pattern by a half cycle, and HM is processed again by etching.
  • HM hard mask
  • Non-Patent Documents 1 and 2 there are some proposed processes such as Non-Patent Documents 1 and 2, there has not yet been proposed a specific material that can be suitably used for the double patterning process using such an immersion exposure process. The current situation is not.
  • the proposed process after forming the first resist pattern, when forming the second resist pattern, the first resist pattern may be deformed, and the accuracy of the pattern shape and dimensions is reduced. There's a problem.
  • the resist layer is usually immersed in the liquid.
  • an upper film for immersion In order to avoid lens contamination due to elution into the liquid, it was necessary to use an upper film for immersion.
  • the upper layer film for immersion is formed, there is a problem that the throughput deteriorates as the number of steps increases.
  • the present invention has been made in view of such problems of the prior art, and the problem is that the present invention is used for a double patterning process, and an upper layer film is separately provided for an immersion exposure process such as water.
  • the object is to provide a radiation-sensitive composition that can be used without being formed.
  • the present inventors can achieve the above-mentioned problems by including, as a constituent component, a repeating unit having a crosslinking group and a polymer containing a repeating unit having a fluorine atom. The inventors have found that this is possible and have completed the present invention.
  • the following radiation-sensitive composition and resist pattern forming method are provided.
  • the polymer (B) is a repeating unit represented by at least one of the repeating unit represented by the following general formula (1-1) and the repeating unit represented by the following general formula (1-2).
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 represents a methylene group. Represents an ethylene group or a propylene group, and R 3 represents a group represented by the following general formula (2) or (3):
  • R 4 represents a methylene group or a carbon number; And represents an alkanediyl group of 2 to 6.
  • R 5 represents a hydrogen atom, a methyl group or an ethyl group, and n represents 0 or 1.
  • a plurality of R 6 are each independently a hydrogen atom, a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 10 carbon atoms. Show.
  • the polymer (B) is a repeating unit (2) represented by at least one of the repeating unit represented by the following general formula (4) and the repeating unit represented by the following general formula (5) (The radiation-sensitive composition according to any one of the above [1] to [4], which includes “repeating unit (2)” hereinafter.
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 7 represents a single bond or a linear, branched or cyclic saturated group having 1 to 20 carbon atoms. Alternatively, it represents an unsaturated divalent hydrocarbon group,
  • X represents a methylene group substituted with a fluorine atom or a linear or branched fluoroalkanediyl group having 2 to 20 carbon atoms,
  • R 8 represents hydrogen It represents an atom or a monovalent organic group.
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • A represents a single bond, an ether bond, a thioether bond, a carbonyl group, an ester group, an amide group, or a sulfonamide group.
  • R 9 represents a divalent organic group having a urethane group, R 9 is a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, having at least one fluorine atom, or Represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
  • repeating unit (3) represented by the following general formula (6) (hereinafter also referred to as “repeating unit (3)”). Radiation sensitive composition.
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 10 s are independently of each other a methyl group, an ethyl group, or a straight chain having 3 to 4 carbon atoms.
  • a branched alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms provided that any two R 10s are bonded to each other and together with the carbon atom to which each is bonded, the number of carbon atoms
  • a divalent alicyclic hydrocarbon group having 4 to 20 is formed, and the remaining R 10 is a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 4 carbon atoms, or 4 to 20 carbon atoms
  • the monovalent alicyclic hydrocarbon group may be shown.
  • a step (1) of forming a first resist pattern on a substrate using the radiation-sensitive composition according to any one of [1] to [10], and the first resist A step (2) for insolubilizing the pattern with respect to the second radiation-sensitive composition, and a second pattern on the substrate on which the first resist pattern is formed using the second radiation-sensitive composition. Forming a resist pattern of (3).
  • the first resist pattern has a line portion and a space portion
  • the second resist pattern has a line portion and a space portion, the line portion of the first resist pattern
  • the first resist pattern has a line portion and a space portion
  • the second resist pattern has a line portion and a space portion, and the line portion of the first resist pattern;
  • the radiation-sensitive composition is applied onto the substrate to form a first resist layer, and after heating, the first resist layer is used as the outermost surface, and an exposure process is performed.
  • the resist pattern forming method according to any one of [11] to [13], which is a step of forming the first resist pattern by performing the steps described above.
  • the second radiation-sensitive composition is applied onto the substrate on which the first resist pattern is formed to form a second resist layer, and then heated.
  • the radiation-sensitive composition of the present invention is used in a double patterning process, and has an effect that it can be used in an immersion exposure process such as water without separately forming an upper layer film. .
  • the resist pattern forming method of the present invention in the double patterning process, the first resist pattern is insolubilized in the second radiation-sensitive composition during exposure to form the second resist pattern. Therefore, the second resist pattern can be formed while maintaining the shape and dimensions of the first resist pattern. That is, fluctuations in the line width of the first resist pattern can be suppressed.
  • the resist pattern forming method of the present invention has an effect that it can also be used in an immersion exposure process.
  • Resist pattern formation method is a method including steps (1) to (3).
  • An embodiment of a resist pattern forming method of the present invention including steps (1) to (3) will be described with reference to the drawings.
  • “line pattern” means that the resist pattern is a line-and-space pattern having a line portion and a space portion (hereinafter also referred to as “LS”).
  • Step (1) 1A to 1D are schematic views showing an example of the step (1) in the resist pattern forming method according to the present invention.
  • Step (1) is a step of forming a first resist pattern on the substrate using the first radiation-sensitive composition.
  • steps such as a step of forming the upper layer film with the resist layer as the outermost surface are performed. It is preferable to perform the exposure process without forming the first resist pattern. This is because the material used for forming the upper layer film can be saved, the number of processes can be reduced, and the throughput can be improved.
  • a first resist layer 2 is formed on a substrate 1 using a first radiation-sensitive composition.
  • a mask 4 and a lens 6 having a predetermined pattern are sequentially arranged in a predetermined region, and optionally using an immersion liquid 3 such as water, irradiation of radiation (arrow in the figure).
  • an immersion liquid 3 such as water, irradiation of radiation (arrow in the figure).
  • the alkali developing portion 5 is formed in the first resist layer 2.
  • a first resist pattern 12 having a line portion 12a and a space portion 12b (space for three lines with respect to 1L3S: one line) is formed on the substrate 1. .
  • the first resist layer can be formed by applying the first radiation-sensitive composition on the substrate.
  • the method for applying is not particularly limited. For example, it can be performed by an appropriate coating method such as spin coating, cast coating, roll coating or the like.
  • the thickness of the 1st resist layer formed is not specifically limited. Usually, it is 10 to 1000 nm, and preferably 10 to 500 nm.
  • the solvent in the coating film may be volatilized by pre-baking (hereinafter also referred to as “PB (Pre-Bake)”) as necessary.
  • PB heating conditions are appropriately selected depending on the composition of the first radiation-sensitive composition. Usually, the temperature is about 30 to 200 ° C, and preferably 50 to 150 ° C.
  • the first radiation-sensitive composition is the radiation-sensitive composition of the present invention described later.
  • the substrate is not particularly limited.
  • a conventionally known substrate such as a silicon wafer or a wafer coated with aluminum can be used.
  • an organic or inorganic antireflection film can be formed on the substrate to be used (for example, Japanese Patent Publication No. 6). -12452 and JP-A-59-93448).
  • the radiation used for exposure is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, etc., depending on the type of acid generator (C) contained in the first radiation-sensitive composition. Selected. Among these, far ultraviolet rays represented by ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm) are preferable, and far ultraviolet rays by ArF excimer laser (wavelength 193 nm) are particularly preferable.
  • the exposure conditions such as the exposure amount are appropriately selected according to the blending composition of the first radiation-sensitive composition, the type of additive, and the like.
  • PEB Post-Exposure Bake
  • the heating conditions for PEB are appropriately selected depending on the composition of the first radiation-sensitive composition. Usually, it is 30 to 200 ° C, and preferably 50 to 170 ° C.
  • first resist pattern 12 The alkali developing part is dissolved by developing the first resist layer with a developer. Thereby, the 1st resist pattern 12 which has the line part 12a and the space part 12b as shown to FIG. 1D can be formed. In addition, after developing with a developing solution, it is generally washed with water and dried.
  • the developing method is not particularly limited, and can be performed by a conventionally known method. Among these, development is preferably performed by a paddle method, an LD nozzle method, a GP nozzle method, or the like.
  • a preferred example of the developer is an alkaline aqueous solution in which at least one alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like is dissolved.
  • at least one alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like is dissolved.
  • the concentration of the alkaline aqueous solution is usually 10% by mass or less. If the concentration of the alkaline aqueous solution is more than 10% by mass, the unexposed area may be dissolved in the developer. Moreover, the lower limit of the concentration of the alkaline aqueous solution varies depending on the compound used. However, it is usually 0.5% by mass or more.
  • “alkali-insoluble or hardly-soluble alkali” means that 50% or more of the initial film thickness of a film formed only from a polymer is developed after development under an alkali development condition performed when a resist pattern is formed. The remaining properties.
  • organic solvent can also be added to the alkaline aqueous solution.
  • organic solvent include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; toluene
  • aromatic hydrocarbons such as xylene, phenol, acetonyl acetone, dimethylformamide and the like can be mentioned.
  • the use ratio of the organic solvent is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. If the use ratio of the organic solvent is more than 100 parts by volume, the developability may be reduced, and the development residue in the exposed part may increase. Further, an appropriate amount of a surfactant or the like may be added to the developer.
  • the volume is a volume measured at 25 ° C.
  • FIG. 2 is a schematic diagram showing an example of the step (2) in the resist pattern forming method according to the present invention.
  • the first resist pattern formed in the step (1) is heated at a temperature of 120 ° C. or higher (preferably 140 ° C. or higher) (hereinafter referred to as “PDB (Post-Development Bake)”).
  • PDB Post-Development Bake
  • Pattern 22 may be used. That is, the first resist pattern 22 is inactivated by heating (PB and PEB in step (3)) and radiation irradiation (exposure in step (3)).
  • the radiation irradiation condition examples include a condition of irradiating the radiation with an exposure amount 2 to 20 times the optimum exposure amount for forming the first resist pattern.
  • heating conditions the conditions heated on temperature conditions higher than PEB temperature at the time of forming a 1st resist pattern can be mentioned.
  • a lamp used for radiation irradiation a lamp such as an Ar 2 lamp, a KrCl lamp, a Kr 2 lamp, a XeCl lamp, or an Xe 2 lamp (manufactured by Ushio Inc.) can be used. These inactivation methods may be performed alone or in combination of two or more.
  • inactive with respect to light means that the radiation-sensitive composition does not change from insoluble to soluble in an alkaline aqueous solution even by exposure by irradiation with radiation or the like. . That is, the first resist pattern 22 does not become alkali-soluble even when exposed.
  • inert to heat means that deformation such as decomposition and melting does not occur by heating when forming the second resist pattern using the second radiation-sensitive composition. That is, the pattern shape does not disappear by heating.
  • Step (3) is a step of forming a second resist pattern on the substrate on which the first resist pattern is formed using the second radiation-sensitive composition.
  • the resist layer is formed in the same manner as in step (1). It is preferably a step of forming a second resist pattern by performing an exposure process without performing other steps such as a step of forming an upper layer film as the outermost surface. This is because the material used for forming the upper layer film can be saved, the number of processes can be reduced, and the throughput can be improved.
  • the second resist layer 32 is formed on the substrate 1 on which the first resist pattern 22 is formed using the second radiation-sensitive composition.
  • a mask 4 and a lens 6 having a predetermined pattern are sequentially arranged on the second resist layer 32 and, optionally, an immersion liquid 33 such as water is used to irradiate radiation (see FIG. 3B). (3B arrow) exposure is performed.
  • an immersion liquid 33 such as water is used to irradiate radiation (see FIG. 3B). (3B arrow) exposure is performed.
  • the alkali developing portion 35 is formed in the second resist layer 32.
  • the second resist pattern (second line portion 42a) is formed on the same surface of the substrate 1 on which the first resist pattern 22 is formed.
  • the second resist layer can be formed by applying the second radiation-sensitive composition onto the substrate on which the first resist pattern is formed.
  • the method for applying is not particularly limited. For example, it can be performed by an appropriate coating method such as spin coating, cast coating, roll coating or the like.
  • the thickness of the second resist layer is not particularly limited. Usually, it is 10 to 1000 nm, and preferably 10 to 500 nm.
  • the solvent in the coating film may be volatilized by PB if necessary.
  • the heating conditions for this PB are appropriately selected depending on the blending composition of the second radiation-sensitive composition. Usually, it is about 30 to 200 ° C, preferably 50 to 150 ° C.
  • the second radiation sensitive composition will be described later.
  • the same solvent may be sufficient as the solvent contained in a 1st radiation sensitive composition and a 2nd radiation sensitive composition, and a different solvent may be sufficient as it. This is because the first resist pattern is inactivated with respect to heat or light by performing the step (2), and is insolubilized with respect to the second radiation-sensitive composition. Therefore, the second resist layer can be formed without mixing with the first resist pattern.
  • 1L1S (the ratio of the width of the line portion to the space portion) in which the first resist pattern and the second resist pattern are alternately arranged on the substrate by double patterning as in the steps (1) to (3). 1: 1) can be formed.
  • a resist pattern (contact hole pattern 15) as shown in FIG. 4 can be formed by double patterning.
  • the resist pattern includes a first line portion 42a of the second resist pattern 42 formed in the step (3), and the first line portion 22a of the first resist pattern 22 is orthogonal to the first line portion 42a. This is performed by forming the resist pattern 22 on the first line portion 22a.
  • a resist pattern (contact hole pattern 15) as shown in FIG. 6 can be formed by double patterning.
  • This resist pattern is formed by forming the second resist pattern 42 formed in the step (3) in the space 22 b of the first resist pattern 22. Further, the resist pattern is formed in a lattice shape partitioned by the first line portion 22 a of the first resist pattern 22 and the second line portion 42 a of the second resist pattern 42.
  • a finer line pattern or a finer contact hole can be formed (hereinafter, obtained by the resist pattern forming method (double patterning) of the present invention.
  • a resist pattern (a line pattern or a contact hole pattern) is also referred to as a “DP pattern”).
  • the first resist pattern 22 has a line portion 22a and the second resist pattern 42 has a line portion 42a orthogonal to each other. It is also preferable to form the second resist pattern 42 on the resist pattern 22.
  • the width of the line portion and the space portion is preferably 40 to 100 nm (1L1S), more preferably 40 to 65 nm (1L1S), More preferably, it is 40 to 50 nm (1L1S).
  • Radiation sensitive composition In the radiation-sensitive composition, an acid labile group present in the composition is dissociated by the action of an acid generated from the radiation-sensitive acid generator upon exposure to generate a carboxy group. As a result, the exposed portion becomes highly soluble in an alkali developer, and is dissolved and removed by the alkali developer, so that a resist pattern can be formed. That is, the radiation-sensitive composition is a composition containing an alkali-insoluble or hardly soluble polymer that becomes alkali-soluble by the action of an acid, a radiation-sensitive acid generator, and a solvent.
  • the first radiation-sensitive composition used in forming the first resist layer which is the radiation-sensitive composition of the present invention, and the second used in forming the second resist layer. The radiation-sensitive composition is described separately.
  • a 1st radiation sensitive composition contains a polymer (A), a polymer (B), an acid generator (C), and (D) solvent.
  • the first resist pattern is inactivated against light or heat by irradiation with radiation having a wavelength of 300 nm or less and / or by heating at 140 ° C. or higher. It is preferable to make it.
  • This first resist pattern has resistance to the second radiation-sensitive composition. Therefore, it remains without being damaged when the second resist pattern is formed.
  • the “acid labile group” referred to in this specification means a group dissociated by an acid, and does not mean a particularly different group.
  • a polymer insoluble or hardly soluble in an alkali developer having an acid labile group is dissociated by the action of an acid to become a carboxy group, and a polymer soluble in an alkali developer.
  • Polymer (A) contains (A) a repeating unit having an acid labile group, and preferably does not contain a repeating unit having a crosslinking group.
  • the 1st radiation sensitive composition can form the 1st resist layer which melt
  • the repeating unit having a crosslinking group will be described later in “(2) Polymer (B)”.
  • Preferred examples of the polymer (A) include at least one lactone selected from the group consisting of the repeating unit (3) and the general formulas (7-1) to (7-5) and the formula (7-6). Some include a repeating unit having a structure or a repeating unit represented by the general formula (8) (hereinafter also referred to as “repeating unit (4)”).
  • R 11 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms.
  • P represents an integer of 1 to 3.
  • R 12 represents a hydrogen atom or a methoxy group
  • A represents a single bond or a methylene group
  • m represents , 0 or 1.
  • B represents an oxygen atom or a methylene group.
  • R 1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • R C1 represents a single bond or a divalent linking group.
  • R Cc represents 1 having a cyclic carbonate structure. Valent organic group.
  • examples of R Cc include groups represented by the following general formula (Cc-1) or (Cc-2).
  • n C1 represents an integer of 0 to 2.
  • n C2 to n C5 each independently represents an integer of 0 to 2.
  • “*” represents a bond bonded to R C1 in the general formula (8).
  • the group represented by Cc-2) may have a substituent.
  • Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms include norbornane, tricyclodecane, tetracyclododecane, adamantane, and cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.
  • examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed by bonding any two R 10 to each other include, for example, norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclo Groups composed of alicyclic rings derived from pentane, cyclohexane, etc .; groups composed of these alicyclic rings include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 And a group substituted with a linear or branched alkyl group having 3 to 4 carbon atoms, such as a -methylpropyl group, 1-methylpropyl group, t-butyl group, or the like, or a cycloalkyl group.
  • preferred examples of the group represented by —C (R 10 ) 3 include t-butyl group, 1-n- (1,1-dimethyl) propyl group, 1- (1,1 Groups having no alicyclic ring such as -diethyl) propyl group; 1- (1-methyl) cyclopentyl group, 1- (1-ethyl) cyclopentyl group, 1- (1-methyl) cyclohexyl group, 1- (1 -Ethyl) cyclohexyl group, 1- (1-methyl-1- (2-norbornyl)) ethyl group, 1- (1-methyl-1- (2-tetracyclodecanyl)) ethyl group, 1- (1- Methyl-1- (1-adamantyl)) ethyl group, 2- (2-methyl) norbornyl group, 2- (2-ethyl) norbornyl group, 2- (2-n-propyl) norbornyl group, 2- (2- Meth
  • a group substituted with a cycloalkyl group having 4 to 20 carbon atoms such as an alkyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the polymer (A) may contain only one type of repeating unit (3), or may contain two or more types.
  • the content of the repeating unit (3) is preferably 20 to 90 mol%, more preferably 20 to 80 mol%, still more preferably based on 100 mol% of the total repeating units contained in the polymer (A). 20 to 70 mol%.
  • the content ratio of the repeating unit (3) is within this range, it is particularly effective from the viewpoint of coexistence of control of solubility in the developer after coating and resistance to exposure when forming the second resist pattern. is there.
  • Monomers that give a repeating unit represented by the general formula (8) include, for example, Tetrahedron Letters, Vol. 27, no. 32 p. 3741 (1986), Organic Letters, Vol. 4, no. 15 p. 2561 (2002), etc., and can be synthesized by a conventionally known method.
  • repeating unit represented by the general formula (8) include repeating units represented by the general formulas (8-1) to (8-22).
  • R 1 in the general formula (8-1) to (8-22) has the same definition as R 1 in the general formula (8).
  • the polymer (A) may contain only one type of repeating unit (4), or may contain two or more types.
  • the content of the repeating unit (4) is usually 80 mol% or less, preferably 20 to 80 mol%, more preferably 30 to 30 mol% with respect to 100 mol% of the total repeating units contained in the polymer (A). 70 mol%.
  • the content ratio of the repeating unit (4) is within this range, it is particularly effective from the viewpoint of achieving both control of solubility in the developer and resistance to exposure when forming the second resist pattern.
  • the polymer (A) may contain one or more kinds of repeating units other than the repeating unit (3) and the repeating unit (4) (hereinafter also referred to as “other repeating units”).
  • repeating unit (5) examples include a repeating unit represented by the general formula (9) (hereinafter also referred to as “repeating unit (5)”) and a repeating unit represented by the general formula (10) (hereinafter referred to as “repeating unit”).
  • Unit (6) refers to a repeating unit represented by the general formula (9) (hereinafter also referred to as “repeating unit (5)”) and a repeating unit represented by the general formula (10) (hereinafter referred to as “repeating unit”).
  • Unit (6) examples include a repeating unit represented by the general formula (9) (hereinafter also referred to as “repeating unit (5)”) and a repeating unit represented by the general formula (10) (hereinafter referred to as “repeating unit”). Unit (6) ").
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • Z represents a single bond or a divalent organic group having 1 to 3 carbon atoms.
  • W represents a carbon number. 7 to 20 optionally substituted polycyclic alicyclic hydrocarbon groups, provided that when the polycyclic alicyclic hydrocarbon group has a substituent, examples of the substituent include a methyl group, an ethyl group, A linear or branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, or an oxo group. .
  • R 14 represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • R 15 represents a divalent organic group.
  • examples of the optionally substituted polycyclic alicyclic hydrocarbon group represented by W having 7 to 20 carbon atoms include bicyclo [2.2.1] represented by the following formula: ] Heptane (9a), bicyclo [2.2.2] octane (9b), tricyclo [5.2.1.0 2,6 ] decane (9c), tetracyclo [6.2.1.1 3,6 . Hydrocarbon groups derived from cycloalkanes such as 0 2,7 ] dodecane (9d) and tricyclo [3.3.1.1 3,7 ] decane (9e).
  • the hydrocarbon group derived from cycloalkane has a substituent
  • substituents include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methyl.
  • C4-C20 cycloalkyl such as linear or branched alkyl group having 3 to 10 carbon atoms such as propyl group, 1-methylpropyl group and t-butyl group, cyclopentyl group, cyclohexyl group and cyclooctyl group
  • the substituent is not limited to these alkyl groups, and may be a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxy group, or an oxo group.
  • the divalent organic group represented by R 15 is preferably a divalent hydrocarbon group, and more preferably a chain or cyclic divalent hydrocarbon group. It may be an alkylene glycol group, an alkylene ester group, or the like. Specific examples of the divalent organic group include alkanes such as methylene group, ethylene group, icosalen group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, and 2-propylidene group. Diyl group;
  • Monocyclic hydrocarbon ring groups such as cycloalkylene groups having 3 to 10 carbon atoms such as 1,3-cyclobutylene group and 1,3-cyclopentylene group; 1,4-norbornylene group, 1,5-adamantylene Examples thereof include a bridged cyclic hydrocarbon ring group such as a 2-4 cyclic hydrocarbon ring group having 4 to 30 carbon atoms such as a group.
  • a hydrocarbon group containing a 2,5-norbornylene group, a 1,2-ethylene group, and a propylene group are preferable.
  • R 15 contains a divalent aliphatic cyclic hydrocarbon ring group, a bistrifluoromethyl-hydroxy-methyl group (—C (CF 3 ) 2 OH) and a divalent aliphatic cyclic carbonization group It is preferable to arrange an alkanediyl group having 1 to 4 carbon atoms as a spacer between the hydrogen group.
  • the polymer (B) includes a repeating unit having a crosslinking group and a repeating unit having a fluorine atom.
  • the first radiation-sensitive composition contains the oil-repellent polymer (B), so that when the resist film is formed, the distribution tends to be higher on the resist film surface. Therefore, at the time of immersion exposure, it is possible to suppress the acid generator (C), the acid diffusion control agent, and the like in the resist film from being eluted into an immersion liquid such as water. In addition, the receding contact angle between the resist film and the immersion liquid is increased due to the water-repellent characteristics of the polymer (B).
  • the first resist pattern can be insolubilized in the second radiation-sensitive composition by heating or irradiation.
  • the polymer (B) further includes a repeating unit having an acid labile group. This is because the polymer (B) has a property of being dissolved in an alkali developer by the action of an acid.
  • the content of the polymer (B) is usually 1 to 80 parts by weight, preferably 2 to 50 parts by weight, more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the polymer (A). It is. When the content is in this range, it is possible to have sufficient resistance to the second radiation-sensitive composition, and it is possible to suppress poor resolution when forming the first resist pattern.
  • repeating unit having a crosslinking group is preferably the repeating unit (1).
  • the cross-linking group is preferably a thermosetting reactive group.
  • examples of the linear or branched alkyl group having 3 to 10 carbon atoms represented by R 6 include an n-propyl group, i -Propyl group, 2-methylpropyl group, 1-methylpropyl group, n-butyl group, t-butyl group and the like.
  • repeating unit represented by the general formula (1-1) include repeating units represented by the following general formulas (1-1-a) to (1-1-h). .
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • repeating unit represented by the general formula (1-2) include repeating units represented by the following general formulas (1-2-a) to (1-2-d). .
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • repeating units represented by (1-1-a), (1-1-e), and (1-2-a) are more preferable.
  • the ratio of the repeating unit (1) contained in the polymer (B) is preferably 1 to 30 mol% with respect to 100 mol% of the total repeating units contained in the polymer (B), preferably 1 to 25 mol%. More preferably, it is 5 to 15 mol%.
  • the ratio of the repeating unit (1) is within this range, the alkali developing portion is less likely to swell with the alkali developing solution, and the solubility in the alkali developing solution is maintained, thereby suppressing line width variation and dimensional accuracy reduction. be able to.
  • repeating unit having a fluorine atom is preferably a repeating unit represented by the repeating unit (2) or the general formula (f-4).
  • examples of the linear or branched, saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms include, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group
  • examples of the cyclic saturated or unsaturated divalent hydrocarbon group include groups derived from alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 20 carbon atoms.
  • examples of the alicyclic hydrocarbon include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5.2.1.0 2,6 ].
  • examples of the aromatic hydrocarbon include benzene and naphthalene.
  • the hydrocarbon group for R 7 is a group selected from the group consisting of at least one hydrogen atom in the above-mentioned unsubstituted hydrocarbon group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methyl group.
  • C3-C12 linear or branched alkyl group such as propyl group, 1-methylpropyl group, t-butyl group, cycloalkyl group, hydroxy group, cyano group, hydroxyalkyl group having 1-10 carbon atoms , A carboxy group, a group substituted by one or more of oxygen atoms and the like.
  • R 7 in the general formula (4) include groups represented by the following structures (a1) to (a27).
  • “*” represents a binding site.
  • R 7 in the general formula (4) is preferably a methylene group, an ethylene group, a 1-methylethylene group, a 2-methylethylene group, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or the like.
  • examples of the methylene group substituted with a fluorine atom represented by X or a linear or branched fluoroalkanediyl group having 2 to 20 carbon atoms include, for example, the following formula (X-1) There are groups represented by structures such as (X-8).
  • the repeating unit represented by the general formula (4) is preferably a repeating unit derived from the compounds represented by the formulas (4-1) to (4-6).
  • Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having at least one fluorine atom include a cyclopentyl group, a cyclopentylmethyl group, a 1- (1-cyclopentylethyl) group, 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cyclo Heptylethyl) group, 1- (2-cycloheptylethyl) group, 2-norbornyl group and other alicyclic alkyl groups such as partially fluorinated or perfluoroalkyl groups.
  • Preferred monomers that give the repeating unit (2) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, Perfluoro n-propyl (meth) acrylic acid ester, perfluoro i-propyl (meth) acrylic acid ester, perfluoro n-butyl (meth) acrylic acid ester, perfluoro i-butyl (meth) acrylic acid ester, perfluoro t-butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylic acid ester, 1- (2,2,3,3,4,4 , 5,5-octafluoropentyl) (meth) acrylic acid ester, perfluorocyclohexylmethyl (meth) Acrylic acid ester, 1- (2,2,3,3,3-pentafluoropropyl)
  • the polymer (B) may have a repeating unit (f) represented by the following general formula (f-4) (hereinafter also referred to as “repeating unit (f)”).
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R k4 represents a (m + 1) -valent linking group.
  • X f4 represents a fluorine atom 2
  • R j4 represents a hydrogen atom or a monovalent organic group
  • m is an integer of 1 to 3.
  • a plurality of R j4 are each independently Represents a hydrogen atom or a monovalent organic group.
  • the (m + 1) -valent linking group represented by R k4 is an (m + 1) -valent hydrocarbon having 1 to 10 carbon atoms which may have an ether group or an ester group Group, more preferably an (m + 1) -valent hydrocarbon group having 1 to 8 carbon atoms which may have an ether group or an ester group, and particularly preferably an ether group or an ester group.
  • the divalent linking group having a fluorine atom represented by Xf4 is preferably a C 1-20 divalent chain hydrocarbon group having a fluorine atom. Specific examples include groups represented by the formulas (X-1) to (X-8). Among these, X f4 is preferably a group represented by the formula (X-1) or (X-2).
  • R j4 examples include an acid labile group or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
  • R j4 is preferably a hydrogen atom, a t-butoxycarbonyl group or an alkoxy-substituted methyl group.
  • m is an integer of 1 to 3. Accordingly, 1 to 3 R j4 are introduced into the repeating unit (f-4). When m is 2 or 3, a plurality of X f4 may be bonded to the same carbon atom among the carbon atoms constituting R k4 or may be bonded to different carbon atoms.
  • repeating unit (f-4) include repeating units represented by the following general formulas (f4-1) to (f4-4).
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • the polymer (B) may contain only one type of repeating unit (2), or may contain two or more types.
  • the content of the repeating unit (2) is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, based on 100 mol% of the total repeating units contained in the polymer (B). More preferably, it is ⁇ 45 mol%. When the content ratio of the repeating unit (2) is within this range, it is possible to maintain a sufficient receding contact angle with respect to the immersion liquid and to sufficiently develop with an alkaline developer.
  • the repeating unit having an acid labile group is not particularly limited, and includes the repeating unit (3) described in “(1) Polymer (A)”.
  • a polymer (B) may contain only 1 type of repeating units (3), and may contain 2 or more types.
  • the content of the repeating unit (3) is preferably 10 to 90 mol%, more preferably 10 to 80 mol%, still more preferably based on 100 mol% of the total repeating units contained in the polymer (B). 20 to 70 mol%. When the content ratio of the repeating unit (3) is within this range, it is possible to maintain a sufficient receding contact angle with respect to the immersion liquid and to sufficiently develop with an alkaline developer.
  • the polymer (B) may contain a repeating unit other than the above repeating units (1) to (3) (hereinafter also referred to as “other repeating unit”).
  • the repeating unit (7) represented by the repeating unit (4), the repeating unit (6) and the following general formula (11) described in “(1) Polymer (A)” ( Hereinafter, it is also referred to as “repeat unit (7)”.
  • the content of the repeating unit (4) is preferably 5 to 70 mol%, more preferably 5 to 65 mol%, based on 100 mol% of the total repeating units contained in the polymer (B). It is more preferably from ⁇ 60 mol%, particularly preferably from 10 to 20 mol%. When the content ratio of the repeating unit (4) is within this range, developability as a resist and process margin such as exposure amount and focus can be maintained.
  • the content ratio of the repeating unit (6) is preferably 30 mol% or less, and more preferably 25 mol% or less with respect to 100 mol% of the total repeating units contained in the polymer (B). It can suppress that the top loss of a resist pattern arises because the content rate of a repeating unit (6) exists in this range. In addition, since the repeating unit (6) is an arbitrary component, it may not be included in the polymer (B).
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • X represents a single bond or a divalent linking group.
  • R C represents an optionally substituted carbon.
  • Rf is a monovalent chain hydrocarbon group having a carbon number of 1 to 30 having 1 to 10 fluorine atoms, or 1 to 10 Represents a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms and having one fluorine atom, wherein n is an integer of 1 to 3. When n is 2 or 3, a plurality of Rf are independent of each other.
  • the repeating unit (7) is preferably a repeating unit represented by the following general formula (11-1).
  • R 1 , X, Rf and n are defined as in the general formula (11).
  • R S represents —R P1 , —R P2 —O—R P1 , —R P2 —CO—R P1 , —R P2 —CO—OR P1 , —R P2 —O—CO—R P1 , —R P2 —OH, —R P2 —CN, or —R P2 —COOH
  • R P2 represents a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Represents a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. . It should be noted that some or all of the hydrogen atoms constituting these groups may be substituted with a fluorine atom.).
  • N S is an integer of 0-3.
  • repeating unit represented by the general formula (11-1) include a repeating unit represented by the following formula (11-1-1).
  • the content ratio of the repeating unit (7) is preferably 90 mol% or less, more preferably 75 mol% or less with respect to 100 mol% of the total repeating units contained in the polymer (B). It is preferable for the content ratio of the repeating unit (7) to be within this range since the shape of the resist pattern becomes good. In addition, since a repeating unit (7) is an arbitrary component, it does not need to be contained in a polymer (B).
  • Each polymer for example, using a polymerizable unsaturated monomer that gives each repeating unit described above, a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, If necessary, it can be prepared by polymerization in an appropriate solvent in the presence of a chain transfer agent.
  • a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, If necessary, it can be prepared by polymerization in an appropriate solvent in the presence of a chain transfer agent.
  • Examples of the solvent used for the polymerization include alkanes such as n-pentane and n-hexane; cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; aromatic hydrocarbons such as benzene and toluene; chlorobutane and bromo Halogenated hydrocarbons such as hexane; saturated carboxylic acid esters such as ethyl acetate and n-butyl acetate; ketones such as acetone and 2-butanone; ethers such as tetrahydrofuran and dimethoxyethane.
  • these solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the weight average molecular weight (hereinafter also referred to as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC) of each polymer is not particularly limited. However, it is preferably from 1,000 to 100,000, more preferably from 1,000 to 30,000, and still more preferably from 1,000 to 20,000. When Mw is within this range, both the heat resistance of the first resist layer and the developability of the alkali developing portion can be achieved.
  • the ratio (Mw / Mn) between the Mw of each polymer and the polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) by gel permeation chromatography (GPC) of each polymer is usually: 1 to 5, and preferably 1 to 3.
  • each polymer may contain a low molecular weight component derived from a monomer used in preparation.
  • the content of this low molecular weight component is preferably 0.1% by mass or less, more preferably 0.07% by mass or less, and still more preferably 100% by mass (in terms of solid content) of each polymer. It is 0.05 mass% or less.
  • the content ratio of the low molecular weight component is 0.1% by mass or less, it is possible to reduce the amount of the eluate in the immersion liquid such as water that is in contact during the immersion exposure.
  • foreign matters are less likely to occur in the resist during resist storage, and coating unevenness is less likely to occur during resist application, so that the occurrence of defects during resist pattern formation can be sufficiently suppressed. It is particularly preferred that each polymer does not contain a low molecular weight component.
  • low molecular weight component means a component having an Mw of 500 or less, and specifically includes a monomer, a dimer, a trimer, and an oligomer.
  • the low molecular weight component can be removed by, for example, chemical purification methods such as washing with water and liquid-liquid extraction, or a combination of these chemical purification methods and physical purification methods such as ultrafiltration and centrifugation.
  • the analysis can be performed by high performance liquid chromatography (HPLC).
  • each polymer has few impurities such as halogen and metal. This is because by reducing the impurities, it is possible to further improve the etching resistance of the first resist layer to be formed, the prevention of deterioration of the electrical characteristics of the device due to the impurities derived from the resist pattern, and the like.
  • Examples of the purification method for each polymer include chemical purification methods such as washing with water and liquid-liquid extraction, and combinations of these chemical purification methods with physical purification methods such as ultrafiltration and centrifugation.
  • Acid generator (C) An acid generator (C) means what generate
  • the first radiation-sensitive composition contains the acid generator (C)
  • the acid labile group possessed by can be dissociated (the protecting group is eliminated).
  • the alkali developing part becomes readily soluble in the alkali developer, and a resist pattern can be formed.
  • an acid generator (C) what contains the compound (henceforth "acid generator (1)") represented by General formula (12) is preferable.
  • the content of the acid generator (C) is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of ensuring the sensitivity and developability as a resist, preferably The amount is 0.5 to 10 parts by mass, and more preferably 5 to 10 parts by mass. When the content is within this range, sufficient transparency to radiation can be obtained without lowering the sensitivity and developability, and a rectangular resist pattern can be obtained.
  • Acid generator (1) is a compound represented by the general formula (12).
  • R 16 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, or a carbon number.
  • R 18 are independently of each other, a methyl group, an ethyl group, 3 carbon atoms, 1 Linear or branched alkyl group, a phenyl group, or a naphthyl group.
  • a divalent group having 2 to 10 carbon atoms containing sulfur cations two R 18 are bonded to each other
  • the phenyl group, naphthyl group, and divalent group having 2 to 10 carbon atoms may have a substituent
  • k represents an integer of 0 to 2
  • r represents 0 to 8 integer (preferably an integer of 0 to 2) shows the .
  • X - is an anion represented by the formula (12-1) to (12-4)).
  • R 19 represents a fluorine atom or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms.
  • q represents an integer of 1 to 10.
  • R 20 independently of each other is a methyl group, an ethyl group, or a carbon number substituted with a fluorine atom.
  • the acid generator (C) may contain one acid generator (1) alone or two or more kinds.
  • the acid generator (C) may contain a radiation-sensitive acid generator other than the acid generator (1) (hereinafter also referred to as “acid generator (2)”).
  • Acid generator (2) examples include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds.
  • an acid generator (C) may contain 1 type of acid generators (2) individually, and may contain 2 or more types.
  • the usage-ratio is 80 mass% or less normally with respect to 100 mass% of acid generators (C), Preferably it is 60 mass% or less.
  • solvent (D) examples include linear or branched ketones such as 2-butanone and 2-pentanone; cyclic ketones such as cyclopentanone, 3-methylcyclopentanone and cyclohexanone; propylene glycol monomethyl Propylene glycol monoalkyl ether acetates such as ether acetate and propylene glycol monoethyl ether acetate; 2-hydroxypropionates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; methyl 3-methoxypropionate, 3 -Alkyl 3-alkoxypropionates such as ethyl methoxypropionate and methyl 3-ethoxypropionate,
  • alcohols such as n-propyl alcohol and i-propyl alcohol
  • ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether
  • diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether
  • linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, ⁇ -butyrolactone and the like are preferable.
  • the first radiation-sensitive composition may contain one type of solvent (D) or two or more types.
  • the amount of the solvent (D) used is such that the total solid concentration of the first radiation-sensitive composition is usually 1 to 50% by mass, preferably 1 to 25% by mass.
  • the first radiation-sensitive composition may contain various additives such as an acid diffusion controller, an alicyclic additive, a surfactant, and a sensitizer as necessary.
  • the acid diffusion control agent is a component having an action of controlling a diffusion phenomenon of an acid generated from the acid generator (C) by exposure in the first resist layer and suppressing an undesirable chemical reaction in a non-exposed region.
  • the acid diffusion control agent is a component having an action of controlling a diffusion phenomenon of an acid generated from the acid generator (C) by exposure in the first resist layer and suppressing an undesirable chemical reaction in a non-exposed region.
  • the pattern shape of the first radiation-sensitive composition is improved.
  • the resolution as a resist is further improved, and it is possible to suppress changes in the line width of the resist pattern due to fluctuations in the holding time (PED) from exposure to post-exposure heat treatment, and an extremely excellent process stability. Things are obtained.
  • Examples of the acid diffusion controller include mono (cyclo) alkylamines, di (cyclo) alkylamines, tri (cyclo) alkylamines, substituted alkylanilines or derivatives thereof, ethylenediamine, N, N, N ′, N Amine compounds such as' -tetramethylethylenediamine and tetramethylenediamine; Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonylpyrrolidine, formamide, N Amide group-containing compounds such as methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone; urea, methylurea, 1,1 -Dimethyl Urea compounds such as rare, imidazoles; pyridines; other piperaz
  • An example of a photo-degradable base is an onium salt compound that decomposes upon exposure to deactivate acid diffusion controllability.
  • an onium salt compound include a sulfonium salt compound represented by the general formula (13) and an iodonium salt compound represented by the general formula (14).
  • R 21 to R 23 in the general formula (13) and R 24 to R 25 in the general formula (14) each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom.
  • Z ⁇ represents OH ⁇ , R 26 —COO ⁇ , R 26 —SO 3 — (wherein R 26 represents an alkyl group, an aryl group, or an alkaryl group).
  • R 27 is a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 12 carbon atoms, a methoxy group, an ethoxy group, or a linear group having 3 to 12 carbon atoms. Or a branched alkoxy group, provided that a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 12 carbon atoms may be substituted with a fluorine atom, and n is 0 to 2 Indicates an integer.
  • these acid diffusion control agents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the content of the acid diffusion control agent is preferably 0.001 to 15 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymer (A).
  • the amount is more preferably 05 to 5 parts by mass, and particularly preferably 0.5 to 1.5 parts by mass. When the content is within this range, the pattern shape and dimensional fidelity as a resist can be maintained without reducing the sensitivity as a resist.
  • Alicyclic additives An alicyclic additive is a component that exhibits an action of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.
  • alicyclic additives examples include polar group-substituted adamantanes; deoxycholic acid esters; lithocholic acid esters; alkyl carboxylic acid esters; 3- (2-hydroxy-2,2-bis (trifluoromethyl) Ethyl) tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodecane and the like. In addition, you may use these alicyclic additives individually by 1 type or in mixture of 2 or more types.
  • a surfactant is a component that exhibits an effect of improving coating properties, striation, developability, and the like.
  • surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol
  • nonionic surfactants such as distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
  • (Iv) Sensitizer The sensitizer absorbs radiation energy and transmits the energy to the acid generator (C), thereby increasing the amount of acid produced.
  • the sensitizer of the first radiation-sensitive composition It has the effect of improving the apparent sensitivity.
  • Sensitizers include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. In addition, these sensitizers may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the first radiation-sensitive composition may contain additives other than the additives described above (hereinafter also referred to as “other additives”).
  • other additives include a low-molecular alkali solubility controller having an acid-dissociable protecting group, an antihalation agent, a storage stabilizer, and an antifoaming agent.
  • a dye or a pigment by including a dye or a pigment, the latent image of the exposed portion can be visualized, and the influence of halation during exposure can be reduced.
  • substrate can be improved by containing an adhesion assistant.
  • the first radiation-sensitive composition can be prepared as a coating solution by dissolving each component in the solvent (D) and then filtering with a filter having a pore size of about 0.2 ⁇ m, and can be applied onto the substrate. it can.
  • the second radiation-sensitive composition used when forming the second resist layer is a polymer (a) that becomes alkali-soluble by the action of an acid (hereinafter also referred to as “polymer (a)”), And a solvent (b).
  • Polymer (a) is not particularly limited as long as it is an alkali-insoluble or hardly alkali-soluble polymer that becomes alkali-soluble by the action of an acid. Specifically, there is one containing the repeating unit (3).
  • the polymer (a) can contain a repeating unit represented by the general formula (16) (hereinafter also referred to as repeating unit (8)).
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 28 represents a single bond, a methylene group, a linear or branched alkanediyl having 2 to 6 carbon atoms. Or a monocyclic or polycyclic alicyclic alkanediyl group having 4 to 12 carbon atoms.
  • Preferable examples of the monomer giving the repeating unit (8) include (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester, (meth) Acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2 -Hydroxy-5-pentyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester, (meth) acrylic acid 2-((5 -(1 ', 1', 1'-trifluoro-2'-trifluoromethyl-2'-hydroxy) propyl) bicyclo [2.2.1] heptyl) ester, (meth) acrylic acid 3- ( 8- (1 ', 1', 1'-trifluoro-2'-trifluoromethyl-2'-
  • the polymer (a) may contain only one type of repeating unit (8) or may contain two or more types.
  • the polymer (a) may contain other repeating units in addition to the repeating unit (3) and the repeating unit (8).
  • the ratio of the repeating unit (3) contained in the polymer (a) is preferably 10 to 70 mol% with respect to the total of 100 mol% of the repeating units contained in the polymer (a), and is preferably 10 to 60 mol%. More preferably, it is more preferably 20 to 60 mol%. When the ratio of the repeating unit (3) is within this range, both the resolution and developability of the alkali developing part can be achieved.
  • the ratio of the repeating unit (8) contained in the polymer (a) is preferably 0 to 90 mol%, and preferably 30 to 80 mol% with respect to 100 mol% of the repeating units contained in the polymer (a). More preferred is 40 to 80 mol%.
  • the ratio of the repeating unit (3) is within this range, the resolution of the alkali developing portion can be maintained.
  • the proportion of other repeating units contained in the polymer (a) is preferably 50 mol% or less, preferably 40 mol% or less, with respect to 100 mol% in total of the repeating units contained in the polymer (a). More preferred.
  • another repeating unit is an arbitrary component, it does not need to be contained in a polymer (B).
  • the second radiation-sensitive composition may contain the polymer (a) alone or in combination of two or more.
  • the polymer (a) can be prepared in the same manner as the polymer (A) or the polymer (B), for example, using a polymerizable unsaturated monomer that gives each repeating unit.
  • the Mw of the polymer (a) is not particularly limited. However, it is preferably 1000 to 100,000, more preferably 1000 to 30000, and still more preferably 1000 to 20000. When the Mw of the polymer (a) is within this range, both the heat resistance of the second resist layer and the developability of the alkali developing part can be achieved.
  • the ratio (Mw / Mn) between Mw and Mn of the polymer (a) is usually 1 to 5, preferably 1 to 3.
  • the polymer (a) may contain a low molecular weight component derived from a monomer used in preparation.
  • the content ratio of the low molecular weight component is preferably 0.1% by mass or less, more preferably 0.07% by mass or less, with respect to 100% by mass (in terms of solid content) of the polymer (a). More preferably, it is 0.05 mass% or less.
  • the content ratio of the low molecular weight component is 0.1% by mass or less, it is possible to reduce the amount of the eluate in the immersion liquid such as water that has been contacted during the immersion exposure. Furthermore, foreign matters are not generated in the resist during resist storage, and coating unevenness does not occur during resist application, and the occurrence of defects during resist pattern formation can be sufficiently suppressed.
  • the polymer (a) particularly preferably does not contain a low molecular weight component.
  • the polymer (a) is preferably one having few impurities such as halogen and metal.
  • impurities such as halogen and metal.
  • Examples of the purification method of the polymer (a) include the same methods as described above.
  • the solvent (b) is not particularly limited. However, it is preferable to dissolve the polymer (a) but not the first resist pattern. Examples include linear or branched ketones, cyclic ketones, alkylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, and ⁇ -butyrolactone. it can. Among these, propylene glycol monomethyl ether acetate and cyclohexanone are preferable.
  • the amount of the solvent (b) used is such that the total solid concentration of the second radiation-sensitive composition is usually 1 to 50% by mass, preferably 1 to 25% by mass.
  • the second radiation-sensitive composition usually contains a radiation-sensitive acid generator.
  • a radiation sensitive acid generator the same thing as the acid generator (C) in the above-mentioned 1st radiation sensitive composition can be used.
  • the acid generator (C) contained in the first radiation-sensitive composition and the radiation-sensitive acid generator contained in the second radiation-sensitive composition may be the same or different. May be.
  • the content of the radiation sensitive acid generator is usually 0.1 to 20 parts by mass, preferably 100 to 20 parts by mass with respect to 100 parts by mass of the polymer (a), from the viewpoint of ensuring sensitivity and developability as a resist.
  • the amount is 0.5 to 10 parts by mass, and more preferably 5 to 10 parts by mass. When the content is within this range, transparency to radiation can be maintained without lowering sensitivity and developability, and a rectangular second resist pattern can be obtained.
  • the second radiation sensitive composition may contain an additive.
  • this additive the same thing as various additives, such as the acid diffusion control agent mentioned above in the 1st radiation sensitive composition, can be said.
  • the content is preferably 0.001 to 15 parts by mass with respect to 100 parts by mass of the polymer (a).
  • the content is more preferably 0.01 to 10 parts by mass, still more preferably 0.05 to 5 parts by mass, and particularly preferably 0.5 to 1.5 parts by mass.
  • the content is in this range, the pattern shape and dimensional fidelity as a resist can be maintained without reducing the sensitivity as a resist.
  • the second radiation-sensitive composition can be prepared as a coating solution by dissolving each component in the solvent (b) and then filtering with a filter having a pore size of about 0.2 ⁇ m, and can be applied on the substrate. it can.
  • the wafer stage position of the contact angle meter is adjusted, and the substrate is set on the adjusted stage.
  • water is injected into the needle, and the position of the needle is finely adjusted to an initial position where water droplets can be formed on the set substrate.
  • water is discharged from the needle to form a 25 ⁇ L water droplet on the substrate.
  • the needle is once withdrawn from the water droplet, and the needle is pulled down to the initial position again and placed in the water droplet.
  • a water droplet is sucked with a needle at a speed of 10 ⁇ L / min for 90 seconds, and at the same time, the contact angle between the liquid surface and the substrate is measured once per second (90 times in total).
  • the average value for the contact angle for 20 seconds from the time when the measured value of the contact angle was stabilized was calculated as the receding contact angle.
  • Line width variation The line width variation of the resist pattern on the substrate C was observed using a scanning electron microscope (trade name “CG-4000”, manufactured by Hitachi Keiki Co., Ltd.). The line width of each of the arbitrary five line portions of the resist pattern line portion of the evaluation substrate C was measured at 20 arbitrary points. The average value of the line widths (total 100 points) of any five line portions was defined as the average line width. The difference between the average line width after forming the first resist pattern and the average line width after double patterning (forming the second resist pattern) was taken as the fluctuation value of the line width variation. A measured line width variation value of less than 4 nm is evaluated as “ ⁇ (excellent)”, 4-7 nm is evaluated as “ ⁇ (good)”, and a value exceeding 7 nm is evaluated as “ ⁇ (defect). "
  • Preparation Example 1 Preparation of polymer (A-1)) First, 15 mol% of the compound (M-14), 35 mol% of the compound (M-13), 50 mol% of the compound (M-8) as monomers, and a polymerization initiator (dimethyl-2,2′-azobisisobutyrate) A monomer solution in which (MAIB)) was dissolved in 100 g of methyl ethyl ketone was prepared. The total amount of monomers at the time of preparation was adjusted to 50 g. In addition, mol% of each monomer represents mol% with respect to the total amount of the monomer, and the use ratio of the polymerization initiator was 2 mol% with respect to the total amount of the monomer and the polymerization initiator.
  • a polymerization initiator dimethyl-2,2′-azobisisobutyrate
  • methyl ethyl ketone was added to a 500 mL three-necked flask equipped with a thermometer and a dropping funnel, and purged with nitrogen for 30 minutes. Then, it heated so that it might become 80 degreeC, stirring the inside of a flask with a magnetic stirrer. Subsequently, the prepared monomer solution was dripped in the flask over 3 hours using the dropping funnel. After completion of dropping, the mixture was aged for 3 hours and then cooled to 30 ° C. or lower to obtain a polymer solution. Thereafter, the polymer solution was added to 1000 g of methanol and mixed. Then suction filtration was performed.
  • methyl ethyl ketone was added to a 500 mL three-necked flask equipped with a thermometer and a dropping funnel, and purged with nitrogen for 30 minutes. Then, it heated so that it might become 80 degreeC, stirring the inside of a flask with a magnetic stirrer. Subsequently, the prepared monomer solution was dripped in the flask over 3 hours using the dropping funnel. After completion of dropping, the mixture was aged for 3 hours and then cooled to 30 ° C. or lower to obtain a polymer solution. Thereafter, the polymer solution was added to 1000 g of methanol and mixed. Then suction filtration was performed.
  • polymer (B-1) This polymer (B-1) has an Mw of 5500 and an Mw / Mn of 1.5.
  • Example 1 Preparation of first radiation-sensitive composition
  • the coating liquid (1) which consists of a 1st radiation sensitive composition was prepared by filtering using a membrane filter with a hole diameter of 200 nm.
  • Examples 2 to 22 and Comparative Examples 1 to 5 Preparation of first radiation-sensitive composition
  • Each coating solution was prepared in the same manner as in Example 1 except that the formulation described in Table 3 was used.
  • the usage-amount of each component makes a total amount of a polymer (A), a polymer (B), and a polymer (F) 100 parts.
  • Acid generator (C-1) Triphenylsulfonium nonafluoro-n-butanesulfonate
  • Second radiation-sensitive composition 100 parts of the polymer (B-9) represented by the formula (B-9) as the polymer (a), 7.0 parts of triphenylsulfonium nonafluoro-n-butanesulfonate as the radiation sensitive acid generator, acid diffusion 2.64 parts of the compound (E-2) as an inhibitor (E) and 2014 parts of propylene glycol monomethyl ether acetate as a solvent (b) were added, and the respective components were mixed to obtain a homogeneous solution. Then, the coating liquid (28) which consists of a 2nd radiation sensitive composition was prepared by filtering using a membrane filter with a hole diameter of 200 nm.
  • Example 23 Formation of resist pattern
  • a 12-inch silicon wafer was spin-coated with a lower antireflection film (trade name “ARC66”, manufactured by Brewer Science) using a coater / developer (trade name “Lithius Pro-i”, manufactured by Tokyo Electron). Thereafter, PB (205 ° C., 60 seconds) was performed to form a coating film having a thickness of 77 nm.
  • the coating liquid (1) (first radiation-sensitive composition) prepared in Example 1 was spin-coated, After PB (130 ° C., 60 seconds), a first resist layer having a thickness of 90 nm was formed by cooling (23 ° C., 30 seconds).
  • the obtained first resist pattern of the evaluation substrate A was subjected to PDB (200 ° C., 60 seconds) on the hot plate of the SOD coating film forming apparatus to obtain an evaluation substrate B.
  • the substrate B for evaluation is spin-coated with the coating liquid (28) (second radiation sensitive composition) using the SOD coating film forming apparatus, PB (100 ° C., 60 seconds), and then cooled ( And a second resist layer having a thickness of 70 nm was formed.
  • the coating liquid (28) second radiation sensitive composition
  • PB 100 ° C., 60 seconds
  • a second resist layer having a thickness of 70 nm was formed.
  • exposure was performed using a line pattern mask in a state where pure water was disposed on the surface of the second resist layer under the optical conditions of NA: 1.30 and Dipole. .
  • PEB 105 ° C., 60 seconds
  • the coater / developer hot plate and cooling 23 ° C., 30 seconds
  • a 2.38% tetramethylammonium hydroxide aqueous solution was added with a GP nozzle of the developing cup.
  • Paddle development (10 seconds) was performed as a developer, and rinsed with ultrapure water.
  • an evaluation substrate C on which a second resist pattern having a 26 nm line / 104 nm pitch was formed was obtained.
  • the evaluation of the DP pattern of the evaluation substrate C was “good”, and the evaluation of the line width variation was “ ⁇ (excellent)”.
  • Examples 24-44 Each evaluation substrate C was obtained in the same manner as in Example 23 except that the conditions described in Table 4 were used. The evaluation results of the obtained evaluation substrates C are also shown in Table 4.
  • the first resist pattern was exposed using a mask for forming a 48 nm line / 96 nm pitch (48 nm 1 L / 1 S) and placing pure water on the surface of the first resist layer.
  • a contact hole pattern was formed by immersion exposure using a mask for forming a 48 nm line / 96 nm pitch (48 nm 1 L / 1 S) so as to be orthogonal to the surface.
  • Example 25 instead of PDB, UV irradiation (172 nm, 10 seconds) was applied to the first resist pattern of the obtained evaluation substrate A with a lamp (manufactured by Ushio Inc.) containing Xe gas. Then, an evaluation substrate C was obtained.
  • the DP pattern is good, and a pattern exceeding the wavelength limit is obtained without performing large line width fluctuations. Can be formed.
  • the DP pattern is evaluated. Was “defective”, the line width variation was “ ⁇ (defective)”, and the receding contact angle was 55 °. (Comparative Examples 6 and 7).
  • a pattern exceeding the wavelength limit can be formed satisfactorily and economically. Therefore, it can be used very suitably in the field of microfabrication represented by the manufacture of integrated circuit elements that are expected to become increasingly finer in the future.

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  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

La présente invention concerne une composition sensible aux rayonnements qui est utilisée dans l'étape 1 d'un procédé permettant de former un motif de photorésine. Ledit procédé comprend : (1) une étape permettant de former un premier motif de photorésine sur un substrat à l'aide d'une première composition sensible aux rayonnements ; (2) une étape permettant d'insolubiliser le premier motif de photorésine par rapport à une seconde composition sensible aux rayonnements ; et (3) une étape permettant d'utiliser la seconde composition sensible aux rayonnements afin de former un second motif de photorésine sur le substrat sur lequel le premier motif de photorésine a été formé. La composition sensible aux rayonnements contient : (A) un polymère contenant un motif récurrent qui comporte un groupe labile acide ; (B) un polymère contenant un motif récurrent qui comporte un atome de fluor et un motif récurrent qui comporte un groupe de réticulation ; (C) un générateur d'acide sensible aux rayonnements ; et (D) un solvant.
PCT/JP2010/069732 2009-11-30 2010-11-05 Composition sensible aux rayonnements et procédés de formation d'un motif de photorésine WO2011065207A1 (fr)

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JP2012088449A (ja) * 2010-10-18 2012-05-10 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物、レジストパターン形成方法
JP2013092590A (ja) * 2011-10-25 2013-05-16 Shin Etsu Chem Co Ltd ポジ型レジスト組成物及びパターン形成方法
JP2013156563A (ja) * 2012-01-31 2013-08-15 Fujifilm Corp 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置及び液晶表示装置
JP2013186450A (ja) * 2012-03-12 2013-09-19 Fujifilm Corp ポジ型感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機ｅｌ表示装置および液晶表示装置
JP2013190676A (ja) * 2012-03-14 2013-09-26 Tokyo Ohka Kogyo Co Ltd 溶剤現像ネガ型レジスト組成物、レジストパターン形成方法
WO2015046295A1 (fr) * 2013-09-25 2015-04-02 富士フイルム株式会社 Composition de résine photosensible, procédé de fabrication d'un film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage el organique
JP2015072455A (ja) * 2013-09-04 2015-04-16 Jsr株式会社 感放射線性樹脂組成物、重合体組成物、硬化膜、その形成方法、及び電子デバイス
JP2015114336A (ja) * 2013-12-06 2015-06-22 東京応化工業株式会社 溶剤現像ネガ型レジスト組成物、レジストパターン形成方法
JP2017027040A (ja) * 2015-07-24 2017-02-02 住友化学株式会社 レジスト組成物
WO2017086213A1 (fr) * 2015-11-17 2017-05-26 日産化学工業株式会社 Additif pour composition filmogène de sous-couche de résist et composition filmogène de sous-couche de résist contenant un tel additif
WO2018043371A1 (fr) * 2016-09-02 2018-03-08 住友化学株式会社 Composé polymère, film dans lequel le composé polymère est durci et dispositif électronique comprenant le film
WO2018052127A1 (fr) * 2016-09-15 2018-03-22 日産化学工業株式会社 Composition de formation de film de sous-couche de réserve
JP2020092274A (ja) * 2015-04-10 2020-06-11 東京エレクトロン株式会社 イメージ反転、誘導自己組織化、および選択的堆積を補助するための、サブ解像度開口部の使用
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WO2008149947A1 (fr) * 2007-06-05 2008-12-11 Fujifilm Corporation Composition de résine photosensible positive et procédé de formation d'un film durci à partir de celle-ci
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JP2013092590A (ja) * 2011-10-25 2013-05-16 Shin Etsu Chem Co Ltd ポジ型レジスト組成物及びパターン形成方法
JP2013156563A (ja) * 2012-01-31 2013-08-15 Fujifilm Corp 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置及び液晶表示装置
JP2013186450A (ja) * 2012-03-12 2013-09-19 Fujifilm Corp ポジ型感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機ｅｌ表示装置および液晶表示装置
KR20130105420A (ko) * 2012-03-12 2013-09-25 후지필름 가부시키가이샤 포지티브형 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 유기 ｅｌ 표시 장치, 및 액정 표시 장치
KR102095312B1 (ko) * 2012-03-12 2020-03-31 후지필름 가부시키가이샤 포지티브형 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 유기 ｅｌ 표시 장치, 및 액정 표시 장치
JP2013190676A (ja) * 2012-03-14 2013-09-26 Tokyo Ohka Kogyo Co Ltd 溶剤現像ネガ型レジスト組成物、レジストパターン形成方法
JP2015072455A (ja) * 2013-09-04 2015-04-16 Jsr株式会社 感放射線性樹脂組成物、重合体組成物、硬化膜、その形成方法、及び電子デバイス
KR101819625B1 (ko) 2013-09-25 2018-01-17 후지필름 가부시키가이샤 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 액정 표시 장치 및 유기 el 표시 장치
CN105917274A (zh) * 2013-09-25 2016-08-31 富士胶片株式会社 感光性树脂组合物、硬化膜的制造方法、硬化膜、液晶显示装置及有机el显示装置
WO2015046295A1 (fr) * 2013-09-25 2015-04-02 富士フイルム株式会社 Composition de résine photosensible, procédé de fabrication d'un film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage el organique
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JP7209429B2 (ja) 2015-04-10 2023-01-20 東京エレクトロン株式会社 イメージ反転、誘導自己組織化、および選択的堆積を補助するための、サブ解像度開口部の使用
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JP2017027040A (ja) * 2015-07-24 2017-02-02 住友化学株式会社 レジスト組成物
JPWO2017086213A1 (ja) * 2015-11-17 2018-09-06 日産化学株式会社 レジスト下層膜形成組成物用添加剤及び該添加剤を含むレジスト下層膜形成組成物
US10795261B2 (en) 2015-11-17 2020-10-06 Nissan Chemical Industries, Ltd. Additive for resist underlayer film-forming composition and resist underlayer film-forming composition containing the same
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JPWO2018043371A1 (ja) * 2016-09-02 2018-09-13 住友化学株式会社 高分子化合物、該高分子化合物を硬化した膜及び該膜を含む電子デバイス
US10676554B2 (en) 2016-09-02 2020-06-09 Sumitomo Chemical Company, Limited Polymer compound, film obtained by hardening this polymer compound and electronic device comprising this film
WO2018043371A1 (fr) * 2016-09-02 2018-03-08 住友化学株式会社 Composé polymère, film dans lequel le composé polymère est durci et dispositif électronique comprenant le film
WO2018052127A1 (fr) * 2016-09-15 2018-03-22 日産化学工業株式会社 Composition de formation de film de sous-couche de réserve
US11675270B2 (en) 2016-09-15 2023-06-13 Nissan Chemical Corporation Resist underlayer film-forming composition
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