CN116888539A - Pattern forming method and method for manufacturing electronic device - Google Patents
Pattern forming method and method for manufacturing electronic device Download PDFInfo
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- CN116888539A CN116888539A CN202280011183.XA CN202280011183A CN116888539A CN 116888539 A CN116888539 A CN 116888539A CN 202280011183 A CN202280011183 A CN 202280011183A CN 116888539 A CN116888539 A CN 116888539A
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Abstract
The present invention provides a pattern forming method and a pattern forming method capable of obtaining a pattern excellent in-plane uniformity of line width by a manufacturing method of an electronic device including the pattern forming method, the pattern forming method including: (1) A step of forming a film using a actinic ray-or radiation-sensitive resin composition containing a resin (A) which is decomposed by the action of an acid and has an increased polarity and a compound (B) which generates an acid by irradiation with actinic rays or radiation; (2) exposing the film; and (3) developing and/or rinsing the exposed film with an organic treatment liquid containing butyl acetate and a hydrocarbon having 11 or more carbon atoms, wherein the content of the hydrocarbon having 11 or more carbon atoms in the organic treatment liquid is 1 mass% or more and 35 mass% or less.
Description
Technical Field
The present invention relates to a pattern forming method and a manufacturing method of an electronic device. More specifically, the present invention relates to a pattern forming method and a method for manufacturing an electronic device which can be preferably used in an ultra-microlithography process such as a process for manufacturing ultra LSI (Large Scale Integration) and high-capacity microchip, a process for manufacturing a mold for nanoimprint, and a process for manufacturing a high-density information recording medium, and other photosensitive etching processes.
Background
Conventionally, in a process for manufacturing a semiconductor device such as an IC (Integrated Circuit ) or LSI, micromachining by photolithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, ultra-fine pattern formation in a submicron region or a quarter-micron region has been demanded. Accordingly, exposure wavelength tends to be shorter from g-ray to i-ray and further to KrF excimer laser, and exposure machines using ArF excimer laser having a wavelength of 193nm as a light source have been developed. As a technique for further improving the resolution, a so-called immersion method has been developed in which a space between a projection lens and a sample is filled with a liquid having a high refractive index (hereinafter, also referred to as "immersion liquid").
In addition to excimer lasers, lithography using Electron Beams (EB), X-rays, extreme ultraviolet rays (EUV: extreme Ultraviolet), and the like have been developed. Accordingly, chemically amplified resist compositions which are effective in sensing various types of radiation and have excellent sensitivity and resolution have been developed.
For example, patent document 1 describes a pattern formation method in which an resist film is developed or washed (rinsed) with an organic processing liquid having an oxidizing agent content within a specific range.
Patent document 2 describes a pattern formation method in which a resist film is formed using a negative-type chemically amplified resist composition that is negatively charged by a crosslinking reaction, and after exposure, development is performed using a developer containing an organic solvent that satisfies specific conditions.
Patent document 3 describes a pattern formation method in which a resist film containing a resin having an acid-decomposable repeating unit which is decomposed by the action of an acid to generate an acid having a pKa in a specific range is exposed to light and developed using a developer containing an organic solvent.
Technical literature of the prior art
Patent literature
Patent document 1: international publication No. 2016/104565
Patent document 2: japanese patent application laid-open No. 2011-065105
Patent document 3: international publication No. 2016/158711
Disclosure of Invention
Technical problem to be solved by the invention
As described in patent documents 1 to 3, it has been conventionally known to use an organic solvent for development or rinsing in a pattern forming method. However, as a result of the studies by the present inventors, it has been found that, in particular, there is room for improvement in the in-plane uniformity of the line width of the obtained pattern in the case of using a developer or rinse containing a conventional organic solvent for a resist film formed using a polarity-conversion type resist composition containing an acid-decomposable resin and a photoacid generator.
Accordingly, an object of the present invention is to provide a pattern forming method capable of obtaining a pattern excellent in-plane uniformity of line width, and a method for manufacturing an electronic device including the pattern forming method.
Means for solving the technical problems
The present inventors have found that the above problems can be solved by the following configuration.
[1]
A pattern forming method, comprising:
(1) A step of forming a film using a actinic ray-or radiation-sensitive resin composition containing a resin (A) which is decomposed by the action of an acid and has an increased polarity and a compound (B) which generates an acid by irradiation with actinic rays or radiation;
(2) Exposing the film; a kind of electronic device with high-pressure air-conditioning system
(3) A step of developing and rinsing the exposed film with an organic treatment liquid containing butyl acetate and a hydrocarbon having 11 or more carbon atoms,
the content of the hydrocarbon having 11 or more carbon atoms in the organic treatment liquid is 1 mass% or more and 35 mass% or less.
[2]
The pattern forming method according to [1], wherein,
the hydrocarbon having 11 or more carbon atoms is undecane.
[3]
The pattern forming method according to [1] or [2], wherein,
the resin (a) having an increased polarity by decomposition with the action of an acid contains at least one selected from the group consisting of a group in which a hydrogen atom of a carboxyl group is replaced with a releasing group released by the action of an acid, a group in which a hydrogen atom of an alcoholic hydroxyl group is replaced with a releasing group released by the action of an acid, and a group in which a hydrogen atom of a phenolic hydroxyl group is replaced with a releasing group released by the action of an acid.
[4]
The pattern forming method according to any one of [1] to [3], wherein,
the resin (a) having increased polarity by decomposition by the action of an acid has a repeating unit represented by the following general formula (AX).
[ chemical formula 1]
In the general formula (AX),
Xa 1 represents a hydrogen atom or an alkyl group.
Rx 1 ～Rx 3 Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
Rx 1 ～Rx 3 May be bonded to form a ring.
[5]
The pattern forming method according to any one of [1] to [4], wherein,
the resin (a) having increased polarity by decomposition with an acid has at least one ring group selected from a lactone group, a carbonate group, a sultone group and a hydroxyl group.
[6]
The pattern forming method according to any one of [1] to [5], wherein,
the resin (a) having increased polarity by decomposition by the action of an acid has a repeating unit represented by the following general formula (Y).
[ chemical formula 2]
In the general formula (Y), the components are as follows,
a represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.
L represents a single bond or a 2-valent linking group having an oxygen atom.
R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and when a plurality of R's are present, they may be the same or different. With a plurality of R, they may form a ring together with each other.
a represents an integer of 1 to 3.
b represents an integer of 0 to (5-a).
[7]
The pattern forming method according to any one of [1] to [6], wherein,
the above-mentioned compound (B) which generates an acid by irradiation with actinic rays or radiation has a cation represented by the following general formula (ZaI) or a cation represented by the following general formula (ZaII).
[ chemical formula 3]
R 204 -I + -R 205 (ZaII)
In the general formula (ZaI), R 201 、R 202 R is R 203 Each independently represents an organic group.
In the general formula (ZaII), R 204 R is R 205 Each independently represents an organic group.
[8]
The pattern forming method according to [7], wherein,
r in the above general formula (ZaI) 201 、R 202 R is R 203 At least one of them is aryl or R in the above formula (ZaII) 204 R is R 205 At least one of which is aryl.
[9]
The pattern forming method according to [7] or [8], wherein,
r in the above general formula (ZaI) 201 、R 202 R is R 203 At least one of them has an acid-decomposable group, or R in the above general formula (ZaII) 204 R is R 205 At least one of them has an acid-decomposable group.
[10]
The pattern forming method according to any one of [1] to [9], wherein,
the molecular weight of the acid generated by the compound (B) generating an acid upon irradiation with actinic rays or radiation is 250 or more.
[11]
The pattern forming method according to any one of [1] to [10], wherein,
The content of the compound (B) that generates an acid upon irradiation with actinic rays or radiation is 10 mass% or more with respect to the total solid content of the actinic-ray-or radiation-sensitive resin composition.
[12]
The pattern forming method according to any one of [1] to [11], wherein,
the actinic-ray-or radiation-sensitive resin composition contains 2 or more kinds of the compound (B) that generates an acid upon irradiation with actinic rays or radiation, or at least one kind of compound (B) selected from the following compounds (I) and (II) upon irradiation with actinic rays or radiation.
Compound (I):
is a compound having 1 or more of the following structural sites X and 1 or more of the following structural sites Y, and is a compound which generates an acid containing the following 1 st acid site derived from the following structural site X and the following 2 nd acid site derived from the following structural site Y by irradiation with actinic rays or radiation.
Structural part X: from anionic site A 1 - Cation site M 1 + Composition, and formed by irradiation of actinic rays or radiation 1 The structural part of the 1 st acid part
Structural part Y: from anionic site A 2 - Cation site M 2 + Composition, and formed by irradiation of actinic rays or radiation 2 The structural part of the 2 nd acid part
Wherein the compound (I) satisfies the following condition I.
Condition I: in the above compound (I), the above cation site M in the above structural site X 1 + And the cationic site M in the structural site Y 2 + Take the place of H + The resulting compound PI has: acid dissociation constant a1 derived from the cation site M in the structural site X 1 + Take the place of H + Made of HA 1 An acidic moiety represented; and an acid dissociation constant a2 derived from the cation site M in the structural site Y 2 + Take the place of H + Made of HA 2 An acid site represented by the formula (I), and the acid dissociation constant a2 is greater than the acid dissociation constantNumber a1.
Compound (II):
is a compound having 2 or more structural sites X and 1 or more structural sites Z described below, and is a compound which generates an acid containing 2 or more 1 st acid sites derived from the structural sites X and the structural sites Z by irradiation with actinic rays or radioactive rays.
Structural part Z: nonionic sites capable of neutralizing acids
[13]
A manufacturing method of an electronic device, comprising the pattern forming method of any one of [1] to [12 ].
Effects of the invention
According to the present invention, a pattern forming method capable of obtaining a pattern excellent in-plane uniformity of line width and a method for manufacturing an electronic device including the pattern forming method can be provided.
Detailed Description
The present invention will be described in detail below.
The constituent elements described below are described in terms of representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the labeling of groups (atomic groups) in the present specification, unless contrary to the gist of the present invention, unsubstituted and substituted labels are described to include groups having substituents in addition to groups having no substituents. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the term "organic group" means a group containing at least one carbon atom.
As a substituent, a substituent having a valence of 1 is preferable unless otherwise specified.
In the present specification, "actinic rays" or "radiation" means, for example, an open line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV: extreme Ultraviolet), X-rays, and electron beams (EB: electron Beam).
In the present specification, "light" means actinic rays or radiation.
In the present specification, unless otherwise specified, "exposure" includes not only exposure by an open line spectrum using a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays, X-rays, EUV light, and the like, but also drawing by a particle beam such as an electron beam and an ion beam.
In the present specification, "to" is used to indicate the meaning of including the numerical values described before and after the "to the" as the lower limit value and the upper limit value.
In the present specification, the bonding direction of the labeled 2-valent group is not limited unless otherwise specified. For example, when Y in the compound represented by the formula "X-Y-Z" is-COO-, Y may be-CO-O-, or-O-CO-. And the above-mentioned compound may be "X-CO-O-Z", or "X-O-CO-Z".
In the present specification, (meth) acrylate means acrylate and methacrylate, and (meth) acrylic acid means acrylic acid and methacrylic acid.
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersity (hereinafter, also referred to as "molecular weight distribution") (Mw/Mn) are defined as polystyrene conversion values by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10. Mu.L, column (column): TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 ℃, flow rate: 1.0 mL/min, detector: differential refractive index detector (Refractive Index Detector)) using a GPC (Gel Permeation Chromatography ) apparatus (HLC-8120 GPC manufactured by TOSOH CORPORATION).
In the present specification, the acid dissociation constant (pKa) represents the pKa in an aqueous solution, and specifically, is a value obtained by calculating a database based on a substituent constant of hamett (Hammett) and a known literature value using the software package 1 described below. The pKa values described in the present specification each represent a value obtained by calculation using the software package.
Software package 1: advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
The pKa can also be obtained by a molecular orbital algorithm. As a specific method, there may be mentioned a method of calculating H in an aqueous solution based on a thermodynamic cycle + A method for calculating the dissociation free energy. Concerning H + The method of calculating the dissociation free energy may be calculated by DFT (density functional method), for example, but other various methods have been reported in literature and the like, and are not limited thereto. In addition, there are a plurality of software capable of implementing DFT, for example, gaussian16.
As described above, in the present specification, pKa refers to a value obtained by calculating a value based on a database of substituent constants of hamite and well-known literature values using the software package 1, but when pKa cannot be calculated by this method, a value obtained by Gaussian16 based on DFT (density functional method) is adopted.
Further, as described above, in the present specification, pKa means "pKa in aqueous solution", but when pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" is used.
[ method of Forming Pattern ]
The pattern forming method of the present invention includes:
(1) A step of forming a film using a actinic ray-or radiation-sensitive resin composition containing a resin (A) which is decomposed by the action of an acid and has an increased polarity and a compound (B) which generates an acid by irradiation with actinic rays or radiation;
(2) Exposing the film; a kind of electronic device with high-pressure air-conditioning system
(3) A step of developing and rinsing the exposed film with an organic treatment liquid containing butyl acetate and a hydrocarbon having 11 or more carbon atoms, wherein,
the content of the hydrocarbon having 11 or more carbon atoms in the organic treatment liquid is 1 mass% or more and 35 mass% or less.
The details of the mechanism by which a pattern excellent in-plane uniformity of line width can be obtained by the pattern forming method of the present invention are not clear, but the present inventors speculate as follows.
An organic treatment liquid comprising butyl acetate and a hydrocarbon having 11 or more carbon atoms, wherein the content of the hydrocarbon having 11 or more carbon atoms is 1 to 35 mass% inclusive, has excellent affinity for a film formed of a actinic ray-or radiation-sensitive resin composition comprising a resin (A) having an increased polarity by decomposition by the action of an acid and a compound (B) generating an acid by irradiation with actinic rays or radiation. Therefore, it is considered that by at least one of development and rinsing with the organic processing liquid, the organic processing liquid uniformly wets and spreads over the entire wafer, and the in-plane uniformity of the line width is improved.
The steps of the above steps will be described in detail below.
< procedure (1) >
The step (1) is a step of forming a film using a actinic ray-or radiation-sensitive resin composition containing a resin (a) which is decomposed by the action of an acid and has an increased polarity, and a compound (B) which generates an acid by irradiation with an actinic ray or radiation.
The actinic-ray-or radiation-sensitive resin composition used in the step (1) is typically a resist composition, and hereinafter, the actinic-ray-or radiation-sensitive resin composition is also referred to as "resist composition". The film formed using the actinic-ray-or radiation-sensitive resin composition is typically a resist film, and hereinafter, the film formed using the actinic-ray-or radiation-sensitive resin composition is also referred to as a "resist film".
Details of the actinic-ray-sensitive or radiation-sensitive resin composition will be described later.
The step (1) is typically a step of forming a resist film on a substrate using the resist composition.
As a method for forming a resist film on a substrate using the resist composition, for example, a method of applying the resist composition to a substrate is mentioned.
In addition, the resist composition is preferably subjected to filter filtration as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon.
The resist composition can be coated on a substrate (e.g., silicon dioxide coating) used in the manufacture of, for example, integrated circuit elements by a suitable coating method such as a spin coater or coater. The coating method is preferably spin coating using a spin coater. The spin speed at the time of spin coating using a spin coater is preferably 1000 to 3000rpm (rotational 0ns per minute).
The substrate may be dried to form a resist film after the resist composition is applied. In addition, various base films (inorganic films, organic films, antireflection films) may be formed on the lower layer of the resist film as needed.
Examples of the drying method include a method of drying by heating. Heating can be performed by a device provided in a general exposure machine and/or development machine, or heating can be performed by a hot plate or the like. The heating temperature is preferably 80 to 150 ℃, more preferably 80 to 140 ℃, and still more preferably 80 to 130 ℃. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.
The thickness of the resist film is not particularly limited, but is preferably 10 to 120nm in view of forming a fine pattern with higher accuracy. In the case of EUV exposure, the thickness of the resist film is more preferably 10 to 65nm, and still more preferably 15 to 50nm. In the case of ArF immersion exposure, the thickness of the resist film is more preferably 10 to 120nm, and still more preferably 15 to 90nm.
In addition, a top coat layer may be formed on top of the resist film using the top coat composition.
It is preferable that the top coat composition can be further uniformly coated on the upper layer of the resist film without mixing with the resist film. The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method, and for example, the top coat layer can be formed based on the descriptions in paragraphs [0072] to [0082] in Japanese patent application laid-open No. 2014-059543.
For example, it is preferable to form a top coat layer containing an alkaline compound as described in japanese patent application laid-open No. 2013-61648 on a resist film. Specific examples of the basic compound that the topcoat layer can contain include basic compounds that the resist composition can contain.
Also, the top coat layer preferably further comprises a compound comprising at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
< procedure (2) >
The step (2) is a step of exposing the resist film to light.
As a method of exposure, a method of irradiating a formed resist film with actinic rays or radiation through a predetermined mask is exemplified.
Examples of the actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays and electron beams, preferably far ultraviolet light having a wavelength of 250nm or less, more preferably 220nm or less, particularly preferably 1 to 200nm, and specifically KrF excimer laser (248 nm), arF excimer laser (193 nm) and F 2 Excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams.
The baking (heating) is preferably performed before development after exposure. The response of the exposed portion is promoted by baking, and the sensitivity and pattern shape become more excellent.
The heating temperature is preferably 80 to 150 ℃, more preferably 80 to 140 ℃, and still more preferably 80 to 130 ℃.
The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and still more preferably 30 to 120 seconds.
The heating may be performed by a device provided in a general exposure machine and/or developing machine, or may be performed by a hot plate or the like.
This process is also called post exposure bake.
< procedure (3) >
The step (3) is a step of developing and/or rinsing the resist film exposed in the step (2) with an organic treatment liquid containing butyl acetate and a hydrocarbon having 11 or more carbon atoms. The content of the hydrocarbon having 11 or more carbon atoms in the organic treatment liquid is 1 mass% or more and 35 mass% or less.
The organic treatment liquid used in the step (3) contains butyl acetate and a hydrocarbon having 11 or more carbon atoms. The hydrocarbon having 11 or more carbon atoms is preferably an alkane, more preferably an alkane having 11 to 15 carbon atoms, still more preferably an alkane having 11 to 13 carbon atoms, particularly preferably undecane or dodecane, and most preferably undecane. In the case where a structural isomer exists such as undecane or dodecane, the hydrocarbon having 11 or more carbon atoms may contain the structural isomer.
The number of hydrocarbons having 11 or more carbon atoms contained in the organic treatment liquid may be 1 or 2 or more.
The content of hydrocarbons having 11 or more carbon atoms (the total amount when a plurality of hydrocarbons having 11 or more carbon atoms are contained) in the organic treatment liquid is 1 mass% or more and 35 mass% or less, preferably 5 mass% or more and 30 mass% or less, and more preferably 10 mass% or more and 25 mass% or less, based on 100 mass% of the entire organic treatment liquid.
The organic treatment liquid used in the step (3) contains butyl acetate (n-butyl acetate).
The content of butyl acetate in the organic treatment liquid is preferably 65 mass% or more and 99 mass% or less, more preferably 70 mass% or more and 95 mass% or less, and still more preferably 75 mass% or more and 90 mass% or less, based on 100 mass% of the entire organic treatment liquid.
The organic treatment liquid may contain other components in addition to butyl acetate and hydrocarbons having 11 or more carbon atoms. Examples of the other component include surfactants, antioxidants, and basic compounds. The content of the other component in the organic treatment liquid is preferably 0 mass% or more and 5 mass% or less, more preferably 0 mass% or more and 1 mass% or less, still more preferably 0 mass% or more and 0.5 mass% or less, and particularly preferably 0 mass% (i.e., no other component is contained) based on 100 mass% of the entire organic treatment liquid.
The step (3) is a step of at least one of developing and rinsing (cleaning) the exposed resist film in the step (2) using the organic processing liquid. In the step (3), development may be performed alone, rinsing may be performed alone, or development and rinsing may be performed.
Hereinafter, a case where development is performed in the step (3) (hereinafter, a step of developing using the organic-based processing liquid will be referred to as a step (3A)), and a case where rinsing is performed in the step (3) (hereinafter, a step of rinsing using the organic-based processing liquid will be referred to as a step (3B)), will be described.
The step (3) may be a step including only the step (3A), a step including only the step (3B), or a step including the steps (3A) and (3B). When the step (3) includes the step (3A) and the step (3B), the organic treatment liquid used as the developing solution in the step (3A) may be the same as or different from the organic treatment liquid used as the eluent in the step (3B).
A particularly preferred embodiment of the present invention is a method in which an organic treatment liquid containing butyl acetate and undecane and having a mass ratio of "butyl acetate/undecane" of "90/10" is used as a eluent.
[ procedure (3A) ]
In the step (3), a case of developing with the organic processing liquid (step (3A)) will be described. In the step (3A), the organic treatment liquid is used as a developer.
Examples of the developing method include: a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method); a method (spin immersion method) in which a developer is raised on the surface of a substrate by surface tension and left for a predetermined period of time to develop; a method of spraying a developer solution onto a substrate surface (spray method); and a method (dynamic dispense method, dynamic dispensing method) of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed.
After the development step, a step of stopping development while replacing with another solvent may be performed.
The development time is not particularly limited as long as the resin in the portion to be removed is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
The temperature of the developing solution is preferably 0 to 50 ℃, more preferably 15 to 35 ℃.
By performing the step (3A), a resist pattern (also simply referred to as "pattern") is formed.
Preferably, the rinsing is performed after the step (3A) is performed. The rinsing can be performed in the step (3B) described later, or can be performed using a rinsing liquid other than the organic treatment liquid.
The eluent other than the organic processing liquid is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The eluting solution other than the organic treatment solution preferably contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Even when the washing is performed using a washing solution other than the organic treatment solution, the washing method can be performed in the same manner as the washing method in the step (3B) described later.
[ procedure (3B) ]
In the step (3), a case of developing with the organic processing liquid (step (3B)) will be described. In the step (3B), the organic treatment liquid is used as a eluent.
The rinsing method is not particularly limited, and examples thereof include a method of continuously spraying a rinsing liquid onto a substrate rotated at a constant speed (spin coating method), a method of immersing the substrate in a bath filled with the rinsing liquid for a constant time (immersion method), and a method of spraying the rinsing liquid onto the surface of the substrate (spray coating method).
The development is preferably performed before the step (3B). The development can be performed in the step (3A) or using a developer other than the organic processing liquid.
As the developer other than the organic processing liquid, an organic developer is preferably used.
Even in the case of performing development using a developer other than the organic processing liquid, the development method can be performed in the same manner as the development method in the step (3A).
The organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
The organic solvent may be mixed in plural, or may be mixed with a solvent other than the above or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially no water.
The content of the organic solvent in the organic-based developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, relative to the total amount of the developer.
Also, the pattern forming method of the present invention may include a heating process (Post rake) after the rinsing process. The developer and the rinse remaining between the patterns and in the patterns can be removed by this step. Further, this step has an effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually carried out at 40 to 250 ℃ (preferably 90 to 200 ℃) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
Further, the etching process of the substrate may be performed using the formed pattern as a mask. That is, the pattern formed in the step (3) may be used as a mask, and the substrate (or the underlying film and the substrate) may be processed to form a pattern on the substrate.
The method of processing the substrate (or the underlayer film and the substrate) is not particularly limited, and a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in the step (3) as a mask is preferable. The dry etch is preferably an oxygen plasma etch.
The organic processing liquid, the resist composition, and other various materials (for example, a solvent, a developer, a rinse, an anti-reflective coating forming composition, a top coat forming composition, and the like) used in the pattern forming method of the present invention preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million: parts per million) or less, more preferably 10 mass ppb (parts per billion ) or less, further preferably 100 mass ppt (parts per trillion, parts per million) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit is not particularly limited, but is preferably 0 mass ppt or more. Examples of the metal impurities include Na, K, ca, fe, cu, mg, al, li, cr, ni, sn, ag, as, au, ba, cd, co, pb, ti, V, W and Zn.
Examples of the method for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph [0321] of International publication No. 2020/004306.
Examples of the method for reducing impurities such as metals contained in the respective materials include a method for selecting a raw material having a small metal content as a raw material constituting the respective materials, a method for filtering the raw material constituting the respective materials by a filter, and a method for distilling the raw material by lining the inside of the apparatus with teflon (registered trademark) or the like while suppressing contamination as much as possible.
In addition to the filter filtration, impurities can be removed by the adsorbent material, and the filter filtration and the adsorbent material can be used in combination. As the adsorbent, a known adsorbent can be used, and for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in the above-mentioned various materials, it is necessary to prevent the mixing of metal impurities in the manufacturing process. It is possible to confirm whether or not the metal impurities are sufficiently removed from the manufacturing apparatus by measuring the content of the metal component contained in the cleaning liquid used when cleaning the manufacturing apparatus. The content of the metal component contained in the used cleaning liquid is preferably 100 mass ppt or less, more preferably 10 mass ppt or less, and still more preferably 1 mass ppt or less. The lower limit is not particularly limited, but is preferably 0 mass ppt or more.
In order to prevent failures of chemical liquid piping and various components (filters, O-rings, hoses, etc.) caused by electrostatic discharge accompanied by electrification of static electricity, the organic treatment liquid such as a rinse liquid may be added with a conductive compound. The conductive compound is not particularly limited, and examples thereof include methanol. The amount to be added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable development characteristics or rinsing characteristics. The lower limit is not particularly limited, but is preferably 0.01 mass% or more.
As the chemical liquid piping, various piping coated with SUS (stainless steel) or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, or the like) subjected to antistatic treatment can be used, for example. Similarly, as for the filter and the O-ring, polyethylene, polypropylene, or a fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, or the like) subjected to antistatic treatment can be used.
[ photosensitive ray-or radiation-sensitive resin composition ]
The actinic-ray-sensitive or radiation-sensitive resin composition used in the present invention will be described.
The actinic-ray-or radiation-sensitive resin composition (also referred to as "resist composition") used in the present invention contains a resin (a) (also referred to as "acid-decomposable resin" or "resin (a)") that is decomposed by the action of an acid and has an increased polarity, and a compound (B) (also referred to as "photoacid generator" or "compound (B)") that generates an acid by irradiation with actinic rays or radiation.
The resist composition is preferably a negative resist composition. The resist composition is preferably an organic solvent developing resist composition.
The resist composition is typically a chemically amplified resist composition.
[ acid-decomposable resin (A)) ]
The resist composition contains a resin (a).
In the pattern forming method of the present invention, typically, when an organic-based developer is used as the developer, a negative pattern is preferably formed.
The resin (a) generally contains a group (also referred to as an "acid-decomposable group") whose polarity is increased by decomposition by the action of an acid, and preferably contains a repeating unit having an acid-decomposable group.
As the repeating unit having an acid-decomposable group, in addition to the following (repeating unit having an acid-decomposable group), it is preferable (repeating unit having an acid-decomposable group containing an unsaturated bond).
< recurring Unit having acid-decomposable group >
(repeating units having acid-decomposable groups)
The acid-decomposable group is preferably a group which is decomposed by the action of an acid to produce a polar group.
The acid-decomposable group preferably has a structure in which a polar group is protected by a release group released by the action of an acid. That is, the resin (a) preferably contains a repeating unit having a group that is decomposed by the action of an acid and generates a polar group. The resin having the repeating unit increases in polarity by the action of an acid, so that the solubility in an alkaline developer increases, and the solubility in an organic solvent decreases.
The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric acid group, sulfonamide group, sulfonylimino group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group and tris (alkylsulfonyl) methylene group, and alcoholic hydroxyl group.
The polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), or a sulfonic acid group.
Examples of the releasing group released by the action of an acid include groups represented by formulae (Y1) to (Y4).
Formula (Y1): -C (Rx) 1 )(Rx 2 )(Rx 3 )
Formula (Y2): -C (=o) OC (Rx 1 )(Rx 2 )(Rx 3 )
Formula (Y3): -C (R) 36 )(R 37 )(OR 38 )
Formula (Y4): c (Rn) (H) (Ar) A-5,
in the formula (Y1) and the formula (Y2), rx 1 ～Rx 3 Each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). In addition, when Rx 1 ～Rx 3 When all of (a) are alkyl groups (straight chain or branched), rx is preferable 1 ～Rx 3 At least 2 of which are methyl groups.
Of these, rx is preferred 1 ～Rx 3 Each independently represents a linear or branched alkyl group, more preferably Rx 1 ～Rx 3 Each independently represents a linear alkyl group.
Rx 1 ～Rx 3 Or 2 of them may be bonded to form a single ring or multiple rings.
As Rx 1 ～Rx 3 The alkyl group of (a) is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
As Rx 1 ～Rx 3 The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl.
As Rx 1 ～Rx 3 The aryl group of (a) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl.
As Rx 1 ～Rx 3 Alkenyl groups of (2) are preferably vinyl groups.
As Rx 1 ～Rx 3 The ring formed by bonding 2 of these are preferably cycloalkyl groups. As Rx 1 ～Rx 3 The cycloalkyl group bonded to 2 of the above groups is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl, more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
Rx 1 ～Rx 3 Of cycloalkyl groups formed by bonding, for example, 1 of methylene groups constituting the ring may be substituted with a group containing a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. Of these cycloalkyl groups, 1 or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinyl group (vinyl).
The group represented by the formula (Y1) or the formula (Y2) is preferably, for example, rx 1 Is methyl or ethyl, and Rx 2 With Rx 3 Bonding to form the cycloalkyl group.
When the resist composition is, for example, a resist composition for EUV exposure, rx is also preferable 1 ～Rx 3 Represented alkyl, cycloalkyl, alkenyl, aryl and Rx 1 ～Rx 3 The ring formed by bonding 2 of the above groups further has a fluorine atom or an iodine atom as a substituent.
In the formula (Y3), R 36 ～R 38 Each independently represents a hydrogen atom or a 1-valent organic group. R is R 37 And R is R 38 May bond to each other to form a ring. Examples of the 1-valent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R is R 36 Hydrogen atoms are also preferred.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a heteroatom such as a carbonyl group. For example, in the above alkyl group, cycloalkyl group, aryl group and aralkyl group, for example, 1 or more of methylene groups may be substituted with a group containing a heteroatom such as an oxygen atom and/or a heteroatom such as a carbonyl group.
And R is 38 Can be bonded to each other with another substituent of the main chain of the repeating unitAnd are combined to form a ring. R is R 38 The group bonded to another substituent of the main chain of the repeating unit is preferably an alkylene group such as a methylene group.
When the resist composition is, for example, a resist composition for EUV exposure, R is also preferably used 36 ～R 38 Represented 1-valent organic group and R 37 And R is R 38 The ring formed by bonding each other further has a fluorine atom or an iodine atom as a substituent.
The formula (Y3) is preferably a group represented by the following formula (Y3-1).
[ chemical formula 4]
Here, L 1 L and L 2 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining them (for example, a group formed by combining an alkyl group and an aryl group).
M represents a single bond or a 2-valent linking group.
Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group).
In the alkyl group and the cycloalkyl group, for example, 1 of the methylene groups may be substituted with a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.
In addition, L is preferable 1 L and L 2 One of which is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group with an aryl group.
Q, M and L 1 May be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).
L is preferable from the viewpoint of miniaturization of the pattern 2 Is a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl and norbornyl groups, and examples of the tertiary alkyl group include,examples thereof include t-butyl and adamantyl. In these modes, tg (glass transition temperature) and activation energy increase, so that film strength can be ensured and blurring can be suppressed.
When the resist composition is, for example, a resist composition for EUV exposure, L is also preferably used 1 L and L 2 The alkyl group, cycloalkyl group, aryl group, and a group formed by combining them further have a fluorine atom or an iodine atom as a substituent. Further, it is preferable that the alkyl group, cycloalkyl group, aryl group, and aralkyl group contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom (that is, for example, 1 methylene group in the alkyl group, cycloalkyl group, aryl group, and aralkyl group is substituted with a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group).
In the case where the resist composition is, for example, an EUV exposure resist composition, the heteroatom is preferably a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom, among an alkyl group which may contain a heteroatom represented by Q, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group and a combination thereof.
In the formula (Y4), ar represents an aromatic ring group. Rn represents alkyl, cycloalkyl or aryl. Rn and Ar may bond to each other to form a non-aromatic ring. Ar is preferably an aryl group.
When the resist composition is, for example, a resist composition for EUV exposure, it is also preferable that an aromatic ring group represented by Ar and alkyl, cycloalkyl, and aryl groups represented by Rn have fluorine atoms and iodine atoms as substituents.
From the viewpoint of excellent acid degradability of the repeating unit, it is also preferable that, when the non-aromatic ring is directly bonded to the polar group (or a residue thereof) in the protecting group for the polar group, a halogen atom such as a fluorine atom is not contained as a substituent in the ring member atom adjacent to the ring member atom directly bonded to the polar group (or a residue thereof) in the non-aromatic ring.
Further, the release group released by the action of an acid may also be a 2-cyclopentenyl group having a substituent (alkyl group or the like) such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (alkyl group or the like) such as a 1, 4-tetramethylcyclohexyl group.
The resin (a) preferably contains at least one selected from the group consisting of a group in which a hydrogen atom of a carboxyl group is replaced with a releasing group released by the action of an acid, a group in which a hydrogen atom of an alcoholic hydroxyl group is replaced with a releasing group released by the action of an acid, and a group in which a hydrogen atom of a phenolic hydroxyl group is replaced with a releasing group released by the action of an acid.
The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the formula (a).
[ chemical formula 5]
L 1 Represents a 2-valent linking group which may have a fluorine atom or an iodine atom, R 1 Represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, R 2 Represents a group which is detached by the action of an acid and may have a fluorine atom or an iodine atom. Wherein L is 1 、R 1 R is R 2 Having a fluorine atom or an iodine atom.
L 1 Represents a 2-valent linking group which may have a fluorine atom or an iodine atom. As the 2-valent linking group which may have a fluorine atom or an iodine atom, can be exemplified by-CO-, -O-; -S-, -SO 2 -, a hydrocarbon group which may have a fluorine atom or an iodine atom (for example, alkylene, cycloalkylene, alkenylene, arylene, etc.), and a plurality of them. Wherein, as L 1 preferably-CO-, arylene or alkylene having an-arylene-fluorine atom or iodine atom, more preferably-CO-or alkylene having-arylene-fluorine atom or iodine atom.
As the arylene group, a phenylene group is preferable.
The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
The total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and still more preferably 3 to 6.
R 1 Represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and still more preferably 1 to 3.
The alkyl group may contain a hetero atom such as an oxygen atom other than a halogen atom.
R 2 Represents a group which is detached by the action of an acid and may have a fluorine atom or an iodine atom. Examples of the releasing group which may have a fluorine atom or an iodine atom include releasing groups represented by the above formulas (Y1) to (Y4) and having a fluorine atom or an iodine atom.
The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the following general formula (AI).
[ chemical formula 6]
In the general formula (AI) as described above,
Xa 1 represents a hydrogen atom or an alkyl group.
T represents a single bond or a 2-valent linking group.
Rx 1 ～Rx 3 Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
Rx 1 ～Rx 3 May be bonded to form a ring.
From Xa 1 The alkyl group represented may be linear orMay be branched. The alkyl group may have a substituent. Examples of the alkyl group include methyl group and-CH group 2 -R 11 A group represented by the formula (I). R is R 11 Examples of the organic group which represents a halogen atom (fluorine atom or the like), a hydroxyl group or a 1-valent organic group include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. As Xa 1 Preferably a hydrogen atom, methyl, trifluoromethyl or hydroxymethyl group.
Examples of the 2-valent linking group for T include an alkylene group, an aromatic ring group, -COO-Rt-group and-O-Rt-group. Wherein Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or-COO-Rt-group, more preferably a single bond. When T represents a-COO-Rt-group, rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably-CH 2 -group, - (CH) 2 ) 2 -group or- (CH) 2 ) 3 -a radical.
Rx 1 ～Rx 3 The alkyl group of (2) may be linear or branched. The alkyl group may have a substituent. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.
Rx 1 ～Rx 3 The cycloalkyl group of (2) may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The cycloalkyl group may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl. In the cycloalkyl group, for example, 1 of the methylene groups constituting the ring may be substituted with a group containing a heteroatom such as an oxygen atom or a sulfur atom, a heteroatom such as a carbonyl group, or a vinylidene group. Of these cycloalkyl groups, 1 or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinyl group (vinyl).
Rx 1 ～Rx 3 The aryl group of (2) may beMonocyclic aryl groups, and also polycyclic aryl groups. The aryl group may have a substituent. The aryl group is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl.
Rx 1 ～Rx 3 The alkenyl group (c) may be linear or branched. The alkenyl group may have a substituent. The alkenyl group is preferably a vinyl group.
When Rx is 1 ～Rx 3 When the two groups are bonded to form a ring, the ring may be a single ring or multiple rings. The ring formed is preferably cycloalkyl. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Also, polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferable. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
Rx 1 ～Rx 3 Of cycloalkyl groups formed by bonding, for example, 1 of methylene groups constituting the ring may be substituted with a group containing a heteroatom such as an oxygen atom or a sulfur atom, a heteroatom such as a carbonyl group, or a vinylidene group. Of these cycloalkyl groups, 1 or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinyl group (vinyl).
When each of the above groups has a substituent, the substituent is not particularly limited, and examples thereof include an alkyl group (having 1 to 4 carbon atoms and the like), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms and the like), an alkylthio group (having 1 to 4 carbon atoms and the like), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms and the like). The number of carbon atoms in the substituent is preferably 8 or less.
The repeating unit represented by the general formula (AI) is preferably a repeating unit represented by the following general formula (AX).
[ chemical formula 7]
In the general formula (AX),
Xa 1 represents a hydrogen atom or an alkaneA base.
Rx 1 ～Rx 3 Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
Rx 1 ～Rx 3 May be bonded to form a ring.
Xa in the general formula (AX) 1 Represents Xa in the general formula (AI) 1 The meaning is the same, and specific examples and preferred ranges are also the same.
Rx in the general formula (AX) 1 ～Rx 3 Represents Rx in the general formula (AI) 1 ～Rx 3 The meaning is the same, and specific examples and preferred ranges are also the same.
The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the following general formula (AX 2).
[ chemical formula 8]
In the general formula (AX 2),
Xa 1 represents a hydrogen atom or an alkyl group.
Rx 1 ～Rx 3 Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
Rx 1 ～Rx 3 May be bonded to form a ring.
Ar represents a 2-valent aromatic hydrocarbon group.
Xa in the general formula (AX 2) 1 Represents Xa in the general formula (AI) 1 The meaning is the same, and specific examples and preferred ranges are also the same.
Rx in the general formula (AX 2) 1 ～Rx 3 Represents Rx in the general formula (AI) 1 ～Rx 3 The meaning is the same, and specific examples and preferred ranges are also the same.
Ar in the general formula (AX 2) is preferably an arylene group, more preferably an arylene group having 6 to 20 carbon atoms, still more preferably an arylene group having 6 to 10 carbon atoms, and particularly preferably a phenylene group. Ar may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and is preferably a group having 8 or less carbon atoms.
When the resin (a) contains a group in which a hydrogen atom of a phenolic hydroxyl group is substituted with a releasing group released by the action of an acid, the resin (a) preferably contains a repeating unit having a structure in which a hydrogen atom in a phenolic hydroxyl group is protected by groups represented by formulae (Y1) to (Y4).
The repeating unit of the group including a hydrogen atom of the phenolic hydroxyl group substituted with a releasing group released by the action of an acid is preferably a repeating unit represented by the following general formula (AII).
[ chemical formula 9]
In the general formula (AII),
R 61 、R 62 r is R 63 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is 62 Can be combined with Ar 6 Bonding to form a ring, R at this time 62 Represents a single bond or an alkylene group.
X 6 Represents a single bond, -COO-or-CONR 64 -。R 64 Represents a hydrogen atom or an alkyl group.
L 6 Represents a single bond or an alkylene group.
Ar 6 An aromatic hydrocarbon group having a valence of (n+1), when it is combined with R 62 When bonded to form a ring, an (n+2) -valent aromatic hydrocarbon group is represented.
In the case where n.gtoreq.2, Y 2 Each independently represents a hydrogen atom or a group which is detached by the action of an acid. Wherein Y is 2 Represents a group that is detached by the action of an acid.
As Y 2 The groups to be released by the action of the acid are preferably groups represented by the above formulas (Y1) to (Y4).
n represents an integer of 1 to 4.
Each of the above-mentioned groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like, and a group having 8 or less carbon atoms is preferable.
The content of the repeating unit having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, with respect to all the repeating units in the resin (a). The upper limit of the amount is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all the repeating units in the resin (a).
Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, xa1 represents any one of H, CH, CF3 and CH2OH, and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.
[ chemical formula 10]
[ chemical formula 11]
[ chemical formula 12]
[ chemical formula 13]
/>
[ chemical formula 14]
[ chemical formula 15]
/>
(repeating units having an acid-decomposable group containing an unsaturated bond)
The resin (a) may contain a repeating unit having an acid-decomposable group containing an unsaturated bond.
The repeating unit having an acid-decomposable group containing an unsaturated bond is preferably a repeating unit represented by the formula (B).
Formula (B):
[ chemical formula 16]
In the formula (B), the amino acid sequence of the formula (B),
xb represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.
L represents a single bond or a 2-valent linking group which may have a substituent.
Ry 1 ～Ry 3 Each independently represents a linear, branched alkyl group, a monocyclic, polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, a monocyclic or polycyclic aryl group. Wherein Ry 1 ～Ry 3 Represents alkenyl, alkynyl, monocyclic or polycyclic cycloalkenyl or monocyclic or polycyclic aryl.
Ry 1 ～Ry 3 May be bonded to form a single ring or multiple rings (a cycloalkyl group, a cycloalkenyl group, etc. of a single ring or multiple rings).
Examples of the alkyl group which may have a substituent(s) and is represented by Xb include a methyl group and a group represented by-CH 2 -R 11 A group represented by the formula (I). R is R 11 Examples of the organic group which represents a halogen atom (fluorine atom or the like), a hydroxyl group or a 1-valent organic group include halogen atoms which may be takenSubstituted alkyl groups having 5 or less carbon atoms, acyl groups having 5 or less carbon atoms in which a halogen atom may be substituted, and alkoxy groups having 5 or less carbon atoms in which a halogen atom may be substituted, preferably alkyl groups having 3 or less carbon atoms, more preferably methyl groups. As Xb, a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is preferable.
As the 2-valent linking group of L, examples thereof include a-Rt-group, -CO-group, -COO-Rt-group-COO-Rt-CO-yl, -Rt-CO-yl and-O-Rt-yl. Wherein Rt represents an alkylene group, a cycloalkylene group or an aromatic ring group, preferably an aromatic ring group.
As a result of the fact that as a result of the L, preferably-Rt-group, -CO-group, -COO-Rt-CO-group or-Rt-CO-group. Rt may have a substituent such as a halogen atom, a hydroxyl group, an alkoxy group, or the like. Aromatic groups are preferred.
As Ry 1 ～Ry 3 The alkyl group of (a) is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
As Ry 1 ～Ry 3 Preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl.
As Ry 1 ～Ry 3 The aryl group of (a) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl.
As Ry 1 ～Ry 3 Alkenyl groups of (2) are preferably vinyl groups.
As Ry 1 ～Ry 3 Preferably an ethynyl group.
As Ry 1 ～Ry 3 The cycloalkenyl group (c) is preferably a structure in which a double bond is contained in a part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.
As Ry 1 ～Ry 3 Cycloalkyl groups bonded to 2 of the above groups are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl. Also, polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferable. Of these, a monocyclic ring having 5 to 6 carbon atoms is more preferable Cycloalkyl groups of (a).
Ry 1 ～Ry 3 Of cycloalkyl or cycloalkenyl groups formed by bonding 2 of the above groups, for example, 1 of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom, a carbonyl group, -SO 2 -group, -SO 3 -a group of heteroatoms such as a group or a vinylidene group or a combination thereof. In these cycloalkyl groups and cycloalkenyl groups, 1 or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be substituted with a vinyl group (vinyl group).
The repeating unit represented by the formula (B) is preferably, for example, ry 1 Is methyl, ethyl, vinyl, allyl, aryl, ry 2 With Ry 3 And a cycloalkyl group and a cycloalkenyl group bonded to each other.
When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.
As the repeating unit represented by the formula (B), an acid-decomposable tertiary (meth) acrylic acid ester repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a repeating unit of a-CO-group), an acid-decomposable tertiary hydroxystyrene alkyl ether repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a repeating unit of a phenyl group), an acid-decomposable tertiary styrene carboxylic acid ester repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a repeating unit of a-Rt-CO-group (Rt is an aromatic group) are preferable.
The content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, with respect to all the repeating units in the resin (a). The upper limit of the amount is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total amount of the repeating units in the resin (a).
Specific examples of the repeating unit having an acid-decomposable group containing an unsaturated bond are shown below, but the present invention is not limited thereto. In addition, in the formula, the catalyst,Xb、L 1 ar represents any one of the substituents and the linking groups described above, R represents an aromatic group, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR '"or-COOR'" wherein R '"is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a substituent such as a carboxyl group, R' represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, a monocyclic or polycyclic aryl group, and Q represents a hetero atom such as an oxygen atom, a carbonyl group or-SO group 2 -group, -SO 3 A group having a hetero atom such as a group, or a vinylidene group or a combination thereof, and l, n and m represent an integer of 0 or more.
[ chemical formula 17]
[ chemical formula 18]
[ chemical formula 19]
[ chemical formula 20]
(repeating units having polar groups)
The resin (a) may also contain a repeating unit having a polar group.
Examples of the polar group include a hydroxyl group, a cyano group, and a carboxyl group.
The repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. The repeating unit having a polar group preferably does not have an acid-decomposable group. As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group or a norbornyl group is preferable.
Specific examples of the monomer corresponding to the repeating unit having a polar group are given below, but the present invention is not limited to these specific examples. The following specific examples are described as methacrylate compounds, but may be acrylate compounds.
[ chemical formula 21]
Further, specific examples of the repeating unit having a polar group include structural units disclosed in paragraphs 0415 to 0433 of U.S. patent application publication 2016/007067.
The resin (a) may contain only 1 kind of repeating unit having a polar group, or may contain 2 or more kinds of repeating units together.
When the resin (a) contains a repeating unit having a polar group, the content thereof is preferably 0.1 to 40 mol%, more preferably 1 to 30 mol%, with respect to all the repeating units in the resin (a).
The resin (a) may contain a repeating unit other than the repeating unit.
For example, the resin (a) may also contain at least one repeating unit selected from the following group a and/or at least one repeating unit selected from the following group B.
Group A: the group comprising the following repeating units (20) to (29).
(20) Repeating units having an acid group as described later
(21) Repeating units having fluorine or iodine atoms, to be described later
(22) Repeating units having lactone, sultone or carbonate groups as described later
(23) Repeating units having photoacid-generating groups described later
(24) The repeating unit represented by the formula (V-1) or the following formula (V-2)
(25) The repeating unit represented by the formula (A)
(26) The repeating unit represented by the formula (B)
(27) The repeating unit represented by the formula (C)
(28) The repeating unit represented by the formula (D)
(29) The repeating unit represented by the formula (E)
Group B: the group comprising the following repeating units (30) to (32).
(30) The repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group and an alkali-soluble group
(31) Repeating units having alicyclic hydrocarbon structure and exhibiting no acid decomposition property, which will be described later
(32) The repeating unit represented by the formula (III) having no hydroxyl group or cyano group
The resin (a) preferably has an acid group, and as described later, preferably contains a repeating unit having an acid group. The definition of the acid group will be described in the latter stage together with a preferred embodiment of the repeating unit having the acid group. When the resin (a) has an acid group, the resin (a) is more excellent in the interactivity with the acid generated from the compound (B). As a result, the cross-sectional shape of the pattern formed can be made more rectangular while suppressing the diffusion of the acid.
When a resist composition is used as the actinic-ray-or radiation-sensitive resin composition for EUV, the resin (a) preferably has at least one repeating unit selected from the above group a.
When the resist composition is used as a actinic-ray-or radiation-sensitive resin composition for EUV, the resin CA) preferably contains at least one of fluorine atoms and iodine atoms. When the resin (a) contains both fluorine atoms and iodine atoms, the resin (a) may have 1 repeating unit containing both fluorine atoms and iodine atoms, and the resin (a) may contain 2 repeating units containing fluorine atoms and repeating units containing iodine atoms.
When the resist composition is used as a actinic-ray-or radiation-sensitive resin composition for EUV, the resin (a) preferably further contains a repeating unit having an aromatic group.
When a resist composition is used as the actinic-ray-or radiation-sensitive resin composition for ArF, the resin (a) preferably has at least one repeating unit selected from the above group B.
In addition, when the resist composition is used as a actinic-ray-or radiation-sensitive resin composition for ArF, the resin (a) preferably does not contain any one of fluorine atoms and silicon atoms.
When the resist composition is used as a actinic-ray-or radiation-sensitive resin composition for ArF, the resin (a) preferably has no aromatic group.
The resin (a) preferably has at least one ring group selected from a lactone group, a carbonate group, a sultone group and a hydroxyl group. The lactone group, carbonate group or sultone group will be described later. The cyclic group having a hydroxyl group is preferably an alicyclic group having a hydroxyl group, and specific examples thereof include those exemplified as repeating units having an acid group described later.
< repeating units having an acid group >
The resin (a) preferably contains a repeating unit having an acid group.
The acid group is preferably an acid group having a pKa of 13 or less. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and further preferably 5 to 10, as described above.
When the resin (A) has an acid group having a pKa of 13 or less, the content of the acid group in the resin (A) is not particularly limited, but is usually 0.2 to 6.0mmol/g. Among them, the concentration is preferably 0.8 to 6.0mmol/g, more preferably 1.2 to 5.0mmol/g, still more preferably 1.6 to 4.0mmol/g. If the content of the acid group is within the above range, development proceeds well, and the formed pattern is excellent in shape and resolution.
The acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
In the hexafluoroisopropanol group, L or more (preferably 1 to 2) fluorine atoms may be substituted with groups other than fluorine atoms (e.g., alkoxycarbonyl groups). As the acid group, preference is also given to-C (CF) 3 )(OH)-CF 2 -. In addition, 1 or more of the fluorine atoms may be substituted with groups other than fluorine atoms to form a group containing-C (CF) 3 )(OH)-CF 2 -a ring.
The repeating unit having an acid group is preferably a repeating unit different from the repeating unit including: a repeating unit having a structure in which a polar group is protected by a release group released by the action of the acid; and a repeating unit having a lactone group, a sultone group or a carbonate group, which will be described later.
The repeating unit having an acid group may have a fluorine atom or an iodine atom.
The following repeating units are exemplified as the repeating units having an acid group.
[ chemical formula 22]
The repeating unit having an acid group is preferably a repeating unit represented by the following formula (Y).
The resin (a) preferably has a repeating unit represented by the following general formula (Y).
[ chemical formula 23]
In the general formula (Y), the components are as follows,
a represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.
L represents a single bond or a 2-valent linking group having an oxygen atom.
R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and when a plurality of R's are present, they may be the same or different. With a plurality of R, they may form a ring together with each other. R is preferably a hydrogen atom.
a represents an integer of 1 to 3.
b represents an integer of 0 to (5-a).
R in the formula (Y) is preferably a hydrogen atom. L is preferably a single bond.
The repeating unit having an acid group is exemplified below. Wherein a represents 1 or 2.
[ chemical formula 24]
[ chemical formula 25]
[ chemical formula 26]
/>
Among the repeating units, the repeating units described below are preferable. Wherein R represents a hydrogen atom or a methyl group, and a represents 2 or 3.
[ chemical formula 27]
[ chemical formula 28]
The content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, with respect to all the repeating units in the resin (a). The upper limit of the amount is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on the total amount of the repeating units in the resin (a).
< repeating units having fluorine atom, bromine atom or iodine atom >
Unlike the above-mentioned < repeating unit having an acid-decomposable group > and < repeating unit having an acid group >, the resin (a) may contain a repeating unit having a fluorine atom, a bromine atom or an iodine atom. The term "repeating unit having a fluorine atom, a bromine atom or an iodine atom" herein is preferably different from other types of repeating units belonging to group a, such as the following term "repeating unit having a lactone group, a sultone group or a carbonate group", and the term "repeating unit having a photoacid generator group".
The repeating unit having a fluorine atom, a bromine atom or an iodine atom is preferably a repeating unit represented by the formula (C).
[ chemical formula 29]
L 5 Represents a single bond or an ester group.
R 9 Represents a hydrogen atom or an alkyl group which may have a fluorine atom, a bromine atom or an iodine atom.
R 10 Represents a hydrogen atom, an alkyl group which may have a fluorine atom, a bromine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom, a bromine atom or an iodine atom, an aryl group which may have a fluorine atom, a bromine atom or an iodine atom, or a combination thereof.
The repeating unit having a fluorine atom or an iodine atom is exemplified below.
[ chemical formula 30]
The content of the repeating unit having a fluorine atom, a bromine atom or an iodine atom is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, with respect to all the repeating units in the resin (a). The upper limit of the amount is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on the total amount of the repeating units in the resin (a).
In addition, as described above, since the repeating unit having a fluorine atom, a bromine atom or an iodine atom contains no repeating unit having an acid-decomposable group and no repeating unit having an acid group, the content of the repeating unit having a fluorine atom, a bromine atom or an iodine atom described above also means the content of the repeating unit having a fluorine atom, a bromine atom or an iodine atom other than the repeating unit having an acid-decomposable group and the repeating unit having an acid group.
The total content of repeating units containing at least one of fluorine atoms, bromine atoms and iodine atoms in the repeating units of the resin (a) is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and particularly preferably 40 mol% or more, with respect to all the repeating units of the resin (a). The upper limit is not particularly limited, and is, for example, 100 mol% or less with respect to all the repeating units of the resin (a).
Examples of the repeating unit containing at least one of a fluorine atom, a bromine atom and an iodine atom include a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid-decomposable group, a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid group, and a repeating unit having a fluorine atom, a bromine atom or an iodine atom.
< recurring Unit having at least one group selected from the group consisting of lactone group, sultone group, carbonate group, hydroxyl group, cyano group and alkali-soluble group >
The resin (a) may contain a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
First, a description will be given of a repeating unit having at least one selected from a lactone group, a sultone group and a carbonate group (hereinafter, also collectively referred to as "a repeating unit having a lactone group, a sultone group or a carbonate group").
The repeating unit having a lactone group, a sultone group or a carbonate group preferably does not have an acid group such as a hydroxyl group or a hexafluoropropanol group.
The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. Of these, a structure in which another ring structure is condensed on a 5-to 7-membered ring lactone structure in the form of a double ring structure or a spiro ring structure, or a structure in which another ring structure is condensed on a 5-to 7-membered ring sultone structure in the form of a double ring structure or a spiro ring structure is more preferable.
The resin (a) preferably contains a repeating unit having a lactone group or a sultone group, wherein 1 or more hydrogen atoms are extracted from a ring member atom of a lactone structure represented by any one of the following formulas (LC 1-1) to (LC 1-21) or a sultone structure represented by any one of the following formulas (SL 1-1) to (SL 1-3).
Also, the lactone group or sultone group may be directly bonded to the main chain. For example, the ring member atom of the lactone group or the sultone group may constitute the main chain of the resin (a).
[ chemical formula 31]
The lactone structure or sultone structure moiety may have a substituent (Rb) 2 ). As a preferred substituent (Rb) 2 ) Examples thereof include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb are present 2 May be different and there are a plurality of Rb 2 May bond to each other to form a ring.
Examples of the repeating unit having a group containing a lactone structure represented by any one of formulas (LC 1-1) to (LC 1-21) or a sultone structure represented by any one of formulas (SL 1-1) to (SL 1-3) include repeating units represented by the following formula (AI).
[ chemical formula 32]
In the formula (AI), rb 0 Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.
As Rb 0 Preferred substituents which may be included in the alkyl group of (a) include hydroxyl groups and halogen atoms.
As Rb 0 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb (Rb) 0 Preferably a hydrogen atom or a methyl group.
Ab represents a single bond, an alkylene group, a 2-valent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a 2-valent group formed by combining them. Of these, preferred is a single bond or a bond consisting of-Ab 1 -CO 2 -a linker represented. Ab (Ab) 1 The alkylene group is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group in which 1 hydrogen atom is extracted from the ring member atom of the lactone structure represented by any one of formulas (LC 1-1) to (LC 1-21), or a group in which 1 hydrogen atom is extracted from the ring member atom of the sultone structure represented by any one of formulas (SL 1-1) to (SL 1-3).
When an optical isomer exists in a repeating unit having a lactone group or a sultone group, any optical isomer may be used. Further, 1 kind of optical isomer may be used alone, or a plurality of kinds of optical isomers may be used in combination. When 1 optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
The carbonate group is preferably a cyclic carbonate group.
The repeating unit having a cyclic carbonate group is preferably a repeating unit represented by the following formula (A-1).
[ chemical formula 33]
In the formula (A-1), R A 1 Represents a hydrogen atom, a halogen atom or a 1-valent organic group (preferably a methyl group).
n represents an integer of 0 or more.
R A 2 Represents a substituent. When n is 2 or more, there are a plurality of R A 2 The two may be the same or different.
A represents a single bond or a 2-valent linking group. The above-mentioned 2-valent linking group is preferably an alkylene group, a 2-valent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a 2-valent group formed by combining them.
Z represents an atomic group forming a single ring or multiple rings together with the group represented by-O-CO-O-in the formula.
The repeating unit having a lactone group, a sultone group or a carbonate group is exemplified below.
[ chemical formula 34]
(wherein Rx represents H, CH) 3 、CH 2 OH or CF 3 )
[ chemical formula 35]
(wherein Rx represents H, CH) 3 、CH 2 OH or CF 3 )
[ chemical formula 36]
(wherein Rx represents H, CH) 3 、CH 2 OH or CF 3 )
Next, a repeating unit having a hydroxyl group or a cyano group will be described.
The resin (a) may contain a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and the developer affinity.
The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
The repeating unit having a hydroxyl group or a cyano group preferably has no acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units described in paragraphs [0081] to [0084] of JP-A-2014-98921.
Next, a repeating unit having an alkali-soluble group will be described.
The resin (a) may also contain a repeating unit having an alkali-soluble group.
Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol having an electron withdrawing group substituted at the α -position (for example, hexafluoroisopropanol group), and preferably a carboxyl group. By making the resin (a) contain a repeating unit having an alkali-soluble group, resolution in contact hole use is improved. Examples of the repeating unit having an alkali-soluble group include repeating units described in paragraphs [0085] and [0086] of JP-A2014-98921.
The content of the repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group and an alkali-soluble group is preferably 1 mol% or more, more preferably 10 mol% or more, with respect to all the repeating units in the resin (a). The upper limit of the amount is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all the repeating units in the resin (a).
< repeat Unit having photoacid-generating group >
The resin (a) may contain a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid generating group") as a repeating unit other than the above.
In this case, the repeating unit having the photoacid generator group can be considered to correspond to the photoacid generator (B) described above.
Examples of such a repeating unit include a repeating unit represented by the following formula (4).
[ chemical formula 37]
R 41 Represents a hydrogen atom or a methyl group. L (L) 41 Represents a single bond or a 2-valent linking group. L (L) 42 Represents a 2-valent linking group. R is R 40 The structural site is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain.
The following examples illustrate repeating units having photoacid generating groups.
[ chemical formula 38]
In addition, examples of the repeating unit represented by the general formula (4) include repeating units described in paragraphs [0094] to [0105] of Japanese patent application laid-open No. 2014-04327 and repeating units described in paragraph [0094] of International publication No. 2018/193954.
The content of the repeating unit having a photoacid-generating group is preferably 1 mol% or more, more preferably 5 mol% or more, with respect to all the repeating units in the resin (a). The upper limit of the amount is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on the total amount of the repeating units in the resin (a).
< recurring Unit represented by the formula (V-1) or the following formula (V-2) >)
The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
The repeating unit represented by the following formula (V-1) and the following formula (V-2) is preferably a repeating unit different from the repeating unit described above.
[ chemical formula 39]
In the method, in the process of the invention,
R 6 r is R 7 Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or-COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group) or a carboxyl group. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
n 3 An integer of 0 to 6.
n 4 And represents an integer of 0 to 4.
X 4 Is methylene, oxygen atom or sulfur atom.
The repeating unit represented by the formula (V-1) or (V-2) is exemplified below.
Examples of the repeating unit represented by the formula (V-1) or (V-2) include repeating units described in paragraph [0100] of Japanese patent application laid-open No. 2018/193954.
< repeating units for reducing the motility of the Main chain >
From the viewpoint of being able to suppress excessive diffusion of the generated acid or pattern disintegration upon development, the resin (a) is preferably high in glass transition temperature (Tg). The Tg is preferably greater than 90℃and more preferably greater than 100℃and even more preferably greater than 110℃and particularly preferably greater than 125 ℃. Further, since an excessively high Tg leads to a decrease in dissolution rate in the developer, tg is preferably 400℃or lower, more preferably 350℃or lower.
In the present specification, the glass transition temperature (Tg) (hereinafter, "Tg of repeating unit") of a polymer such as the resin (a) is calculated by the following method. First, tg of a homopolymer consisting only of each repeating unit contained in the polymer was calculated by the Bicerano method, respectively. Next, the mass ratio (%) of each repeating unit to all repeating units in the polymer was calculated. Next, tg in each mass ratio is calculated using Fox formula (Materials Letters, 62 (2008) 3152, etc.), and the sum of these is set as Tg (°c) of the polymer.
Bicerano method is described in predictions of polymer properties (Prediction of polymer properties), marcel Dekker Inc, new York (1993). The Tg calculation by the Bicerano method can be performed using Polymer physical property estimation software MDL Polymer (MDL Information Systems, inc.).
In order to increase the Tg of the resin (A) (preferably to make the Tg more than 90 ℃), it is preferable to decrease the mobility of the main chain of the resin (A). The method of reducing the mobility of the main chain of the resin (A) includes the following methods (a) to (e).
(a) Introduction of bulky substituents into the main chain
(b) Introducing multiple substituents into the main chain
(c) Introduction of substituents initiating interactions between resins (A) near the main chain
(d) Forming a backbone in a cyclic structure
(e) Linking cyclic structures to the main chain
In addition, the resin (A) preferably has a repeating unit having a Tg of a homopolymer of 130 ℃ or higher.
The type of the repeating unit having a Tg of 130 ℃ or higher in the homopolymer is not particularly limited, as long as the Tg of the homopolymer calculated by the Bicerano method is 130 ℃ or higher. The type of functional group in the repeating unit represented by the following formulas (a) to (E) corresponds to a repeating unit having a Tg of 130 ℃ or higher in the homopolymer.
(repeating units represented by the formula (A))
As an example of a specific implementation means of the above (a), a method of introducing a repeating unit represented by the formula (a) into the resin (a) is given.
[ chemical formula 40]
In the formula (A), R A Represents a group comprising a polycyclic structure. R is R x Represents a hydrogen atom, a methyl group or an ethyl group. The group containing a polycyclic structure is a group containing a plurality of ring structures, which may or may not be fused.
Specific examples of the repeating unit represented by the formula (A) include repeating units described in paragraphs [0107] to [0119] of Japanese patent application laid-open No. 2018/193954.
(repeating units represented by the formula (B))
As an example of a specific implementation means of the above (B), a method of introducing a repeating unit represented by the formula (B) into the resin (a) is given.
[ chemical formula 41]
In the formula (B), R b1 ～R b4 Each independently represents a hydrogen atom or an organic group, R b1 ～R b4 At least 2 or more of them represent an organic group.
Also, when at least one of the organic groups is a group in which a ring structure is directly connected to the main chain of the repeating unit, the kind of other organic groups is not particularly limited.
In the case where none of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, at least 2 or more of the organic groups are substituents having 3 or more constituent atoms other than hydrogen atoms.
Specific examples of the repeating unit represented by the formula (B) include repeating units described in paragraphs [0113] to [0115] of Japanese patent application laid-open No. 2018/193954.
(repeating units represented by the formula (C))
As an example of a specific implementation means of the above (C), a method of introducing a repeating unit represented by the formula (C) into the resin (a) is given.
[ chemical formula 42]
In the formula (C), R c1 ～R c4 Each independently represents a hydrogen atom or an organic group, R c1 ～R c4 At least one of (2) is a group containing a hydrogen-bonding hydrogen atom within 3 atoms from the main chain carbon. Among them, it is preferable that the resin (a) has hydrogen-bonding hydrogen atoms in an atomic number of 2 or less (closer to the main chain side) in addition to causing interaction between the main chains.
Specific examples of the repeating unit represented by the formula (C) include repeating units described in paragraphs [0119] to [0121] of Japanese patent application laid-open No. 2018/193954.
(repeating units represented by the formula (D))
As an example of a specific implementation means of the above (D), a method of introducing a repeating unit represented by the formula (D) into the resin (a) is given.
[ chemical formula 43]
In the formula (D), "cylic" represents a group having a cyclic structure forming a main chain. The number of ring constituent atoms is not particularly limited.
Specific examples of the repeating unit represented by the formula (D) include repeating units described in paragraphs [0126] to [0127] of Japanese patent application laid-open No. 2018/193954.
(repeating units represented by the formula (E))
As an example of a specific implementation means of the above (E), a method of introducing a repeating unit represented by the formula (E) into the resin (a) is given.
[ chemical formula 44]
In the formula (E), re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group which may have a substituent.
"cylic" is a cyclic group containing carbon atoms of the backbone. The number of atoms contained in the cyclic group is not particularly limited.
Specific examples of the repeating unit represented by the formula (E) include repeating units described in paragraphs [0131] to [0133] of Japanese patent application laid-open No. 2018/193954.
< repeating units having an alicyclic hydrocarbon Structure and exhibiting no acid decomposability >
The resin (a) may contain a repeating unit having an alicyclic hydrocarbon structure and exhibiting no acid decomposition property. This reduces the elution of low molecular components from the resist film into the immersion liquid during immersion exposure. Examples of such a repeating unit include a repeating unit derived from 1-adamantyl (meth) acrylate, diamantanyl (meth) acrylate, tricyclodecane (meth) acrylate or cyclohexyl (meth) acrylate.
< repeating unit having neither hydroxyl group nor cyano group and represented by the formula (III) >
The resin (a) may contain a repeating unit represented by the formula (III) without any of a hydroxyl group and a cyano group.
[ chemical formula 45]
In the formula (III), R 5 Represents a hydrocarbon group having at least one cyclic structure and not having any one of a hydroxyl group and a cyano group.
Ra represents a hydrogen atom, an alkyl group or-CH 2 -O-Ra 2 A base. Wherein Ra is 2 Represents a hydrogen atom, an alkyl group or an acyl group.
Examples of the repeating unit represented by the formula (III) having neither a hydroxyl group nor a cyano group include repeating units described in paragraphs [0087] to [0094] of JP-A2014-98921.
< other repeating units >
The resin (a) may have a repeating unit other than the repeating unit.
For example, the resin (a) may have a repeating unit selected from the group consisting of a repeating unit having a thioxane (Oxathiane) ring group, a repeating unit having a hydroxy-morpholine-coumarin (oxazoron) ring group, a repeating unit having a dioxane ring group, and a repeating unit having a Hydantoin (Hydantoin) ring group.
Such a repeating unit is exemplified below.
[ chemical formula 46]
In addition to the above-described repeating structural units, the resin (a) may have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer adaptability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.
As the resin (A), it is preferable that all the repeating units are constituted of repeating units derived from a compound having an ethylenically unsaturated bond (particularly when the composition is used as a actinic ray-or radiation-sensitive resin composition for ArF). In particular, it is also preferable that the repeating units are all composed of (meth) acrylate-based repeating units. In this case, any of the repeating units may be used, that is, all the repeating units are repeating units of methacrylate repeating units, all the repeating units are repeating units of acrylate repeating units, all the repeating units are repeating units formed of methacrylate repeating units and acrylate repeating units, and the acrylate repeating units are preferably 50 mol% or less of all the repeating units.
The resin (a) can be synthesized according to a conventional method (e.g., radical polymerization).
The weight average molecular weight of the resin (a) is preferably 30,000 or less, preferably 1,000 to 30,000, more preferably 3,000 to 30,000, and even more preferably 5,000 to 15,000, as a polystyrene equivalent based on GPC.
The dispersity (molecular weight distribution) of the resin (a) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and further preferably 1.2 to 2.0. The smaller the dispersity, the more excellent the resolution and resist shape, and the smoother the sidewall of the resist pattern, the more excellent the roughness.
In the resist composition, the content of the resin (a) is preferably 40.0 to 99.9 mass%, more preferably 60.0 to 90.0 mass%, relative to the total solid content of the composition.
The resin (A) may be used in an amount of 1 or more.
[ solvent (F) ]
The resist composition preferably contains a solvent (preferably an organic solvent).
The solvent preferably contains at least one of (M1) a propylene glycol monoalkyl ether carboxylate and (M2), and (M2) is at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone and alkylene carbonate. The solvent may contain components other than the components (M1) and (M2).
Details of the component (M1) and the component (M2) are described in paragraphs [0218] to [0226] of International publication No. 2020/004306, which are incorporated herein by reference.
When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30% by mass with respect to the total amount of the solvent.
The content of the solvent in the resist composition is preferably set to 0.5 to 30% by mass, more preferably 1 to 20% by mass, of the solid content concentration. In this way, the coatability of the resist composition can be further improved.
The solid component means all components except the solvent.
[ Compound (B) which generates acid upon irradiation with actinic rays or radiation (photoacid generator) ]
The resist composition contains a compound (B) (photoacid generator) that generates an acid by irradiation with actinic rays or radiation.
The compound (B) may be in the form of a low-molecular compound or may be incorporated into a part of a polymer (for example, the resin (a)). The low-molecular compound may be used in combination with a form of being incorporated into a part of the polymer (for example, the resin (a)).
When the compound (B) is in the form of a low molecular compound, the molecular weight of the compound (B) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less. The lower limit is not particularly limited, but is preferably 100 or more.
When the compound (B) is in a form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (a) or into a resin different from the resin (a).
The compound (B) is preferably a low molecular compound.
Examples of the compound (B) include compounds represented by the formula "M + X - The compound (onium salt) represented by "is preferably a compound that generates an organic acid by exposure to light.
Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, and the like), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, and the like), carbonylsulfonylimide acids, bis (alkylsulfonyl) imide acids, and tris (alkylsulfonyl) methylated acids.
The molecular weight of the acid produced by the compound (B) is preferably 240 or more, more preferably 250 or more, further preferably 260 or more, particularly preferably 270 or more, and most preferably 280 or more.
< organic cation >
In the process of "M + X - "in the compound represented by + Representing an organic cation.
The structure of the organic cation is not particularly limited. The valence of the organic cation may be 1 or 2 or more.
The organic cation is preferably a cation represented by the following general formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by the following general formula (ZaII) (hereinafter also referred to as "cation (ZaII)").
[ chemical formula 47]
R 204 -I + -R 205 (ZaII)
In the general formula (ZaI), R 201 、R 202 R is R 203 Each independently represents an organic group.
In the general formula (ZaII), R 204 R is R 205 Each independently represents an organic group.
As for the above general formulae (ZaI) and (ZaII) described in detail below, R in the above general formula (ZaI) is preferable 201 、R 202 R is R 203 At least one of them is aryl or R in the above formula (ZaII) 204 R is R 205 At least one of which is aryl. The aryl group may have a substituent, and as a substituent, a halogen atom (preferably a fluorine atom or an iodine atom) or an organic group is preferable.
Further, R in the above general formula (ZaI) is preferably 201 、R 202 R is R 203 At least one of them has an acid-decomposable group or R in the above general formula (ZaII) 204 R is R 205 At least one of them has an acid-decomposable group. The acid-decomposable group is the same as that in the resin (a). R in the above general formula (ZaI) 201 、R 202 R is R 203 In the form of at least one acid-decomposable group, preferably R 201 、R 202 R is R 203 An aryl group substituted with an organic group containing an acid-decomposable group. As R in the above general formula (ZaII) 204 R is R 205 At least one of them has the form of an acid-decomposable group, preferably R 204 R is R 205 An aryl group substituted with an organic group containing an acid-decomposable group.
Cations (ZaI) are described.
As R 201 、R 202 R is R 203 The number of carbon atoms of the organic group of (2) is usually 1 to 30, preferably 1 to 20. And R is 201 ～R 203 The 2 groups may be bonded to form a ring structure, or may contain an oxygen atom, a sulfur atom, an ester group, an amide group or a carbonyl group in the ring. As R 201 ～R 203 Examples of the groups formed by bonding 2 of the above groups include alkylene groups (e.g., butylene and pentylene) and-CH 2 -CH 2 -O-CH 2 -CH 2 -。
Preferable examples of the organic cation represented by the formula (ZaI) include a cation (ZaI-1), a cation (ZaI-2), an organic cation represented by the formula (ZaI-3 b) (cation (ZaI-3 b)), and an organic cation represented by the formula (ZaI-4 b) (cation (ZaI-4 b)) described later.
First, a cation (ZaI-1) will be described.
The cation (ZaI-1) is R in the above formula (ZaI) 201 ～R 203 At least one of which is an aryl sulfonium cation of an aryl group.
In the aryl sulfonium cation, R can be 201 ～R 203 All being aryl groups, or R 201 ～R 203 Part of which is aryl, and the rest is alkyl or cycloalkyl.
And R is 201 ～R 203 Wherein 1 is aryl, R 201 ～R 203 The remaining 2 of the groups may be bonded to form a ring structure, or may contain an oxygen atom, a sulfur atom, an ester group, an amide group or a carbonyl group in the ring. As R 201 ～R 203 Examples of the groups formed by bonding 2 of (a) include alkylene groups in which 1 or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group (e.g., butylene, pentylene and-CH) 2 -CH 2 -O-CH 2 -CH 2 -)。
Examples of the aryl sulfonium cation include triarylsulfonium cations, diarylalkyl sulfonium cations, aryl dialkyl sulfonium cations, diarylmethyl sulfonium cations, and aryl dicycloalkyl sulfonium cations.
The aryl group contained in the aryl sulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues and benzothiophene residues. When the aryl sulfonium cation has 2 or more aryl groups, the 2 or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group of the aryl sulfonium cation is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group or a cyclohexyl group.
R 201 ～R 203 The substituents which may be included in the aryl group, the alkyl group and the cycloalkyl group in (a) are preferably, independently, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a cycloalkylalkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom (for example, fluorine and iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group and a phenylthio group.
The substituent may have a substituent, and it is preferable that the alkyl group has a halogen atom as a substituent, and is a halogenated alkyl group such as trifluoromethyl.
The substituents are also preferably combined in any manner to form an acid-decomposable group.
The acid-decomposable group is a group that is decomposed by the action of an acid to generate a polar group, and is preferably a structure in which a polar group is protected by a release group that is released by the action of an acid. The polar group and the release group are as described above.
Next, the cation (ZaI-2) will be described.
Cation (ZaI-2) is R in formula (ZaI) 201 ～R 203 Are respectively independentRepresents a cation of an organic group having no aromatic ring. Aromatic rings also include aromatic rings containing heteroatoms.
As R 201 ～R 203 The organic group having no aromatic ring is usually 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R 201 ～R 203 Preferably, each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxo-alkyl group, a 2-oxo-cycloalkyl group or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxo-alkyl group.
R 201 ～R 203 Examples of the alkyl group and cycloalkyl group include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl group).
R 201 ～R 203 May be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.
And R is 201 ～R 203 The substituents of (2) are also preferably each independently forming an acid-decomposable group by any combination of substituents.
Next, the cation (ZaI-3 b) will be described.
The cation (ZaI-3 b) is a cation represented by the following formula (ZaI-3 b).
[ chemical formula 48]
In the formula (ZaI-3 b),
R 1c ～R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.
R 6c R is R 7c Are respectively independent ofAnd standing for a hydrogen atom, an alkyl group (for example, t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R x R is R y Each independently represents alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl or vinyl.
And R is 1c ～R 7c And R is x R is R y The substituents of (2) are also preferably each independently forming an acid-decomposable group by any combination of substituents.
R 1c ～R 5c More than 2 of any one of R 5c And R is R 6c 、R 6c And R is R 7c 、R 5c And R is R x R is as follows x And R is R y May be bonded to each other to form rings, and the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring obtained by combining 2 or more of these rings. The ring may be a 3-to 10-membered ring, preferably a 4-to 8-membered ring, more preferably a 5-or 6-membered ring.
As R 1c ～R 5c More than 2 of any one of R 6c And R is R 7c R is as follows x And R is R y Examples of the group formed by bonding include alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted with a hetero atom such as an oxygen atom.
As R 5c And R is R 6c R is as follows 5c And R is R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
R 1c ～R 5c 、R 6c 、R 7c 、R x 、R y And R is 1c ～R 5c More than 2 of any one of R 5c And R is R 6c 、R 6c And R is R 7c 、R 5c And R is R x R is R x And R is R y The rings formed by bonding each other may have a substituent.
Next, the cation (ZaI-4 b) will be described.
The cation (ZaI-4 b) is a cation represented by the following formula (ZaI-4 b).
[ chemical formula 49]
In the formula (ZaI-4 b),
l represents an integer of 0 to 2.
r represents an integer of 0 to 8.
R 13 Represents a hydrogen atom, a halogen atom (for example, a fluorine atom, an iodine atom, or the like), a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (the cycloalkyl group itself may be a group containing a cycloalkyl group in part). These groups may have a substituent.
R 14 Represents a hydroxyl group, a halogen atom (for example, a fluorine atom, an iodine atom, or the like), an alkyl group, a haloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (the cycloalkyl group itself may be a group containing a cycloalkyl group in part). These groups may have a substituent. When there are a plurality of R 14 In this case, each of the above groups independently represents a hydroxyl group or the like.
R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. 2R 15 Can be bonded to each other to form a ring. When 2R 15 When the two are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one embodiment, 2R are preferred 15 Is alkylene, and is bonded to each other to form a ring structure. In addition, the alkyl, the cycloalkyl and the naphthyl, and 2R 15 The rings bonded to each other may have a substituent.
In formula (ZaI-4 b), R 13 、R 14 R is R 15 The alkyl group of (2) may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10. More preferably alkyl groupsMethyl, ethyl, n-butyl, t-butyl, etc.
And R is 13 ～R 15 And R is x R is R y Each substituent of (2) also preferably forms an acid-decomposable group independently of each other through any combination of substituents.
Next, the formula (ZaII) will be described.
In the formula (ZaII), R 204 R is R 205 Each independently represents an organic group, preferably an aryl, alkyl or cycloalkyl group.
R 204 R is R 205 Preferably phenyl or naphthyl, more preferably phenyl. R is R 204 R is R 205 The aryl group of (a) may be an aryl group containing a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene.
R 204 R is R 205 The alkyl group and cycloalkyl group of (a) are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl or pentyl) or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl or norbornyl).
R 204 R is R 205 The aryl, alkyl and cycloalkyl groups of (a) may each independently have a substituent. As R 204 R is R 205 Examples of the substituent that may be contained in the aryl group, the alkyl group and the cycloalkyl group include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group. And R is 204 R is R 205 The substituents of (2) are also preferably each independently forming an acid-decomposable group by any combination of substituents.
The following shows that M + Specific examples of the organic cations are shown, but the present invention is not limited to these.
[ chemical formula 50]
[ chemical formula 51]
[ chemical formula 52]
[ chemical formula 53]
< organic anion >
In the process of "M + X - "in the compound represented by X - Representing an organic anion.
The organic anion is not particularly limited, and examples thereof include organic anions having a valence of 1 or 2 or more.
The organic anion is preferably an anion having a significantly low ability to cause nucleophilic reaction, and more preferably a non-nucleophilic anion.
Examples of the non-nucleophilic anions include sulfonic acid anions (e.g., aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphorsulfonic acid anions), carboxylic acid anions (e.g., aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkylcarboxylic acid anions), sulfonyl imide anions, bis (alkylsulfonyl) imide anions, and tris (alkylsulfonyl) methide anions.
The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms.
The alkyl group may be, for example, a fluoroalkyl group (may have a substituent other than a fluorine atom).
The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include phenyl group, tolyl group and naphthyl group.
The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. The substituent is not particularly limited, and specifically includes a halogen atom such as a nitro group, a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkylsulfinyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).
As the aralkyl group in the aralkyl carboxylic acid anion, an aralkyl group having 7 to 14 carbon atoms is preferable.
Examples of the aralkyl group having 7 to 14 carbon atoms include benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl.
Examples of the sulfonyl imide anion include saccharin anions.
The alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent for the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.
Also, the alkyl groups in the bis (alkylsulfonyl) imide anions may be bonded to each other to form a ring structure. Thereby, the acid strength increases.
Examples of the other non-nucleophilic anions include fluoroolefins (e.g., PF 6 - )、Boron fluoride (e.g., BF 4 - ) And antimony fluoride (e.g., sbF 6 - )。
As the non-nucleophilic anion, preferred is an aliphatic sulfonic acid anion in which at least the α -position of the sulfonic acid is substituted with a fluorine atom, a fluorine atom or an aromatic sulfonic acid anion in which the group having a fluorine atom is substituted, a bis (alkylsulfonyl) imide anion in which the alkyl group is substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. Of these, a perfluoroaliphatic sulfonic acid anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonic acid anion having a fluorine atom is more preferable, and a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluorobenzenesulfonic acid anion or a 3, 5-bis (trifluoromethyl) benzenesulfonic acid anion is further preferable.
As a preferred example of the non-nucleophilic anion, AN anion represented by the following formula (AN 4) can be given.
[ chemical formula 54]
In the formula (AN 4), R 1 ～R 3 Each independently represents an organic group or a hydrogen atom. L represents a 2-valent linking group.
In the formula (AN 4), L represents a 2-valent linking group.
When a plurality of L's exist, L's may be the same or different.
As a linking group of the valence of 2, examples include-O-CO-O-; -COO-, -CONH-, -CO-, -O-, -S-, -SO 2 -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene (preferably having 2 to 6 carbon atoms) and a 2-valent linking group obtained by combining a plurality of them. Wherein, as a 2-valent linking group, preferably-O-CO-O-; -COO- -CONH-, -CO-, -O-, -SO 2 -, -O-CO-O-alkylene-, -COO-alkylene-or-CONH-alkylene-, more preferably-O-CO-O-; -O-CO-O-alkylene- -COO-, -CONH-, -SO 2 -or-COO-alkylene-.
L is preferably a group represented by the following formula (AN 4-2), for example.
* a -(CR 2a 2 ) X -Q-(CR 2b 2 ) Y -* b (AN4-2)
In formula (AN 4-2) a R in the expression and formula (AN 4) 3 Is used for the bonding position of the substrate.
* b Represented by the formula (AN 4) and-C (R) 1 )(R 2 ) -a bonding position.
X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3.
R 2a R is R 2b Each independently represents a hydrogen atom or a substituent.
When R is 2a R is R 2b When there are plural R's, plural R's exist 2a R is R 2b May be the same or different.
Wherein when Y is 1 or more, the compound represented by the formula (AN 4) is represented by the formula-C (R 1 )(R 2 ) Direct bonded CR 2b 2 R in (a) 2b Is an atom other than fluorine atom.
Q represents: A -O-CO-O-* B 、* A -CO-* B 、* A -CO-O-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B or A -SO 2 -* B 。
Wherein when X+Y in the formula (AN 4-2) is 1 or more and R in the formula (AN 4-2) 2a R is R 2b When all are hydrogen atoms, Q represents: A -O-CO-O-* B 、* A -CO-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B or A -SO 2 -* B 。
* A R in the expression (AN 4) 3 Lateral bond position B -SO in the expression (AN 4) 3 - Side bonding locations.
In the formula (AN 4), R 1 ～R 3 Each independently represents an organic group.
The organic group is not limited as long as it has 1 or more carbon atoms, and may be a linear group (for example, a linear alkyl group), a branched group (for example, a branched alkyl group such as a tert-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (oxygen atom, sulfur atom, nitrogen atom, or the like).
Examples of the organic group include a substituent other than an electron withdrawing group.
Examples of the substituent other than the electron withdrawing group include a hydrocarbon group, a hydroxyl group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group.
Further, as the substituent other than the electron withdrawing group, each independently is preferably-R ', -OH, -OR ', -OCOR ', -NH 2 、-NR’ 2 -NHR 'or-NHCOR'. R' is a hydrocarbyl group of valence 1.
Examples of the 1-valent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl and butyl; alkenyl groups such as vinyl, propenyl, butenyl, and the like; straight-chain or branched-chain hydrocarbon groups having 1-valence such as alkynyl groups including ethynyl, propynyl and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; a 1-valent alicyclic hydrocarbon group such as a cycloalkenyl group including a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group and a norbornenyl group; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthracenyl, and methylanthracenyl; and 1-valent aromatic hydrocarbon groups such as aralkyl groups, e.g., benzyl, phenethyl, phenylpropyl, naphthylmethyl, anthracenylmethyl, and the like.
Wherein R is 1 R is R 2 Preferably each independently is a hydrocarbyl group (preferably cycloalkyl group) or a hydrogen atom.
Wherein R is 3 Organic groups having a cyclic structure are preferred. The cyclic structure may be a single ring, may be multiple rings, or may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in the formula (AN 4)And (5) combining.
The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, nitrogen atom, or the like), for example. The heteroatom may be substituted with 1 or more carbon atoms forming a cyclic structure.
The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among them, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.
The cycloalkyl group may be a single ring (e.g., cyclohexyl group) or multiple rings (e.g., adamantyl group), and preferably has 5 to 12 carbon atoms.
The lactone group and the sultone group are preferably groups in which 1 hydrogen atom is removed from a ring member atom constituting the lactone structure or the sultone structure in any one of the structures represented by the formulae (LC 1-1) to (LC 1-21) and the structures represented by the formulae (SL 1-1) to (SL 1-3), for example.
As the non-nucleophilic anion, AN anion represented by the following formula (AN 1) is also preferable.
[ chemical formula 55]
In the formula (ANl), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.
Xf represents a fluorine atom or an organic group. The organic group may be an organic group substituted with at least one fluorine atom, or may be an organic group having no fluorine atom. The number of carbon atoms of the organic group (preferably alkyl group) is preferably 1 to 10, more preferably 1 to 4. The organic group substituted with at least one fluorine atom (preferably an alkyl group) is preferably a perfluoroalkyl group.
At least one Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferablyPreferably fluorine atom or CF 3 More preferably, two Xf are fluorine atoms.
R 4 R is R 5 Each independently represents a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R 4 R is R 5 When R is 4 R is R 5 May be the same or different.
From R 4 R is R 5 The alkyl group is preferably one having 1 to 4 carbon atoms. The above alkyl group may have a substituent. As R 4 R is R 5 Preferably a hydrogen atom.
Specific examples and preferred modes of the alkyl group substituted with at least one fluorine atom are the same as those of Xf in the formula (AN 1).
L represents a 2-valent linking group.
When a plurality of L's exist, L's may be the same or different.
As a linking group of the valence of 2, examples include-O-CO-O-; -COO-, -CONH-, -CO-, -O-, -S-, -SO 2 -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene (preferably having 2 to 6 carbon atoms) and a 2-valent linking group obtained by combining a plurality of them. Wherein, as a 2-valent linking group, preferably-O-CO-O-; -COO- -CONH-, -CO-, -O-, -SO 2 -, -O-CO-O-alkylene-, -COO-alkylene-or-CONH-alkylene-, more preferably-O-CO-O-; -O-CO-O-alkylene- -COO-, -CONH-, -SO 2 -or-COO-alkylene-.
W represents an organic group containing a cyclic structure. Among them, a cyclic organic group is preferable.
Examples of the cyclic organic group include alicyclic groups, aryl groups, and heterocyclic groups.
The alicyclic group may be a single ring or multiple rings. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, preferred is an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecyl group, a tetracyclodecyl group, a tetracyclododecyl group and an adamantyl group.
Aryl groups may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthryl and anthracyl.
The heterocyclic group may be monocyclic or polycyclic. In the case of a polycyclic heterocyclic group, the diffusion of the acid can be further suppressed. The heterocyclic group may or may not have aromatic properties. Examples of the heterocyclic ring having an aromatic property include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromatic property include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring.
The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be any of a straight chain and a branched chain, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be any of a monocyclic ring, a polycyclic ring, and a spiro ring, and preferably has 3 to 20 carbon atoms), an aryl group (which may be any of a 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a urea group, a thioether group, a sulfonamide group, and a sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon contributing to the formation of a ring) may be a carbonyl carbon. And, 2 or more substituents may be bonded to each other to form a ring. For example, there may be mentioned a case where 2 alkoxy groups or hydroxyl groups and alkoxy groups are bonded to each other to form a ring having a cyclic acetal group structure. The ring may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).
As the anion represented by the formula (AN 1), SO is preferable 3 - -CF 2 -CH 2 -OCO-(L) q' -W、SO 3 - -CF 2 -CHF-CH 2 -OCO-(L) q' -W、SO 3 - -CF 2 -COO-(L) q' -W、SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L) q W or SO 3 - -CF 2 -CH(CF 3 )-OCO-(L) q' -W. Here, L, q and W are the same as in formula (AN 1). q' represents an integer of 0 to 10.
The anions represented by the formula (AN 1) are also preferably represented by the following modes (AN 2) and (AN 3).
Mode (AN 2): in the formula (ANl), o represents 2, p represents 0, and is bonded to-SO 3 - Each of 2 Xf of directly bonded carbon atoms (hereinafter, this carbon atom is also referred to as "carbon atom Z1") represents a hydrogen atom or an organic group having no fluorine atom, and each of 2 Xf of directly bonded carbon atoms (hereinafter, this carbon atom is also referred to as "carbon atom Z2") represents a hydrogen atom or an organic group. The preferable modes of q, L and W are the same as those described above.
The 2 Xf groups bonded to the carbon atom Z1 are preferably hydrogen atoms.
Preferably, at least one of 2 Xf bonded to the carbon atom Z2 is a fluorine atom or an organic group having a fluorine atom, more preferably two are fluorine atoms or organic groups having a fluorine atom, and further preferably two are alkyl groups substituted with fluorine.
Mode (AN 3): in the formula (AN 1), one of 2 Xf each independently represents a fluorine atom or AN alkyl group substituted with at least one fluorine atom, and the other each independently represents a hydrogen atom or AN organic group having no fluorine atom. o, p, q, R 4 、R 5 The preferable modes of L and W are the same as described above.
The non-nucleophilic anion may be a benzenesulfonic acid anion, and is preferably a benzenesulfonic acid anion substituted with a branched alkyl group or cycloalkyl group.
As the non-nucleophilic anion, AN aromatic sulfonic acid anion represented by the following formula (AN 5) is also preferable.
[ chemical formula 56]
In the formula (AN 5), ar represents AN aryl group (phenyl group or the like), and may have a substituent other than a sulfonic acid anion and a- (D-B) group. Examples of the substituent that may be further contained include a fluorine atom and a hydroxyl group.
n represents an integer of 0 or more. N is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
D represents a single bond or a 2-valent linking group. Examples of the 2-valent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate group, and an ester group, and a group composed of 2 or more of these groups.
B represents a hydrocarbon group.
B is preferably an aliphatic hydrocarbon structure. B is more preferably isopropyl, cyclohexyl or aryl (tricyclohexylphenyl or the like) which may further have a substituent.
And B may also have a formula consisting of "- (L) q -a substituent represented by W ". L, q and W are the same as L, q and W in the above formula (AN 1), and specific examples and preferable ranges are also the same.
As non-nucleophilic anions, disulfonamide anions are also preferred.
Disulfonamide anions are for example represented by N - (SO 2 -R q ) 2 Represented anions.
Here, R is q Represents an alkyl group which may have a substituent(s), preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. 2R q May bond to each other to form a ring. 2R q The group bonded to each other is preferably an alkylene group which may have a substituent, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The number of carbon atoms of the alkylene group is preferably 2 to 4.
Further, as the non-nucleophilic anion, anions represented by the following formulas (d 1-1) to (d 1-4) may be mentioned.
[ chemical formula 57]
[ chemical formula 58]
In the formula (d 1-1), R 51 Represents a hydrocarbon group (e.g., an aryl group such as a phenyl group) which may have a substituent (e.g., a hydroxyl group).
In the formula (d 1-2), Z 2c Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein, the fluorine atom in the carbon atom adjacent to S is unsubstituted).
Z 2c The hydrocarbon group in (a) may be linear or branched, and may have a cyclic structure. The carbon atom in the hydrocarbon group (preferably, the carbon atom as a ring member atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group which may have a substituent. The carbon atoms forming the above-mentioned norbornyl group may be carbonyl carbon.
And "Z" in the formula (d 1-2) 2c -SO 3 - "preferably different from the anion represented by the above formula (AN 4), (AN 1) or (AN 5). For example, Z 2c Groups other than aryl are preferred. And, for example, Z 2c In relation to-SO 3 - The atoms at the α and β positions are preferably atoms other than carbon atoms having fluorine atoms as substituents. For example, Z 2c In relation to-SO 3 - The atom in the alpha position and/or the atom in the beta position is preferably a ring member atom in a cyclic group.
In the formula (d 1-3), R 52 Represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3 Represents a linear, branched or cyclic alkylene group, arylene group or carbonyl group, and Rf represents a hydrocarbon group.
In the formula (d 1-4), R 53 ～R 54 Represents an organic group (preferably a hydrocarbon group having a fluorine atom). R is R 53 ～R 54 May bond to each other to form a ring.
The organic anions may be used alone or in combination of 1 or more than 2.
The resist composition preferably further contains 2 or more compounds (B) or at least one compound selected from the following compounds (I) and (II).
< Compound (I) and Compound (II) >
The compound (B) is also preferably at least one selected from the following compounds (I) and (II).
(Compound (I))
The compound (I) is a compound having 1 or more of the following structural sites X and 1 or more of the following structural sites Y, and is a compound which generates an acid containing the following 1 st acid site derived from the following structural site X and the following 2 nd acid site derived from the following structural site Y by irradiation with actinic rays or radiation.
Structural part X: from anionic site A 1 - Cation site M 1 + Composition, and formed by irradiation of actinic rays or radiation 1 The structural part of the 1 st acid part
Structural part Y: from anionic site A 2 - Cation site M 2 + Composition, and formed by irradiation of actinic rays or radiation 2 The 2 nd acid site of the expression
Cation site M 1 + And cation site M 2 + Preferably, each independently represents an organic cation, and specific examples and preferred ranges and ranges described above for the organic cation are defined by M + The organic cations represented are identical.
The compound (I) satisfies the following condition I.
Condition I: in the above compound (I), the above cation site M in the above structural site X 1 + And the cationic site M in the structural site Y 2 + Take the place of H + The resulting compound PI has: the acid dissociation constant a1 is derived from the structureThe above cation site M in site X 1 + Take the place of H + Made of HA 1 An acidic moiety represented; and an acid dissociation constant a2 derived from the cation site M in the structural site Y 2 + Take the place of H + Made of HA 2 The acid site represented, and the acid dissociation constant a2 is larger than the acid dissociation constant a1.
Condition I will be described more specifically below.
When the compound (I) is, for example, a compound which generates an acid having 1 acid site 1 derived from the structural site X and 1 acid site 2 derived from the structural site Y, the compound PI corresponds to "having HA 1 And HA (alpha) 2 Is a compound of formula (I).
In the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI, the compound PI becomes "having a" when the acid dissociation constant of the compound PI is determined 1 - HA (HA) 2 The pKa of the compound "of (2) is the acid dissociation constant a1, and the above-mentioned" has A 1 - HA (HA) 2 The compounds "become" having A 1 - A is a 2 - The pKa at which the compound of (a) is present is the acid dissociation constant a2.
In addition, when the compound (I) is a compound that generates an acid having 2 acid sites 1 derived from the structural site X and 1 acid site 2 derived from the structural site Y, for example, the compound PI corresponds to "having 2 HA' s 1 And 1 HA 2 Is a compound of formula (I).
When the acid dissociation constant of this compound PI was determined, the compound PI became "having 1 a 1 - 1 HA 1 1 HA 2 Acid dissociation constant at the time of "compound of (2)" having 1A 1 - 1 HA 1 1 HA 2 The compounds "become" having 2A 1 - 1 HA 2 The acid dissociation constant at the time of the compound "corresponds to the acid dissociation constant a1 described above. And, "have 2A 1 - And 1 HA 2 The compound of (2) becomes a "utensilThere are 2A 1 - And A 2 - The acid dissociation constant at the time of the compound "corresponds to the acid dissociation constant a2. That is, in the case of this compound PI, there are a plurality of cationic sites M derived from the structural site X 1 + Take the place of H + Made of HA 1 The acid dissociation constant a2 is a value larger than the maximum value among the plurality of acid dissociation constants a1. In addition, the compound PI was "having 1A 1 - 1 HA 1 1 HA 2 The acid dissociation constant at the time of "Compound (A)" was aa, and "having 1A 1 - 1 HA 1 1 HA 2 The compounds "become" having 2A 1 - 1 HA 2 When the acid dissociation constant of the compound "is ab, aa and ab satisfy aa < ab.
The acid dissociation constant a1 and the acid dissociation constant a2 are obtained by the above-described method for measuring the acid dissociation constant.
When the compound (I) is irradiated with actinic rays or radiation, the above-mentioned compound PI corresponds to the acid produced.
When the compound (I) has 2 or more structural sites X, the structural sites X may be the same or different. And 2 or more of the above A 1 - More than 2M 1 + The two may be the same or different.
In the compound (I), A is as defined above 1 - A is as described above 2 - And M is as described above 1 + M as described above 2 + Each of which may be the same or different, but A is the same as or different from 1 - A is as described above 2 - Preferably different from each other.
In the above-mentioned compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value thereof when a plurality of acid dissociation constants a1 exist) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (maximum value when a plurality of acid dissociation constants a1 exist) and the acid dissociation constant a2 is not particularly limited, and is, for example, 16 or less.
In the above compound PI, the acid dissociation constant a2 is, for example, 20 or less, preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably-4.0 or more.
In the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably-20.0 or more.
Anionic site A 1 - Anion site A 2 - Examples of the structural moiety containing a negatively charged atom or group include structural moieties selected from the following formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6).
As anionic site A 1 - Among them, any one of the formulas (AA-1) to (AA-3) is more preferable, and any one of the formulas (AA-1) and (AA-3) is more preferable.
And, as an anionic site A 2 - Preferably, the anion site A is capable of forming an acid dissociation constant ratio 1 - The large acidic moiety is more preferably any one of formulas (BB-1) to (BB-6), and still more preferably any one of formulas (BB-1) and (BB-4).
In the following formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6), the bonding position is represented.
In the formula (AA-2), R A Each independently represents a 1-valent organic group.
[ chemical formula 59]
[ chemical formula 60]
The specific structure of the compound (I) is not particularly limited, and examples thereof include compounds represented by the following formulas (Ia-1) to (Ia-5).
Compounds represented by the formula (Ia-1)
First, the compound represented by formula (Ia-1) will be described.
M 11 + A 11 - -L 1 -A 12 - M 12 + (Ia-1)
The compound represented by the formula (Ia-1) is produced by irradiation of actinic rays or radiation 11 -L 1 -A 12 And H.
In the formula (Ia-1), M 11 + M and M 12 + Each independently represents an organic cation.
A 11 - A is a 12 - Each independently represents a 1-valent anionic functional group.
L 1 Represents a 2-valent linking group.
M 11 + M and M 12 + The two may be the same or different.
A 11 - A is a 12 - The respective may be the same or different, but are preferably different from each other.
Wherein in the above formula (Ia-1), the reaction is carried out by M 11 + M and M 12 + Represented cation substitution is H + The resulting compound PIa (HA 11 -L 1 -A 12 H) Is derived from A 12 The acid dissociation constant a2 of the acid site represented by H is larger than that derived from HA 11 The acid dissociation constant a1 of the acid site is shown. In addition, preferable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. The compound PIa is the same as an acid generated from the compound represented by the formula (Ia-1) by irradiation with actinic rays or radiation.
And M is 11 + 、M 12 + 、A 11 - 、A 12 - L and L 1 May have an acid-decomposable group as a substituent.
In the formula (Ia-1), the reaction is carried out by M 11 + M and M 12 + Organic cations represented by the formula M + The same applies.
From A 11 - The 1-valent anionic functional group represented by the formula (I) means a compound comprising the above-mentioned anionic site A 1 - Is a 1-valent group. And, from A 12 - The 1-valent anionic functional group represented by the formula (I) means a compound comprising the above-mentioned anionic site A 2 - Is a 1-valent group.
As a result of A 11 - A is a 12 - The 1-valent anionic functional group represented by the formula (AA-1) to (AA-3) is preferably a 1-valent anionic functional group containing an anionic moiety of any one of the formulas (BB-1) to (BB-6), and more preferably a 1-valent anionic functional group selected from the formulas (AX-1) to (AX-3) and the formulas (BX-1) to (BX-7). As a result of A 11 - Among them, the 1-valent anionic functional group represented by any one of the formulas (AX-1) to (AX-3) is preferable. And, as a result of A 12 - Among them, the 1-valent anionic functional group represented by any one of the formulas (BX-1) to (BX-7) is preferable, and the 1-valent anionic functional group represented by any one of the formulas (BX-1) to (BX-6) is more preferable.
[ chemical formula 61]
In the formulae (AX-1) to (AX-3), R A1 R is R A2 Each independently represents a 1-valent organic group. * Indicating the bonding location.
As represented by R A1 Examples of the organic group having a valence of 1 include a cyano group, a trifluoromethyl group and a methanesulfonyl group.
As represented by R A2 The organic group having a valence of 1 is preferably a linear, branched or cyclic alkyl group or an aryl group.
The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
The above alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, and more preferably a fluorine atom. When the above alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 6) or a cyano group, and more preferably a fluorine atom, an iodine atom, or a perfluoroalkyl group.
In the formulae (BX-1) to (BX-4) and (BX-6), R B An organic group having a valence of 1. * Indicating the bonding location.
As represented by R B The organic group having a valence of 1 is preferably a linear, branched or cyclic alkyl group or an aryl group.
The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.
The above alkyl group may have a substituent. The substituent is not particularly limited, but is preferably a fluorine atom or a cyano group, and more preferably a fluorine atom. When the above alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
In addition, the carbon atom which becomes the bonding position in the alkyl group (for example, in the case of the formulae (BX-1) and (BX-4), corresponds to the carbon atom which is directly bonded to-CO-indicated in the formulae in the alkyl group, and in the case of the formulae (BX-2) and (BX-3), corresponds to-SO-indicated in the formulae in the alkyl group 2 The directly bonded carbon atom corresponds to the carbon atom directly bonded to N indicated in the formula in the alkyl group in the case of formula (BX-6). ) In the case of having a substituent, a substituent other than a fluorine atom or a cyano group is also preferable.
In the alkyl group, a carbon atom may be substituted with a carbonyl carbon.
The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), a cyano group, an alkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), an alkoxy group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or an alkoxycarbonyl group (for example, preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms), more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.
In the formula (Ia-1), L is 1 The represented 2-valent linking group is not particularly limited, can be exemplified by-CO-; -NR-, -CO-, -O-, -S-, -SO 2 An alkylene group (preferably a straight chain or branched chain) having 1 to 6 carbon atoms, a cycloalkylene group (preferably a 3 to 15 carbon atoms), an alkenylene group (preferably a 2 to 6 carbon atoms), a 2-valent aliphatic heterocyclic group (preferably a 5 to 10-membered ring having at least one N, O, S or Se atom in the ring structure, more preferably a 5 to 7-membered ring, further preferably a 5 to 6-membered ring), a 2-valent aromatic heterocyclic group (preferably a 5 to 10-membered ring having at least one N, O, S or Se atom in the ring structure, further preferably a 5 to 7-membered ring, further preferably a 5 to 6-membered ring), a 2-valent aromatic hydrocarbon ring group (preferably a 6 to 10-membered ring, further preferably a 6-membered ring), and a 2-valent linking group obtained by combining a plurality of these groups. The R may be a hydrogen atom or a 1-valent organic group. The 1-valent organic group is not particularly limited, and is preferably an alkyl group (preferably having 1 to 6 carbon atoms).
The alkylene group, the cycloalkylene group, the alkenylene group, the aliphatic heterocyclic group having 2 valences, the aromatic heterocyclic group having 2 valences, and the aromatic hydrocarbon ring group having 2 valences may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).
Wherein, as L 1 The 2-valent linking group represented by formula (L1) is preferably a 2-valent linking group.
[ chemical formula 62]
In the formula (L1), L 111 Represents a single bond or a 2-valent linking group.
As represented by L 111 The represented 2-valent linking group is not particularly limited, examples include-CO-, -NH-; -O-, -SO 2 An alkylene group which may have a substituent (preferably, any one of a straight chain and a branched chain) having 1 to 6 carbon atoms, a cycloalkylene group which may have a substituent (preferably, 3 to 15 carbon atoms), an aryl group which may have a substituent (preferably, 6 to 10 carbon atoms), and a 2-valent linking group obtained by combining a plurality of these groups. The substituent is not particularly limited, and examples thereof include a halogen atom.
p represents an integer of 0 to 3, preferably an integer of 1 to 3.
v represents an integer of 0 or 1.
Xf 1 Each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.
Xf 2 Each independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. As Xf 2 Among them, preferred is an alkyl group substituted with at least 1 fluorine atom, and more preferred is a fluorine atom or a perfluoroalkyl group.
Wherein as Xf 1 Xf 2 Preferably each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 . In particular, xf is further preferable 1 Xf 2 Are all fluorine atoms.
* Indicating the bonding location.
When L in formula (Ia-1) 11 When the 2-valent linking group represented by the formula (L1) is represented by the formula (L1), L in the formula (L1) 111 The pendant linkage is preferably linked to A in formula (Ia-1) 12 - And (5) bonding.
Compounds represented by the formulae (Ia-2) to (Ia-4)
Next, the compounds represented by the formulas (Ia-2) to (Ia-4) will be described.
[ chemical formula 63]
In the formula (Ia-2), A 21a - A is a 21b - Each independently represents a 1-valent anionic functional group. Here, by A 21a - A is a 21b - The 1-valent anionic functional group represented by the formula (I) means a compound comprising the above-mentioned anionic site A 1 - Is a 1-valent group. As a result of A 21a - A is a 21b - The 1-valent anionic functional group represented by the formula (AX-1) is not particularly limited, and examples thereof include 1-valent anionic functional groups selected from the formulae (AX-1) to (AX-3).
A 22 - Represents a 2-valent anionic functional group. Here, by A 22 - The anionic functional group having a valence of 2 represented by the formula (I) means a compound comprising the above-mentioned anionic site A 2 - Is a 2-valent group. As a result of A 22 - Examples of the anionic functional group having a valence of 2 include anionic functional groups having a valence of 2 represented by the following formulas (BX-8) to (BX-11).
[ chemical formula 64]
M 21a + 、M 21b + M and M 22 + Each independently represents an organic cation. As represented by M 21a + 、M 21b + M and M 22 + Organic cations represented by the formula M 1 + Meaning is the same, excellentThe same applies to the selection.
L 21 L and L 22 Each independently represents a 2-valent organic group.
In the above formula (Ia-2), M is represented by 21a + 、M 21b + M and M 22 + Represented organic cations are replaced by H + The compound PIa-2 is derived from A 22 The acid dissociation constant a2 of the acid site represented by H is larger than that derived from A 21a H acid dissociation constant a1-1 and derived from A 21b Acid dissociation constant a1-2 of the acid site represented by H. In addition, the acid dissociation constants a1-1 and a1-2 correspond to the acid dissociation constant a1 described above.
In addition, A 21a - A is a 21b - May be the same as or different from each other. And M is 21a + 、M 21b + M and M 22 + May be the same as or different from each other.
And M is 21a + 、M 21b + 、M 22 + 、A 21a - 、A 21b - 、L 21 L and L 22 At least one of them may have an acid-decomposable group as a substituent.
In the formula (Ia-3), A 31a - A is a 32 - Each independently represents a 1-valent anionic functional group. In addition, from A 31a - Definition of 1-valent anionic functional group represented by the above formula (Ia-2) and A 21a - A is a 21b - The meaning is the same, and the preferred mode is the same.
From A 32 - The 1-valent anionic functional group represented by the formula (I) means a compound comprising the above-mentioned anionic site A 2 - Is a 1-valent group. As a result of A 32 - The 1-valent anionic functional group represented by the formula (BX-1) to (BX-7) is not particularly limited, and examples thereof include 1-valent anionic functional groups selected from the above formulae.
A 31b - Represents a 2-valent anionic functional group. Here, by A 31b - The anionic functional group having a valence of 2 represented by the formula (I) means a compound comprising the above-mentioned anionic site A 1 - Is a 2-valent group. As a result of A 31b - Examples of the 2-valent anionic functional group include 2-valent anionic functional groups represented by the following formula (AX-4).
[ chemical formula 65]
M 31a + 、M 31b + M and M 32 + Each independently represents a 1-valent organic cation. As represented by M 31a + 、M 31b + M and M 32 + Organic cations represented by the formula M 1 + The meaning is the same, and the preferred mode is the same.
L 31 L and L 32 Each independently represents a 2-valent organic group.
In the above formula (Ia-3), M is represented by 31a + 、M 31b + M and M 32 + Represented organic cations are replaced by H + The resulting compound PIa-3 is derived from the group A 32 The acid dissociation constant a2 of the acid site represented by H is larger than that derived from A 31a Acid dissociation constant a1-3 of acid site represented by H and derived from A 31b Acid dissociation constant a1-4 of the acid site represented by H. In addition, the acid dissociation constants a1-3 and a1-4 correspond to the acid dissociation constant a1 described above.
In addition, A 31a - A is a 32 - May be the same as or different from each other. And M is 31a + 、M a1b + M and M 32 + May be the same as or different from each other.
And M is 31a + 、M 31b + 、M 32 + 、A 31a - 、A 32 - 、L 31 L and L 32 At least one of (a)Each may have an acid-decomposable group as a substituent.
In the formula (Ia-4), A 41a - 、A 41b - A is a 42 - Each independently represents a 1-valent anionic functional group. In addition, from A 41a - A is a 41b - Definition of 1-valent anionic functional group represented by the above formula (Ia-2) and A 21a - A is a 21b - The meaning is the same. And, from A 42 - Definition of 1-valent anionic functional group represented by the above formula (Ia-3) and A 32 - The meaning is the same, and the preferred mode is the same.
M 41a + 、M 41b + M and M 42 + Each independently represents an organic cation.
L 41 Represents a 3-valent organic group.
In the above formula (Ia-4), M is represented by 41a + 、M 41b + M and M 42 + Represented organic cations are replaced by H + The compound PIa-4 is derived from A 42 The acid dissociation constant a2 of the acid site represented by H is larger than that derived from A 41a Acid dissociation constant a1-5 of acid site represented by H and derived from A 41b Acid dissociation constant a1-6 of the acid site represented by H. In addition, the acid dissociation constants a1 to 5 and a1 to 6 correspond to the acid dissociation constant a1 described above.
In addition, A 41a - 、A 41b - A is a 42 - May be the same as or different from each other. And M is 41a + 、M 41b + M and M 42 + May be the same as or different from each other.
And M is 41a + 、M 41b + 、M 42 + 、A 41a - 、A 41b - 、A 42 - L and L 41 At least one of them may have an acid-decomposable group as a substituent.
As a formula of a formulaL in (Ia-2) 21 L and L 22 And L in formula (Ia-3) 31 L and L 32 The represented organic group having a valence of 2 is not particularly limited, examples include-CO-, -NR-; -O-, -S-, -SO 2 An alkylene group (preferably a straight-chain or branched-chain carbon atom number), a cycloalkylene group (preferably a 3-15-membered carbon atom number), an alkenylene group (preferably a 2-6-membered carbon atom number), a 2-valent aliphatic heterocyclic group (preferably a 5-to 10-membered ring having at least one N, O, S or Se atom in the ring structure, more preferably a 5-to 7-membered ring, further preferably a 5-to 6-membered ring.), a 2-valent aromatic heterocyclic group (preferably a 5-to 10-membered ring having at least one N, O, S or Se atom in the ring structure, further preferably a 5-to 7-membered ring, further preferably a 5-to 6-membered ring), a 2-valent aromatic hydrocarbon group (preferably a 6-to 10-membered ring, further preferably a 6-membered ring), and a 2-valent organic group in which a plurality of these groups are combined. The R may be a hydrogen atom or a 1-valent organic group. The 1-valent organic group is not particularly limited, and is preferably an alkyl group (preferably having 1 to 6 carbon atoms).
The alkylene group, the cycloalkylene group, the alkenylene group, the aliphatic heterocyclic group having 2 valences, the aromatic heterocyclic group having 2 valences, and the aromatic hydrocarbon ring group having 2 valences may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).
As L in the formula (Ia-2) 21 L and L 22 And L in formula (Ia-3) 31 L and L 32 The organic group having a valence of 2 represented by, for example, the following formula (L2) is also preferable.
[ chemical formula 66]
In the formula (L2), q represents an integer of 1 to 3. * Indicating the bonding location.
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xf are fluorine atoms.
L A Represents a single bond or a 2-valent linking group.
As represented by L A The represented 2-valent linking group is not particularly limited, for example, it is exemplified by-CO-; -O-, -SO 2 Alkylene (preferably having 1 to 6 carbon atoms and optionally branched), cycloalkylene (preferably having 3 to 15 carbon atoms), a 2-valent aromatic hydrocarbon ring group (preferably a 6 to 10-membered ring, more preferably a 6-membered ring), and a 2-valent linking group formed by combining a plurality of these groups.
The alkylene group, the cycloalkylene group, and the 2-valent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).
Examples of the organic group having a valence of 2 represented by the formula (L2) include-CF 2 -*、*-CF 2 -CF 2 -*、*-CF 2 -CF 2 -CF 2 -*、*-Ph-O-SO 2 -CF 2 -*、*-Ph-O-SO 2 -CF 2 -CF 2 -*、*-Ph-O-SO 2 -CF 2 -CF 2 -CF 2 -A kind of electronic device with high-pressure air-conditioning system? Ph-OCO-CF 2 - *. Further, ph is a phenylene group which may have a substituent, preferably 1, 4-phenylene group. The substituent is not particularly limited, and is preferably an alkyl group (for example, preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 6), an alkoxy group (for example, preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 6), or an alkoxycarbonyl group (for example, preferably a carbon number of 2 to 10, more preferably a carbon number of 2 to 6).
When L in formula (Ia-2) 21 L and L 22 When the organic group having a valence of 2 represented by formula (L2) is represented by formula (L2), L in formula (L2) A The pendant linkage is preferably with A in formula (Ia-2) 21a - A is a 21b - And (5) bonding.
And, when L in formula (Ia-3) 31 L and L 32 When the organic group having a valence of 2 represented by formula (L2) is represented by formula (L2), L in formula (L2) A The pendant linkage is preferably with A in formula (Ia-3) 31a - A is a 32 - And (5) bonding.
Compounds represented by the formula (Ia-5)
Next, the formula (Ia-5) will be described.
[ chemical formula 67]
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In the formulae (Ia-5), A 51a - 、A 51b - A is a 51c - Each independently represents a 1-valent anionic functional group. Here, by A 51a - 、A 51b - A is a 51c - The 1-valent anionic functional group represented by the formula (I) means a compound comprising the above-mentioned anionic site A 1 - Is a 1-valent group. As a result of A 51a - 、A 51b - A is a 51c - The 1-valent anionic functional group represented by the formula (AX-1) is not particularly limited, and examples thereof include J-valent anionic functional groups selected from the above formulae (AX-1) to (AX-3).
A 52a - A is a 52b - Represents a 2-valent anionic functional group. Here, by A 52a - A is a 52b - The anionic functional group having a valence of 2 represented by the formula (I) means a compound comprising the above-mentioned anionic site A 2 - Is a 2-valent group. As a result of A 52a - A is a 52b - Examples of the anionic functional group having a valence of 2 include anionic functional groups having a valence of 2 selected from the above formulae (BX-8) to (BX-11).
M 51a + 、M 51b + 、M 51c + 、M 52a + M and M 52b + Each independently represents an organic cation. As a means ofFrom M 51a + 、M 51b + 、M 51c + 、M 52a + M and M 52b + Organic cations represented by the formula M 1 + The meaning is the same, and the preferred mode is the same.
L 51 L and L 53 Each independently represents a 2-valent organic group. As represented by L 51 L and L 53 An organic group having a valence of 2 and L in the above formula (Ia-2) 21 L and L 22 The meaning is the same, and the preferred mode is the same.
L 52 Represents a 3-valent organic group. As represented by L 52 An organic group having a valence of 3 and L in the above formula (Ia-4) 41 The meaning is the same, and the preferred mode is the same.
In the above formula (Ia-5), M is represented by 51a + 、M 51b + 、M 51c + 、M 52a + M and M 52b + Represented organic cations are replaced by H + The compound PIa-5 is derived from A 52a Acid dissociation constant a2-1 of acid site represented by H and derived from A 52b The acid dissociation constant a2-2 of the acid site represented by H is larger than that derived from A 51a H acid dissociation constant a1-1, derived from A 51b Acid dissociation constant a1-2 of acid site represented by H and derived from A 51c Acid dissociation constant a1-3 of the acid site represented by H. The acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1, and the acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2.
In addition, A 51a - 、A 51b - A is a 51c - May be the same as or different from each other. And A is 52a - A is a 52b - May be the same as or different from each other. And M is 51a + 、M 51b + 、M 51c + 、M 52a + M and M 52b + May be the same as or different from each other.
And M is 51b + 、M 51c + 、M 52a + 、M 52b + 、A 51a - 、A 51b - 、A 51c - 、L 51 、L 52 L and L 53 At least one of them may have an acid-decomposable group as a substituent.
(Compound (II))
The compound (II) is a compound having 2 or more structural sites X and 1 or more structural sites Z described below, and generating an acid containing 2 or more 1 st acid sites derived from the structural sites X and the structural sites Z by irradiation with actinic rays or radiation.
Structural part Z: nonionic sites capable of neutralizing acids
In the compound (II), the structural site X is defined and A is 1 - M and M 1 + Definition of (2) and definition of structural site X in the above-mentioned compound (1), and A 1 - M and M 1 + The definition of (c) is the same, and the preferred mode is the same.
In the above compound (II), the cation site M in the structural site X 1 + Take the place of H + In the compound PII obtained, the cation site M is derived from the structural site X 1 + Take the place of H + Made of HA 1 The preferable range of the acid dissociation constant a1 of the acid site is the same as the acid dissociation constant a1 of the compound PI.
In addition, when the compound (II) is, for example, a compound that generates an acid having 2 acid sites 1 derived from the structural site X and the structural site Z, the compound PII corresponds to "having 2 HA 1 Is a compound of formula (I). When the acid dissociation constant of the compound PII was determined, the compound PII became "having 1A 1 - And 1 HA 1 Acid dissociation constant at the time of "compound of (2)" having 1A 1 - And 1 HA 1 The compounds "become" having 2A 1 - The acid dissociation constant at the time of the compound "of (2) corresponds to the acid dissociation constanta1。
The acid dissociation constant a1 was obtained by the method for measuring the acid dissociation constant.
When the compound (II) is irradiated with actinic rays or radiation, the above-mentioned compound PII corresponds to the acid produced.
The 2 or more structural sites X may be the same or different. And 2 or more of the above A 1 - More than 2M 1 + The two may be the same or different.
The nonionic moiety capable of neutralizing the acid in the structural moiety Z is not particularly limited, and for example, a moiety containing a group capable of electrostatic interaction with a proton or a functional group having an electron is preferable.
Examples of the functional group capable of electrostatic interaction with protons or the functional group having electrons include a functional group having a macrocyclic compound structure such as a cyclic polyether, and a functional group having a nitrogen atom having an unshared electron pair that does not contribute to pi conjugation. The nitrogen atom having an unshared pair of electrons that does not contribute to pi conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
[ chemical formula 68]
Unshared electron pair
Examples of the partial structure of the group capable of electrostatic interaction with a proton or the functional group having an electron include a crown ether structure, an aza crown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure, and among these, a primary amine structure, a secondary amine structure, and a tertiary amine structure are preferable.
The compound (II) is not particularly limited, and examples thereof include compounds represented by the following formulas (IIa-1) and (IIa-2).
[ chemical formula 69]
In the above formula (IIa-1), A 61a - A is a 61b - Respectively with A in the above formula (Ia-1) 11 - The meaning is the same, and the preferred mode is the same. And M is 61a + M and M 61b + Respectively with M in the above formula (Ia-1) 11 + The meaning is the same, and the preferred mode is the same.
In the above formula (IIa-1), L 61 L and L 62 Respectively with L in the above formula (Ia-1) 1 The meaning is the same, and the preferred mode is the same.
In the formula (IIa-1), R 2X An organic group having a valence of 1. As represented by R 2X The organic group having a valence of 1 is not particularly limited, and examples thereof include-CH 2 Can be selected from-CO-, -NH-, -O-, -S-, -SO-and-SO-, and 2 1 or 2 or more kinds of the groups are substituted in combination, and are preferably an alkyl group (preferably having 1 to 10 carbon atoms, which may be straight-chain or branched), a cycloalkyl group (preferably having 3 to 15 carbon atoms), or an alkenyl group (preferably having 2 to 6 carbon atoms).
The alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom (preferably a fluorine atom).
In the above formula (IIa-1), the reaction of M 61a + M and M 61b + Represented organic cations are replaced by H + The PIIa-1 compound is derived from A 61a Acid dissociation constant a1-7 of acid site represented by H and derived from A 61b The acid dissociation constants a1 to 8 of the acid sites represented by H correspond to the acid dissociation constant a1 described above.
In the compound (IIa-1), the cation site M in the structural site X is replaced with 61a + M and M 61b + Take the place of H + The PIIa-1 compound corresponds to HA 61a -L 61 -N(R 2X )-L 62 -A 61b H. And, the compound PIIa-1 is prepared by reacting with actinic raysOr the same acid generated by the compound represented by formula (IIa-1) upon irradiation with radiation.
And M is 61a + 、M 61b + 、A 61a - 、A 61b - 、L 61 、L 62 R is R 2X At least one of them may have an acid-decomposable group as a substituent.
In the above formula (IIa-2), A 71a - 、A 71b - A is a 71c - Respectively with A in the above formula (Ia-J) 11 - The meaning is the same, and the preferred mode is the same. And M is 71a + 、M 71b + M and M 71c + Respectively with M in the above formula (Ia-1) 11 + The meaning is the same, and the preferred mode is the same.
In the above formula (IIa-2), L 71 、L 72 L and L 73 Respectively with L in the above formula (Ia-1) 1 The meaning is the same, and the preferred mode is the same.
In the above formula (IIa-2), the reaction of M 71a + 、M 71b + M and M 71c + Represented organic cations are replaced by H + The PIIa-2 compound is derived from A 71a Acid dissociation constant a1-9 of acid site represented by H derived from A 71b Acid dissociation constant a1-10 of acid site represented by H and derived from A 71c The acid dissociation constants a1 to 11 of the acid sites represented by H correspond to the acid dissociation constant a1 described above.
In the compound (IIa-1), the cation site M in the structural site X is replaced with 71a + 、M 71b + M and M 71c + Take the place of H + The PIIa-2 compound corresponds to HA 71a -L 71 -N(L 73 -A 71c H)-L 72 -A 71b H. The compound PIIa-2 is the same as an acid produced by the compound represented by the formula (IIa-2) upon irradiation with actinic rays or radiation.
And M is 71a + 、M 71b + 、M 71c + 、A 71a - 、A 71b - 、A 71c - 、L 71 、L 72 L and L 73 At least one of them may have an acid-decomposable group as a substituent.
The anionic sites that compound (I) and compound (II) may have are exemplified, but the present invention is not limited to these.
[ chemical formula 70]
[ chemical formula 71]
As the compound (B), for example, photoacid generators disclosed in paragraphs [0135] to [0171] of International publication No. 2018/193954, paragraphs [0077] to [0116] of International publication No. 2020/066824, paragraphs [0018] to [0075] and paragraphs [0334] to [0335] of International publication No. 2017/154345 are also preferably used.
The content of the compound (B) in the resist composition is not particularly limited, but is preferably 1 mass% or more, more preferably 5 mass% or more, and still more preferably 10 mass% or more, based on the total solid content of the resist composition, from the viewpoint of further squaring the cross-sectional shape of the formed pattern. The content of the compound (B) is preferably 80 mass% or less, more preferably 70 mass% or less, and further preferably 60 mass% or less, based on the total solid content of the resist composition.
The compound (B) may be used alone or in combination of 1 or 2 or more.
The compound (B) may be the following compound (X).
< Compound (X) >)
The compound (X) is a salt containing a cation (specific cation) represented by the following formula (X).
[ chemical formula 72]
In the formula (X), ar X Represents an aryl group substituted with a group containing a halogen atom.
From Ar x The aryl groups represented may be monocyclic or polycyclic. The aryl group may be a heterocyclic ring containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
Examples of the heterocycle include a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring.
The number of carbon atoms of the above aryl group (Ar) X The number of carbon atoms) is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 to 10.
The group containing a halogen atom means a group containing a halogen atom as a part of a substituent and itself.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or an iodine atom is preferable.
Examples of the group containing a halogen atom include a halogen atom, a halogenated alkyl group, a halogenated alkoxy group, and a halogenated aryl group.
The number of halogen atoms in the aryl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.
The number of groups containing a halogen atom of the aryl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
The above aryl group may be substituted for a group containing no halogen atom in addition to a group containing a halogen atom. The halogen-free group is preferably an alkyl group (preferably having 1 to 6 carbon atoms), an alkoxy group or an alkoxycarbonyl group, more preferably an alkyl group (preferably having 1 to 6 carbon atoms) or an alkoxy group (preferably having 1 to 6 carbon atoms).
The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
R X11 ～R X16 Each independently represents a hydrogen atom or a hydrocarbon group.
R X11 ～R X12 Preferably a hydrocarbon group. R is R X13 ～R X16 Preferably represents a hydrogen atom.
The hydrocarbon group may be linear, branched or cyclic.
Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, and an alkyl group is preferable.
The number of carbon atoms of the hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
R X11 And R is R X12 Can be bonded to each other to form a ring, R X11 And R is R X13 ～R X16 At least one of or R X12 And R is R X13 ～R X16 May be bonded to each other to form a ring.
n and m each independently represent an integer of 1 or more.
N and m are preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2. In addition, n and m preferably represent the same integer.
When n represents an integer of 2 or more, 2 or more R' s X13 R of 2 or more X14 May be the same or different from each other. And when m represents an integer of 2 or more, 2 or more R X15 R of 2 or more X16 May be the same or different from each other.
L X Represents a 2-valent linking group.
Examples of the 2-valent linking group include-CO-, -NR A -、-O-、-S-、-SO-、-SO 2 -、-N(SO 2 -R A ) -cycloalkylene radical alkenylene groups and a 2-valent linking group formed by combining a plurality of alkenylene groups, preferred is a 2-valent linking group comprising an oxygen atom.
As the 2-valent linking group containing an oxygen atom, for example, it is exemplified by-CO-; -O-, -SO 2 -、-N(SO 2 -R A ) And a 2-valent linking group formed by combining a plurality of them. As R A Examples thereof includeHydrogen atom or alkyl group having 1 to 6 carbon atoms is produced.
Among them, the 2-valent linking group containing an oxygen atom is preferably-O-, -CO-or-N (SO 2 -R A ) -, more preferably-O-or-CO-.
The 2-valent linking group containing an oxygen atom means a 2-valent linking group containing an oxygen atom as part of the oxygen atom itself and the 2-valent linking group.
The number of oxygen atoms in the 2-valent linking group containing an oxygen atom is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
As the specific cation, a cation represented by the formula (X-1) is preferable.
[ chemical formula 73]
In the formula (X-1), X 1 Represents a group containing a halogen atom.
X 1 Ar is contained in the formula (X) x The halogen atoms are the same in meaning and the preferred ranges are also the same.
Y 1 Represents a group containing no halogen atom.
The halogen-free group is preferably an alkyl group (preferably having 1 to 6 carbon atoms), an alkoxy group or an alkoxycarbonyl group, and more preferably an alkyl group (preferably having 1 to 6 carbon atoms) or an alkoxy group.
The halogen-free group means a group containing no halogen atom as a part of a substituent. Namely Y 1 The representation includes the representation of the sum of X 1 Groups other than the groups of the halogen atom represented.
a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a+b is 1 to 5.
A is preferably 1 to 4. B is preferably 1 to 4.
R X20 ～R X29 Each independently represents a hydrogen atom or a hydrocarbon group.
R X20 ～R X21 R in the formula (X) X11 ～R X12 The meaning is the same, and the preferred ranges are also the same.
From R X22 ～R X29 The hydrocarbyl group represented may be linear, branched or cyclic.
As represented by R X22 ～R X29 Examples of the hydrocarbyl group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, and an alkyl group is preferable.
From R X22 ～R X29 The number of carbon atoms of the hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
R X20 And R is R X21 Can be bonded to each other to form a ring, R 20 And R is R X22 ～R X25 At least one of or R X21 And R is R X26 ～R X29 May be bonded to each other to form a ring.
The specific cations may be used alone or in combination of 1 or more than 2.
The molecular weight of the compound (X) is preferably 100 to 10000, more preferably 100 to 2500, still more preferably 100 to 1500.
The preferable range of the content of the compound (X) is the same as the preferable range of the content of the aforementioned compound (B).
The compound (X) may be used alone or in combination of 1 or 2 or more. When 2 or more kinds are used, the total content thereof is preferably within the above-mentioned preferred content range.
Specific examples of the compound (X) are shown below, but the present invention is not limited to these.
[ chemical formula 74]
[ chemical formula 75]
[ acid diffusion controlling agent ]
The resist composition may contain an acid diffusion control agent.
The acid diffusion controlling agent captures an acid generated from a photoacid generator or the like upon exposure, and functions as a quencher that suppresses a reaction of the acid-decomposable resin in the unexposed portion due to the acid generated in excess.
Examples of the acid diffusion controlling agent include a basic Compound (CA), a low-molecular Compound (CB) having a nitrogen atom and a group which is released by the action of an acid, and a compound (CC) which can reduce or eliminate the acid diffusion controlling agent by irradiation with actinic rays or radiation.
Examples of the compound (CC) include an onium salt Compound (CD) which exhibits a relatively weak acid with respect to the photoacid generator, and an alkali Compound (CE) which has reduced or eliminated alkali upon irradiation with actinic rays or radiation.
As the acid diffusion controlling agent, a known acid diffusion controlling agent can be suitably used.
For example, known compounds disclosed in paragraphs [0627] to [0664] of U.S. patent application publication 2016/007437A 1, paragraphs [0095] to [0187] of U.S. patent application publication 2015/0004544A1, and paragraphs [0403] to [0423] of U.S. patent application publication 2016/0237190A1, and paragraphs [0259] to [0328] of U.S. patent application publication 2016/0274458A1 can be preferably used as the acid diffusion controlling agent.
Further, for example, as a specific example of the basic Compound (CA), those described in paragraphs [0132] to [0136] of Japanese patent application laid-open No. 2020/066824, as a specific example of the basic Compound (CD) whose basicity is reduced or lost by irradiation with actinic rays or radiation, those described in paragraphs [0137] to [0155] of Japanese patent application laid-open No. 2020/066824, as a specific example of the low molecular Compound (CB) having a nitrogen atom and having a group which is detached by the action of an acid, those described in paragraphs [0156] to [0163] of Japanese patent application laid-open No. 2O20/066824, and as a specific example of the onium salt Compound (CE) having a nitrogen atom in the cationic portion, those described in paragraph [ 2020/066824 ] are cited.
Specific examples of onium salt Compounds (CD) which are relatively weak acids of photoacid generators include those described in paragraphs [0305] to [0314] of International publication No. 2020/158337, paragraphs [0455] to [0464] of International publication No. 2020/158467, paragraphs [0298] to [0307] of International publication No. 2020/158366, and paragraphs [0357] to [0366] of International publication No. 2020/158417.
When the acid diffusion controlling agent is contained in the resist composition, the content of the acid diffusion controlling agent (in the case where a plurality of kinds are present, the total thereof) is preferably 0.1 to 15.0% by mass, more preferably 1.0 to 15.0% by mass, relative to the total solid content of the composition.
In the resist composition, 1 kind of the acid diffusion controlling agent may be used alone, or 2 or more kinds may be used in combination.
[ hydrophobic resin (D) ]
The resist composition may further contain a hydrophobic resin different from the resin (a).
The hydrophobic resin is preferably designed to be biased to the surface of the resist film, but unlike the surfactant, it is not necessarily required to have a hydrophilic group in the molecule, and it may not contribute to uniform mixing of the polar substance and the nonpolar substance.
The effect of adding the hydrophobic resin includes control of static and dynamic contact angles of the resist film surface with respect to water and suppression of outgas (outgas).
From the viewpoint of biasing the film surface layer, the hydrophobic resin preferably has fluorine atoms, silicon atoms and CH contained in the side chain portion of the resin 3 Any one of the partial structures is 1 or more, and more preferably 2 or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted with a side chain.
Examples of the hydrophobic resin include those described in paragraphs [0275] to [0279] of Japanese patent application laid-open No. 2020/004306.
When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 15.0% by mass, relative to the total solid content of the resist composition.
[ surfactant (E) ]
The resist composition may also contain a surfactant. When the surfactant is contained, a pattern having more excellent adhesion and fewer development defects can be formed.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant.
Examples of the fluorine-based and/or silicon-based surfactant include surfactants disclosed in paragraphs [0218] and [0219] of Japanese patent application laid-open No. 2018/19395.
These surfactants may be used alone or in combination of 1 or 2 or more.
When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, relative to the total solid content of the composition.
[ other additives ]
The resist composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility to a developer (for example, a phenol compound having a molecular weight of 1000 or less or an alicyclic or aliphatic compound containing a carboxyl group).
The resist composition may further comprise a dissolution inhibiting compound. The "dissolution-inhibiting compound" herein is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid and has reduced solubility in an organic developer.
The resist composition of the present invention is suitably used as a photosensitive composition for EUV light.
Since the wavelength of EUV light is 13.5nm, which is shorter than ArF (wavelength 193 nm) light, the number of incident photons at the time of exposure with the same sensitivity is small. Therefore, the influence of "photon shot noise" having a deviation in the number probability of photons is large, resulting in deterioration of LER and bridging defect. In order to reduce photon shot noise, there is a method of increasing the number of incident photons by increasing the exposure amount, but this is a trade-off with the requirement for high sensitivity.
When the a value obtained by the following formula (1) is high, the absorption efficiency of EUV light and electron beams of a resist film formed from the resist composition becomes high, which is effective for reducing photon shot noise. The a value represents the absorption efficiency of EUV light and electron beams in the mass ratio of the resist film.
Formula (1): a= ([ H ] ×0.04+ [ C ] ×1.0+ [ N ] ×2.1+ [ O ] ×3.6+ [ F ] ×5.6+ [ S ] ×1.5+ [ I ] ×39.5)/([ H ] ×1+ [ C ] ×12+ [ N ] ×14+ [ O ] ×16+ [ F ] ×19+ [ S ] ×32+ [ I ] ×127)
The value A is preferably 0.120 or more. The upper limit is not particularly limited, but if the a value is too large, EUV light and electron beam transmittance of the resist film is reduced, and as a result, an optical image profile in the resist film is deteriorated, and it is difficult to obtain a good pattern shape, so that it is preferably 0.240 or less, more preferably 0.220 or less.
In addition, in the formula (1), [ H ] represents the molar ratio of hydrogen atoms derived from the total solid content to all atoms of the total solid content in the actinic or radiation-sensitive resin composition, [ C ] represents the molar ratio of carbon atoms derived from the total solid content to all atoms of the total solid content in the actinic or radiation-sensitive resin composition, [ N ] represents the molar ratio of nitrogen atoms derived from the total solid content to all atoms of the total solid content in the actinic or radiation-sensitive resin composition, [ O ] represents the molar ratio of oxygen atoms derived from the total solid content to all atoms of the total solid content in the actinic or radiation-sensitive resin composition, [ F ] represents the molar ratio of fluorine atoms derived from the total solid content to all atoms of the total solid content in the actinic or radiation-sensitive resin composition, [ S ] represents the molar ratio of sulfur atoms derived from the total solid content to all atoms of the total solid content in the actinic or radiation-sensitive resin composition, and [ I ] represents the molar ratio of iodine atoms derived from the total solid content to all atoms in the actinic or radiation-sensitive resin composition.
For example, when the resist composition contains a resin (acid-decomposable resin) whose polarity is increased by the action of an acid, a photoacid generator, an acid diffusion control agent, and a solvent, the resin, the photoacid generator, and the acid diffusion control agent correspond to solid components. That is, all atoms of the total solid content correspond to the total of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent. For example, [ H ] represents the molar ratio of hydrogen atoms derived from the total solid content to all atoms of the total solid content, and is described based on the above examples, and [ H ] represents the molar ratio of the total of hydrogen atoms derived from the resin, hydrogen atoms derived from the photoacid generator, and hydrogen atoms derived from the acid diffusion control agent to the total of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent.
Calculation of a value when the structure and content of constituent components of the total solid content in the resist composition are known, the atomic number ratio contained is calculated. Even when the constituent components are unknown, the constituent atomic ratio of the resist film obtained by evaporating the solvent components of the resist composition can be calculated by an analytical method such as elemental analysis.
[ method of manufacturing electronic device ]
The present invention also relates to a method for manufacturing an electronic device including the above-described pattern forming method, and an electronic device manufactured by the manufacturing method.
A preferred embodiment of the electronic device of the present invention is mounted on an electric or electronic device (home appliance, OA (Office Automation, office automation), media-related device, optical device, communication device, or the like).
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts of use, proportions, processing contents and processing steps shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the examples shown below.
[ various Components of resist composition ]
[ resin ]
The resins P0l-1 to P0l-32 were synthesized by a known method. The ratio (content ratio (mol%) of each repeating unit), weight average molecular weight (Mw) and dispersity (Mw/Mn) are shown in tables 1 and 2.
The weight average molecular weight (Mw) and the dispersity (Mw/Mn) (in terms of polystyrene) of the resins Pol-01 to Pol-32 were measured by GPC (carrier: tetrahydrofuran (THF)). And the ratio of each unit passes 13 C-NMR (nuclear magnetic resonance: nuclear magnetic resonance).
TABLE 1
TABLE 2
The structural formulas of the repeating units (units) shown in tables 1 and 2 are shown below.
[ chemical formula 76]
[ chemical formula 77]
[ photo acid generator ]
The structures of photoacid generators (PAG-1 to PAG-27) used are shown below.
[ chemical formula 78]
/>
[ chemical formula 79]
[ chemical formula 80]
[ chemical formula 81]
The molecular weight of the acid produced by the photoacid generator is shown in tables 3 and 4 below.
TABLE 3
| Photoacid generator | Molecular weight of acid production |
| PAG-1 | 200 |
| PAG-2 | 322 |
| PAG-3 | 324 |
| PAG-4 | 405 |
| PAG-5 | 653 |
| PAG-6 | 336 |
| PAG-7 | 356 |
| PAG-8 | 304 |
| PAG-9 | 394 |
| PAG-10 | 472 |
| PAG-11 | 517 |
| PAG-12 | 421 |
| PAG-13 | 428 |
| PAG-14 | 541 |
| PAG-15 | 742 |
| PAG-16 | 493 |
| PAG-17 | 531 |
| PAG-18 | 393 |
| PAG-19 | 322 |
| PAG-20 | 458 |
| PAG-21 | 725 |
TABLE 4
| Photoacid generator | Molecular weight of acid production |
| PAG-22 | 468 |
| PAG-23 | 468 |
| PAG-24 | 795 |
| PAG-25 | 440 |
| PAG-26 | 348 |
| PAG-27 | 906 |
[ acid diffusion control agent, other additives ]
The structures of the acid diffusion controllers (PQ-01 to PQ-08, Q-01 to Q-04) and the structures of the other additives (CL-1) used are shown below. And E-3 is PF656 (fluorine-based surfactant, manufactured by OMNOVA Solutions Inc.).
[ chemical formula 82]
[ chemical formula 83]
[ hydrophobic resin ]
The aqueous resins D-1 to D-3 were synthesized by a known method. The ratio (content ratio (mol%)), weight average molecular weight (Mw) and dispersity (Mw/Mn) of each repeating unit (unit) are shown in Table 5.
The weight average molecular weights (Mw) and the dispersity (Mw/Mn) (in terms of polystyrene) of the hydrophobic resins D-1 to D-3 were measured by GPC (carrier: tetrahydrofuran (THF)). And the composition ratio (molar ratio) of the resin is determined by 13 C-NMR (nucloar magnetic resonance: nuclear magnetic resonance).
TABLE 5
The structural formula of the repeating unit (unit) shown in table 5 is shown below.
[ chemical formula 84]
[ solvent ]
The solvents used are shown below.
F-1: propylene Glycol Monomethyl Ether Acetate (PGMEA)
F-2: propylene Glycol Monomethyl Ether (PGME)
F-3: propylene glycol monoethyl ether (PGEE)
F-4: cyclohexanone
F-5: cyclopentanone (CNG)
F-6: 2-heptanone
F-7: lactic acid ethyl ester
F-8: gamma-butyrolactone
F-9: propylene carbonate
[ preparation of resist composition ]
The components shown in Table 6, table 7 and Table 8 were dissolved in the solvents shown in Table 6, table 7 and Table 8, and the resulting solution was filtered through a polyethylene filter having a pore size of 0.03. Mu.m, to prepare resist compositions (Res-01 to Res-52). The contents (parts by mass) of the components and solvents in the resist compositions are shown in tables 6, 7 and 8.
TABLE 6
TABLE 7
TABLE 8
[ preparation of organic System treatment liquid ]
Organic treatment solutions (R-01 to R-19) were prepared by mixing the organic solvents described in Table 9 below to the content ratios described in Table 9. The obtained organic treatment liquid is used as a developing solution or a rinse solution described later.
TABLE 9
[ formation of resist film, pattern formation, and development ]
An organic film AL412 (manufactured by Brewer Science Co.) was applied on a silicon wafer, and baked at 205℃for 60 seconds, thereby forming a film having a film thickness of 5 nm. Each of the resist compositions prepared as described in tables 10 and 11 was applied thereon, and baked (PB) at the temperatures described in tables 10 and 11 for 60 seconds, to form a resist film having a film thickness of 40 nm.
The silicon wafer having the obtained resist film was subjected to pattern irradiation with the same exposure amount on the entire surface of the wafer using an EUV exposure apparatus (manufactured by Exitech Corporation, miero Exposure Tool, NA0.3, quadrupol, outer sigma 0.68, inner sigma 0.36). In addition, as a mask, a mask having a line size=20 nm and a line width:pitch=1:1 was used. After the irradiation, baking (PEB) was performed on a hot plate at the temperature shown in tables 10 and 11 for 60 seconds. Then, the developing solutions described in the immersion tables 10 and 11 were spun and developed for 30 seconds, and the rinse solutions described in the tables 10 and 11 were poured onto the wafer, and after the wafer was rotated, baking was performed at 100 ℃ for 60 seconds, whereby a 1:1 line width and pitch pattern with a line width of 20nm was obtained.
[ evaluation of in-plane uniformity of line width ]
For the obtained line width and pitch pattern, a line width was measured using a length-measuring scanning electron microscope (SEM, hitachi, ltd. S-9380 II). The 3-fold value of the standard deviation (σ) of the measured line width, that is, 3σ, was calculated as an index of the in-plane uniformity of the line width. Specifically, exposure was performed on a wafer by using 1 lens having a vertical (y-axis direction) of 3.5mm and a horizontal (x-axis direction) of 6.5mm, and a total of 232 lenses having 8 columns in the x-direction and 29 rows in the y-direction, 10 length-measurement photographs (1 to 5 lines) were measured in each lens, and the average of the 10 length-measurement values was taken as the length-measurement value of that lens. The standard deviation of the measured length values of 232 lenses was multiplied by 3 times to be 3 sigma.
The results are shown in tables 10 and 11.
The unit of in-plane uniformity of line widths in tables 10 and 11 below is "nm".
TABLE 10
| Resist composition | PB | PEB | Developing solution | Eluent liquid | In-plane uniformity of line width | |
| Example 1 | Res-01 | 90℃ | 80℃ | R-12 | R-01 | 0.36 |
| Example 2 | Res-02 | 110℃ | 120℃ | R-02 | - | 0.36 |
| Example 3 | Res-03 | 120℃ | 80℃ | R-13 | R-03 | 0.34 |
| Example 4 | Res-04 | 130℃ | 130℃ | R-14 | R-04 | 0.24 |
| Example 5 | Res-05 | 80℃ | 100℃ | R-05 | - | 0.24 |
| Example 6 | Res-06 | 110℃ | 130℃ | R-12 | R-06 | 0.24 |
| Example 7 | Res-07 | 100℃ | 80℃ | R-19 | R-07 | 0.24 |
| Example 8 | Res-08 | 120℃ | 130℃ | R-01 | R-17 | 0.32 |
| Example 9 | Res-09 | 130℃ | 100℃ | R-12 | R-02 | 0.35 |
| Example 10 | Res-10 | 130℃ | 120℃ | R-12 | R-03 | 0.30 |
| Example 11 | Res-11 | 120℃ | 80℃ | R-01 | R-05 | 0.30 |
| Example 12 | Res-12 | 120℃ | 100℃ | R-13 | R-06 | 0.24 |
| Example 13 | Res-13 | 130℃ | 110℃ | R-12 | R-01 | 0.24 |
| Example 14 | Res-14 | 120℃ | 90℃ | R-13 | R-02 | 0.22 |
| Example 15 | Res-15 | 130℃ | 100℃ | R-03 | R-18 | 0.22 |
| Example 16 | Res-16 | 110℃ | 110℃ | R-12 | R-04 | 0.22 |
| Example 17 | Res-17 | 120℃ | 110℃ | R-13 | R-02 | 0.20 |
| Example 18 | Res-18 | 90℃ | 110℃ | R-06 | - | 0.20 |
| Example 19 | Res-19 | 80℃ | 80℃ | R-13 | R-03 | 0.20 |
| Example 20 | Res-20 | 130℃ | 110℃ | R-12 | R-02 | 0.20 |
| Example 21 | Res-21 | 120℃ | 100℃ | R-15 | R-03 | 0.20 |
| Example 22 | Res-22 | 90℃ | 130℃ | R-02 | - | 0.24 |
| Example 23 | Res-23 | 110℃ | 110℃ | R-15 | R-04 | 0.22 |
| Example 24 | Res-24 | 90℃ | 80℃ | R-12 | R-05 | 0.22 |
| Example 25 | Res-25 | 80℃ | 110℃ | R-16 | R-06 | 0.20 |
| Example 26 | Res-26 | 80℃ | 100℃ | R-01 | - | 0.24 |
| Example 27 | Res-27 | 90℃ | 100℃ | R-12 | R-02 | 0.22 |
| Example 28 | Res-28 | 130℃ | 100℃ | R-01 | R-07 | 0.22 |
| Example 29 | Res-29 | 80℃ | 130℃ | R-02 | - | 0.20 |
| Example 30 | Res-30 | 130℃ | 80℃ | R-14 | R-02 | 0.24 |
| Example 31 | Res-31 | 110℃ | 120℃ | R-12 | R-07 | 0.22 |
| Example 32 | Res-32 | 90℃ | 120℃ | R-12 | R-02 | 0.22 |
| Example 33 | Res-33 | 130℃ | 130℃ | R-12 | R-02 | 0.20 |
| Example 34 | Res-34 | 110℃ | 120℃ | R-16 | R-03 | 0.24 |
| Example 35 | Res-35 | 90℃ | 90℃ | R-12 | R-04 | 0.22 |
| Example 36 | Res-36 | 130℃ | 100℃ | R-01 | - | 0.22 |
| Example 37 | Res-37 | 80℃ | 120℃ | R-12 | R-07 | 0.20 |
| Example 38 | Res-38 | 100℃ | 90℃ | R-02 | - | 0.22 |
| Example 39 | Res-39 | 80℃ | 100℃ | R-01 | - | 0.20 |
| Example 40 | Res-40 | 80℃ | 90℃ | R-12 | R-02 | 0.28 |
| Example 41 | Res-41 | 100℃ | 90℃ | R-12 | R-01 | 0.26 |
| Example 42 | Res-42 | 120℃ | 130℃ | R-05 | - | 0.26 |
| Example 43 | Res-43 | 130℃ | 110℃ | R-12 | R-05 | 0.24 |
| Example 44 | Res-44 | 90℃ | 80℃ | R-02 | - | 0.24 |
| Example 45 | Res-45 | 120℃ | 130℃ | R-12 | R-02 | 0.37 |
| Comparative example 1 | Res-46 | 100℃ | 80℃ | R-05 | - | 0.50 |
| Example 46 | Res-27 | 90℃ | 100℃ | R-12 | R-08 | 0.31 |
| Comparative example 2 | Res-27 | 90℃ | 100℃ | R-12 | R-09 | 0.50 |
| Comparative example 3 | Res-27 | 90℃ | 100℃ | R-12 | R-10 | 0.50 |
| Comparative example 4 | Res-27 | 90℃ | 100℃ | R-12 | R-11 | 0.50 |
| Comparative example 5 | Res-27 | 90℃ | 100℃ | R-12 | R-12 | 0.50 |
TABLE 11
| Resist composition | PB | PEB | Developing solution | Eluent liquid | In-plane uniformity of line width | |
| Example 47 | Res-47 | 120℃ | 100℃ | R-01 | - | 0.24 |
| Example 48 | Res-48 | 120℃ | 100℃ | R-02 | - | 0.24 |
| Example 49 | Res-49 | 120℃ | 100℃ | R-03 | - | 0.24 |
| Example 50 | Res-50 | 120℃ | 100℃ | R-04 | - | 0.27 |
| Example 51 | Res-51 | 120℃ | 100℃ | R-02 | - | 0.24 |
| Example 52 | Res-52 | 120℃ | 100℃ | R-02 | - | 0.24 |
As is clear from the evaluation results of table 10 and table 11, the in-plane uniformity of the line width of the obtained pattern was excellent in the pattern formation method of examples.
In example 5 and comparative example 1, development was performed using the organic treatment solution R-05, and in example 5, the line width in-plane uniformity was excellent as compared with comparative example 1. This is considered to be because the organic treatment liquid R-05 did not uniformly wet and spread on the resist film because the negative-type chemically amplified resist composition (Res-46) negatively charged by the crosslinking reaction was used in comparative example 1.
In example 27 and comparative examples 2 to 5, development was performed using the organic treatment solution R-12, and in example 27, the line width in-plane uniformity was excellent as compared with comparative examples 2 to 5. This is considered to be because the rinse solutions used in comparative examples 2 to 5 are not specific organic treatment solutions in the present invention, and thus do not uniformly wet and spread on the resist film.
Industrial applicability
According to the present application, a pattern forming method capable of obtaining a pattern excellent in-plane uniformity of line width and a method for manufacturing an electronic device including the pattern forming method can be provided.
While the present application has been described in detail with reference to specific embodiments, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
The present application is based on japanese patent application (patent application 2021-9169) filed on 1 month 22 of 2021 and japanese patent application (patent application 2021-120391) filed on 7 month 21 of 2021, the contents of which are incorporated herein by reference.
Claims (13)
1. A pattern forming method, comprising:
(1) A step of forming a film using a actinic ray-or radiation-sensitive resin composition containing a resin (A) which is decomposed by the action of an acid and has an increased polarity and a compound (B) which generates an acid by irradiation with actinic rays or radiation;
(2) Exposing the film; a kind of electronic device with high-pressure air-conditioning system
(3) A step of developing and rinsing the exposed film with an organic treatment liquid containing butyl acetate and a hydrocarbon having 11 or more carbon atoms,
The content of the hydrocarbon having 11 or more carbon atoms in the organic treatment liquid is 1 mass% or more and 35 mass% or less.
2. The pattern forming method according to claim 1, wherein,
the hydrocarbon having 11 or more carbon atoms is undecane.
3. The pattern forming method according to claim 1 or 2, wherein,
the resin (A) having an increased polarity by decomposition with the action of an acid contains at least one selected from the group consisting of a group in which a hydrogen atom of a carboxyl group is replaced with a releasing group released by the action of an acid, a group in which a hydrogen atom of an alcoholic hydroxyl group is replaced with a releasing group released by the action of an acid, and a group in which a hydrogen atom of a phenolic hydroxyl group is replaced with a releasing group released by the action of an acid.
4. The pattern forming method according to any one of claims 1 to 3, wherein,
the resin (A) having increased polarity by decomposition by the action of an acid has a repeating unit represented by the following general formula (AX),
in the general formula (AX),
Xa 1 represents a hydrogen atom or an alkyl group,
Rx 1 ～Rx 3 each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group,
Rx 1 ～Rx 3 optionally bonded to form a ring.
5. The pattern forming method according to any one of claims 1 to 4, wherein,
the resin (A) having an increased polarity by decomposition with an acid has at least one ring group selected from a lactone group, a carbonate group, a sultone group and a hydroxyl group.
6. The pattern forming method according to any one of claims 1 to 5, wherein,
the resin (A) having increased polarity by decomposition by the action of an acid has a repeating unit represented by the following general formula (Y),
in the general formula (Y), the components are as follows,
a represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group,
l represents a single bond or a 2-valent linking group having an oxygen atom,
r represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, R being the same or different in the case where there are plural R's, which optionally form a ring together with each other,
a represents an integer of 1 to 3,
b represents an integer of 0 to (5-a).
7. The pattern forming method according to any one of claims 1 to 6, wherein,
the compound (B) which generates an acid by irradiation with actinic rays or radiation has a cation represented by the following general formula (ZaI) or a cation represented by the following general formula (ZaII),
in the general formula (ZaI), R 201 、R 202 R is R 203 Each independently represents an organic group,
in the general formula (ZaII), R 204 R is R 205 Each independently represents an organic group.
8. The pattern forming method as claimed in claim 7, wherein,
R in the general formula (ZaI) 201 、R 202 R is R 203 At least one of them is aryl, or R in the general formula (ZaII) 204 R is R 205 At least one of which is aryl.
9. The pattern forming method according to claim 7 or 8, wherein,
r in the general formula (ZaI) 201 、R 202 R is R 203 At least one of them has an acid-decomposable group, or R in the general formula (ZaII) 204 R is R 205 At least one of them has an acid-decomposable group.
10. The pattern forming method according to any one of claims 1 to 9, wherein,
the molecular weight of the acid produced by the compound (B) which produces an acid upon irradiation with actinic rays or radiation is 250 or more.
11. The pattern forming method according to any one of claims 1 to 10, wherein,
the content of the compound (B) which generates an acid upon irradiation with actinic rays or radiation is 10 mass% or more with respect to the total solid content of the actinic-ray-or radiation-sensitive resin composition.
12. The pattern forming method according to any one of claims 1 to 11, wherein,
the actinic-ray-or radiation-sensitive resin composition contains 2 or more of the above-mentioned compounds (B) which generate an acid upon irradiation with actinic rays or radiation, or at least one compound (B) selected from the following compounds (I) and (II) upon irradiation with actinic rays or radiation,
Compound (I):
is a compound having 1 or more of the following structural sites X and 1 or more of the following structural sites Y, and is a compound which generates an acid containing the following 1 st acid site derived from the following structural site X and the following 2 nd acid site derived from the following structural site Y by irradiation with actinic rays or radioactive rays,
structural part X: from anionic site A 1 - Cation site M 1 + Composition, and formed by irradiation of actinic rays or radiationFrom HA 1 The structural part of the 1 st acid part
Structural part Y: from anionic site A 2 - Cation site M 2 + Composition, and formed by irradiation of actinic rays or radiation 2 The structural part of the 2 nd acid part
Wherein the compound (I) satisfies the following condition I,
condition I: in the compound (I), the cation site M in the structural site X 1 + And the cationic site M in the structural site Y 2 + Take the place of H + The resulting compound PI has: acid dissociation constant a1 derived from cation site M in structural site X 1 + Take the place of H + Made of HA 1 An acidic moiety represented; and an acid dissociation constant a2 derived from the cation site M in the structural site Y 2 + Take the place of H + Made of HA 2 An acidic site represented, and the acid dissociation constant a2 is larger than the acid dissociation constant a1,
compound (II):
is a compound having 2 or more structural sites X and 1 or more structural sites Z described below, and is a compound which generates an acid containing 2 or more 1 st acid sites derived from the structural sites X and the structural sites Z by irradiation with actinic rays or radioactive rays,
structural part Z: the nonionic moiety of the acid can be neutralized.
13. A manufacturing method of an electronic device, comprising the pattern forming method according to any one of claims 1 to 12.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-009169 | 2021-01-22 | ||
| JP2021-120391 | 2021-07-21 | ||
| JP2021120391 | 2021-07-21 | ||
| PCT/JP2022/000432 WO2022158323A1 (en) | 2021-01-22 | 2022-01-07 | Pattern formation method and method for producing electronic device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116888539A true CN116888539A (en) | 2023-10-13 |
Family
ID=88257343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280011183.XA Pending CN116888539A (en) | 2021-01-22 | 2022-01-07 | Pattern forming method and method for manufacturing electronic device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116888539A (en) |
-
2022
- 2022-01-07 CN CN202280011183.XA patent/CN116888539A/en active Pending
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