Resin composition, pattern forming method, method for producing electronic device, and polymer

Abstract

Provided is a resin composition containing a polymer having a structural unit represented by general formula (NB) and a structural unit represented by general formula (MI-1), and a solvent. Also provided is a polymer having a structural unit represented by general formula (NB) and a structural unit represented by general formula (MI-1). In general formula (NB), R1, R2, R3, and R4 are each independently a hydrogen atom or an organic group having 1-30 carbon atoms, provided that at least one of R1, R2, R3 and R4 is a group having a -C(CF3)2OH group; and a1 is 0, 1 or 2. In general formula (MI-1), X is a monovalent organic group containing a cyclic skeleton.

Description

Resin composition, pattern forming method, electronic device manufacturing method and polymer

[0001] The present invention relates to a resin composition, a pattern forming method, a method for manufacturing an electronic device, and a polymer.

[0002] Various resin compositions are used in the manufacture of electronic devices, and as electronic devices become smaller and more complex and the circuits in electronic devices become finer, improvements in resin compositions are also continuing (e.g., Patent Documents 1 and 2).

[0003] Resist compositions are an important type of resin composition in the manufacture of electronic devices. A resin pattern can be formed on a substrate through a first step of applying the resist composition to a substrate to form a resin film, a second step of irradiating the resin film with actinic rays or radiation, and a third step of developing the resin film after the second step. By applying an etching gas to the substrate on which this resin pattern has been formed, only a portion of the substrate can be selectively etched. In other words, the resin pattern functions as an etching mask.

[0004] In the second step, development is often carried out using an alkaline developer, and therefore the resin composition and / or the polymer contained in the resin composition preferably have a suitable alkali solubility.

[0005] Furthermore, in view of the fact that the resin pattern functions as an etching mask, it is preferable that the resin composition and / or the polymer contained in the resin composition have high etching resistance.

[0006] JP 2022-131762 A International Publication No. 2016 / 049123

[0007] The present inventors have now conducted various investigations with the aim of providing a resin composition and a polymer that have suitable solubility in an alkaline developer and are preferably used in resist compositions.

[0008] As a result of their investigations, the inventors have completed the invention provided below.

[0009] 1. A resin composition comprising: a polymer having a structural unit represented by general formula (NB) below and a structural unit represented by general formula (MI-1) below; and a solvent. In the general formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that R １ , R ２ , R ３ and R ４ At least one of the groups is -C(CF ３ ) ２ a group having an OH group, １ is 0, 1 or 2. In general formula (MI-1), X represents a monovalent organic group containing a cyclic skeleton. 2. The resin composition according to 1., wherein the polymer further has a structural unit represented by the following general formula (MI-2): In general formula (MI-2), A is a hydrogen atom or a group containing an alkali-soluble group. 3. The resin composition according to 2., wherein A in general formula (MI-2) is a group containing a phenolic hydroxy group. 4. The resin composition according to any one of 1. to 3., wherein in general formula (NB), R １ , R ２ , R ３ and R ４ At least one of the above is a group represented by the following general formula (fa): ３ ) ２OH (fa) In general formula (fa), L is a single bond or an alkylene group having 1 to 6 carbon atoms. 5. The resin composition according to any one of 1. to 4., wherein X in general formula (MI-1) contains a cyclic aliphatic group. 6. The resin composition according to any one of 1. to 5., wherein the content of the structural unit represented by general formula (NB) in the polymer is 1 to 50 mol %, and the content of the structural unit represented by general formula (MI-1) in the polymer is 10 to 80 mol %. 7. The resin composition according to any one of 1. to 6., wherein the solubility in an alkaline developer changes due to the action of actinic rays or radiation. 8. 7. 8. A pattern forming method comprising: a first step of applying the resin composition described in 1. above onto a substrate to form a resin film; a second step of irradiating the resin film with actinic rays or radiation; and a third step of developing the resin film after the second step to obtain a substrate on which a resin pattern has been formed. 9. A method for manufacturing an electronic device comprising: a fourth step of etching the substrate on which a resin pattern has been formed, obtained by the pattern forming method described in 8. above; and a removal step of removing the resin pattern remaining on the substrate after the fourth step. 10. A polymer having a structural unit represented by the following general formula (NB) and a structural unit represented by the following general formula (MI-1). In the general formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that R １ , R ２ , R ３ and R ４ At least one of the groups is -C(CF ３ ) ２ a group having an OH group, １ is 0, 1 or 2. In general formula (MI-1), X represents a monovalent organic group containing a cyclic skeleton. 11. The polymer according to 10., further comprising a structural unit represented by the following general formula (MI-2): In general formula (MI-2), A is a hydrogen atom or a group containing an alkali-soluble group. 12. The polymer according to 11., wherein A in general formula (MI-2) is a group containing a phenolic hydroxy group. 13. The polymer according to any one of 10. to 12., wherein in general formula (NB), R １ , R ２ , R ３ and R ４ At least one of the above is a group represented by the following general formula (fa): ３ ) ２ OH (fa) In general formula (fa), L is a single bond or an alkylene group having 1 to 6 carbon atoms. 14. The polymer according to any one of 10. to 13., wherein X in general formula (MI-1) contains a cyclic aliphatic group. 15. The resin composition according to any one of 10. to 14., wherein the content of the structural unit represented by general formula (NB) is 1 to 50 mol %, and the content of the structural unit represented by general formula (MI-1) is 10 to 80 mol %.

[0010] According to the present invention, there are provided a resin composition and a polymer that have suitable solubility in an alkaline developer.

[0011] Hereinafter, embodiments of the present invention will be described in detail.

[0012] In this specification, unless otherwise specified, the expression "X to Y" in the description of a numerical range means at least X and at most Y. For example, "1 to 5% by mass" means "at least 1% by mass and at most 5% by mass."

[0013] In the description of groups (atomic groups) herein, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). The term "organic group" herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound. The term "electronic device" herein is used to encompass elements, devices, final products, etc. to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information and communication terminals, light-emitting diodes, physical batteries, and chemical batteries.

[0014] <Resin Composition> The resin composition of the present embodiment contains a polymer having a structural unit represented by the following general formula (NB) and a structural unit represented by the following general formula (MI-1), and a solvent.

[0015]

[0016] In the general formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that R １ , R ２ , R ３ and R ４ At least one of the following is -C(CF ３ ) ２ a group having an OH group, １ is 0, 1 or 2.

[0017] In general formula (MI-1), X represents a monovalent organic group containing a cyclic skeleton.

[0018] In the above polymer, the structural unit represented by general formula (NB) is —C(CF ３ ) ２ It has a group having an OH group. -C(CF３ ) ２ Since the OH group is an alkali-soluble group, the polymer exhibits alkali solubility. On the other hand, although the structural unit represented by general formula (MI-1) has a C═O structure, which is a polar group, it also has an atomic group X that is basically hydrophobic, and therefore has a relatively low affinity with an alkaline developer. It is believed that the polymer contains these two structural units, thereby having appropriate solubility in an alkaline developer. It is believed that such appropriate solubility leads to the ability to obtain a fine pattern and to suppress swelling of the pattern due to development treatment when the resin composition of this embodiment is used as a photosensitive resin composition to form a pattern.

[0019] In addition, the polymer has a polycyclic aliphatic skeleton in the structural unit represented by general formula (NB), and a monovalent organic group containing a cyclic skeleton is present in the structural unit represented by general formula (MI-1). The presence of these cyclic skeletons contributes to the excellent etching resistance of the resin composition of this embodiment. In other words, the resin composition of this embodiment is preferably used as a resist composition.

[0020] The resin composition of this embodiment will be described below, first with respect to the polymer and solvent, which are essential components, and then with respect to the optional components such as the crosslinking agent.

[0021] [Polymer] Structural unit represented by general formula (NB) R in general formula (NB) １ , R ２ , R ３ and R ４ Examples of the organic group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, and a carboxyl group.

[0022] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Examples of alkenyl groups include allyl, pentenyl, and vinyl groups. Examples of alkynyl groups include ethynyl groups. Examples of alkylidene groups include methylidene and ethylidene groups. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups. Examples of aralkyl groups include benzyl and phenethyl groups. Examples of alkaryl groups include tolyl and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, etc. Examples of the heterocyclic group include an epoxy group, an oxetanyl group, etc.

[0023] Considering the reaction with a compound containing two or more diazirine structures in one molecule (the mechanism of insertion of carbene into a C-H bond), R １ , R ２ , R ３ and R ４ It is believed that selecting a compound containing a large amount of C—H as R will lead to a further improvement in sensitivity. １ , R ２ , R ３ and R ４ As the organic group of R, a linear alkyl group having 3 to 30 carbon atoms is preferred. Taking into consideration the balance of other properties, １ , R ２ , R ３ and R ４The organic group R is preferably a linear alkyl group having 4 to 20 carbon atoms, more preferably a linear alkyl group having 4 to 10 carbon atoms. On the other hand, in terms of improving solubility in an alkaline developer, １ , R ２ , R ３ and R ４ It is preferred that one to three of the groups be hydrogen atoms and not be hydrophobic atomic groups such as alkyl groups.

[0024] In general formula (NB), R １ , R ２ , R ３ and R ４ At least one of the groups is -C(CF ３ ) ２ From the viewpoint of ease of synthesis and appropriate alkali solubility, R １ , R ２ , R ３ and R ４ One or two of the -C(CF ３ ) ２ is a group having an OH group, and more preferably R １ , R ２ , R ３ and R ４ One of them is -C(CF ３ ) ２ It is a group having an OH group.

[0025] -C(CF ３ ) ２ The group having an OH group is preferably a group represented by the following general formula (fa): -LC(CF ３ ) ２ OH (fa) In general formula (fa), L is a single bond or an alkylene group having 1 to 6 carbon atoms. This alkylene group having 1 to 6 carbon atoms may be linear or branched. L is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group.

[0026] Structural Unit Represented by General Formula (MI-1) X in general formula (MI-1) may be any monovalent organic group containing a cyclic skeleton. This cyclic skeleton may be an aromatic group such as a benzene ring, or may be a cyclic aliphatic group. In terms of the balance of various performances, X preferably contains a cyclic aliphatic group. The cyclic aliphatic group is preferably saturated and preferably does not contain a carbon-carbon double bond. Specifically, X is preferably a cycloalkyl group or a cyclic aliphatic group. More specifically, X is preferably a cyclopentyl group, cyclohexyl group, cyclooctyl group, norbornyl group, adamantyl group, or the like. X may or may not have a substituent. In terms of appropriately controlling solubility, it is preferable that X does not have a substituent.

[0027] Structural Unit Represented by General Formula (MI-2) From the viewpoint of optimizing alkali solubility and adjusting various performances, it is preferable that the polymer further has a structural unit represented by the following general formula (MI-2). When the polymer has a structural unit represented by general formula (MI-2), swelling of the pattern due to a developer may be more easily suppressed when a pattern is formed using the resin composition of this embodiment.

[0028]

[0029] In general formula (MI-2), A represents a hydrogen atom or a group containing an alkali-soluble group.

[0030] The alkali-soluble group includes a phenolic hydroxy group, a carboxy group, a -C(CF ３ ) ２ From the viewpoint of optimizing solubility and balancing various performances, A is preferably a group containing a phenolic hydroxy group. More specifically, A is -C ６ H ４ Preferably, A is —OH. Incidentally, even when A is a hydrogen atom, the structural unit represented by general formula (MI-2) has the function of improving the alkali solubility of the polymer. This is because the two carbonyl groups in the structural unit attract electrons from the N atom, making it easier for the hydrogen atom to dissociate.

[0031] Other Structural Units The polymer may or may not have structural units other than the above-listed structural units. Examples of structural units other than the above-listed structural units include a structural unit in which the maleimide structure in the structural unit represented by general formula (MI-1) is ring-opened, a structural unit in which the maleimide structure in the structural unit represented by general formula (MI-2) is ring-opened, and a structural unit derived from maleic anhydride or a derivative thereof.

[0032] Specific examples of structural units other than the above-listed structural units include those represented by the general formula (NB): １ , R ２ , R ３ and R ４ are all hydrogen atoms or organic groups having 1 to 30 carbon atoms, and -C(CF ３ ) ２ Specifically, in general formula (NB), R １ , R ２ , R ３ and R ４ Examples of structural units include those in which at least one of the groups is an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and the remaining groups are hydrogen atoms. The alkyl group here may be linear or branched. The alkyl group has, for example, 1 to 20 carbon atoms, preferably 1 to 10, and more preferably 3 to 8 carbon atoms. The cycloalkyl group has, for example, 5 to 8 carbon atoms. The aryl group has, for example, 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. The aralkyl group has, for example, 7 to 13 carbon atoms. This structural unit has the function of making the polymer appropriately hydrophobic, thereby adjusting the solubility in an alkaline developer.

[0033] Incidentally, in consideration of use as a resist composition, the polymer does not contain an epoxy group-containing structural unit, or if it does contain one, its proportion is preferably 5 mol% or less, preferably 3 mol% or less, and preferably 1 mol% or less of the total structural units of the polymer.Similarly, the polymer does not contain an oxetanyl group-containing structural unit, or if it does contain one, its proportion is preferably 5 mol% or less, preferably 3 mol% or less, and preferably 1 mol% or less of the total structural units of the polymer.Furthermore, the polymer does not contain a silicon atom-containing structural unit, or if it does contain one, its proportion is preferably 5 mol% or less, preferably 3 mol% or less, and preferably 1 mol% or less of the total structural units of the polymer.

[0034] Ratio of each structural unit The content ratio of the structural unit represented by general formula (NB) in the polymer is preferably 3 to 45 mol %, more preferably 5 to 35 mol %. Furthermore, the content ratio of the structural unit represented by general formula (MI-1) in the polymer is preferably 20 to 70 mol %, more preferably 30 to 60 mol %. When the polymer has a structural unit represented by general formula (MI-2), the content ratio thereof is preferably 10 to 65 mol %, more preferably 20 to 55 mol %, from the viewpoint of optimizing solubility in an alkaline developer and balancing various performances. When the polymer contains other structural units, for example, R in general formula (NB), １ , R ２ , R ３ and R ４ are all hydrogen atoms or organic groups having 1 to 30 carbon atoms, and -C(CF ３ ) ２ When the polymer contains a structural unit other than a group having an OH group, the content ratio thereof is preferably 1 to 50 mol %, more preferably 10 to 30 mol %, from the viewpoint of obtaining appropriate solubility. By appropriately adjusting the ratio of each structural unit in the polymer, the solubility of the polymer in an alkaline developer can be optimized. Furthermore, by appropriately adjusting the ratio of each structural unit in the polymer, it may be possible to improve the resolution of the pattern and suppress swelling of the pattern when the resin composition is subjected to alkaline development treatment to form a pattern.

[0035] Other Information About the Polymer The resin composition of this embodiment may contain only one polymer, or may contain two or more polymers. When the resin composition of this embodiment contains two or more polymers, all of the polymers may be polymers having a structural unit represented by general formula (NB) and a structural unit represented by general formula (MI-1), or some of the polymers may not be polymers having a structural unit represented by general formula (NB) and a structural unit represented by general formula (MI-1). However, from the viewpoint of reliably obtaining the effects, preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more of all the polymers in the resin composition are polymers having a structural unit represented by general formula (NB) and a structural unit represented by general formula (MI-1).

[0036] The weight-average molecular weight of the polymer may be adjusted as appropriate, taking into consideration factors such as appropriate solubility in an alkaline developer. The weight-average molecular weight of the polymer is, for example, 3,000 to 100,000, preferably 3,000 to 50,000, more preferably 3,000 to 12,000, and particularly preferably 3,000 to 6,000. From the viewpoint of further reducing pattern roughness when used as a resist composition, the polydispersity index (PDI) of the polymer is preferably 1.1 to 2.0, and more preferably 1.1 to 1.6.

[0037] The proportion of the polymer in the non-volatile components (components other than the solvent) of the resin composition is preferably 1 to 20% by mass, more preferably 1 to 15% by mass.

[0038] Polymer Synthesis and Purification Methods Polymers can usually be synthesized (produced) by radical polymerization. That is, a polymer can be synthesized (produced) by polymerizing a monomer (having a radically polymerizable carbon-carbon double bond) corresponding to the structural unit of each of the general formulae above in an appropriate organic solvent by the action of a radical initiator. Specific synthesis conditions can be referenced to publicly known information as appropriate. Furthermore, publicly known information can also be referenced as appropriate for methods for purifying the synthesized polymer (methods for reducing impurities). In particular, when the resin composition of this embodiment is used as a resist composition, it is preferable to reduce impurities as much as possible.

[0039] [Solvent] The resin composition of the present embodiment contains a solvent. In other words, the resin composition of the present embodiment is preferably a composition in which at least the polymer is dissolved or dispersed in a solvent. The solvent typically contains an organic solvent. Specific examples of the solvent include ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, and carbonate-based solvents.

[0040] Preferred solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and mixtures thereof.

[0041] The solvent may be a single solvent or a mixed solvent. The amount of the solvent used is appropriately adjusted so that the concentration of non-volatile components in the composition is usually about 1 to 20% by mass, preferably about 1 to 15% by mass.

[0042] [Components for Making Resin Composition Photosensitive] In order to use the resin composition of the present embodiment as a resist composition, the resin composition is preferably photosensitive. "Photosensitive" means that the solubility in an alkaline developer changes due to the action of actinic rays or radiation.

[0043] For example, the resin composition preferably contains a compound that generates an acid under the action of actinic rays or radiation (acid generator) and a compound that undergoes a crosslinking reaction under the action of acid (crosslinker). A resin film formed from a resin composition containing the acid generator and the crosslinker is irradiated with actinic rays or radiation, and then the resin film is developed, thereby forming a negative resin pattern.

[0044] As another example, the resin composition preferably contains a compound containing two or more diazirine structures in one molecule (hereinafter referred to as a diazirine compound). A negative resin pattern can be formed by irradiating a resin film formed from a resin composition containing a diazirine compound with actinic rays or radiation, and then developing the resin film. When the diazirine compound is irradiated with actinic rays or radiation, N is released from the diazirine structure. ２ is eliminated, generating a carbene (a dicoordinated carbon atom with only six valence electrons and no charge). The generated carbene reacts with a polymer to form a bond. In particular, because the generated carbene is inserted into a C-H bond, the polymer that reacts with the carbene does not need to have any special functional groups. Therefore, the diazirine compound can form bonds with a variety of polymers. In this embodiment, a diazirine compound containing two or more diazirine structures per molecule is used, and the polymer is "crosslinked" by the diazirine compound. As a result, the portions of the resin film that are irradiated with actinic rays or radiation become insoluble or poorly soluble in the developer. Therefore, a pattern can be formed by selectively irradiating a resin film with actinic rays or radiation and then performing a development process.

[0045] The di-diazine compound will be described below.

[0046] The number of diazirine structures in one molecule of the diazirine compound is usually 2 to 6, preferably 2 to 4, and more preferably 2 to 3.

[0047] The di-allyl idine compound preferably contains a structure represented by the following general formula (b): Specifically, the di-allyl idine compound preferably contains two or more structures represented by the following general formula (b) in one molecule.

[0048]

[0049] In general formula (b), R ＥＷＧ represents an electron-withdrawing group, when a plurality of R's are present, each independently represents a monovalent substituent, n represents an integer of 0 to 4, and * represents a bond to another chemical structure.

[0050] The two or more structures represented by general formula (b) present in one molecule of the di-diazine compound may be the same structure or different structures, and an example of the latter is compound (B) having, in one molecule, a structure represented by general formula (b) where n is 0 and a structure represented by general formula (b) where n is 1.

[0051] R ＥＷＧ R can be any group generally recognized in the field of organic chemistry as an electron-withdrawing group. ＥＷＧ Specifically, alkyl fluoride groups, alkyl chloride groups, -NO ２ , -CN, -CHO, -COR, -COOR, -COOH, -SO ２ R, -SO ３ Here, R is a monovalent organic group, and specific examples thereof include the same organic groups having 1 to 30 carbon atoms as in general formula (NB). From the viewpoints of ease of synthesis, cost, and sensitivity to electron beams or EUV light, R ＥＷＧ is preferably a fluorinated alkyl group, more preferably a perfluoroalkyl group, and even more preferably a trifluoromethyl group.

[0052] Specific examples of R include R in general formula (NB): １ , R ２ , R ３ and R ４ Examples of the diamine compound include an organic group having 1 to 30 carbon atoms, a halogen atom, and a hydroxy group. From the viewpoint of ease of synthesis and availability of the diamine compound, n is preferably 0.

[0053] The di-azine compound more preferably contains a structure represented by the following general formula (b1).

[0054]

[0055] In general formula (b1), R ＥＷＧ The definitions of R, n and * are the same as those in general formula (b). ＥＷＧ The preferred embodiments of R and n are the same as those given in formula (b).

[0056] In the structure represented by general formula (b1), the electron-donating property of the oxygen atom increases the reactivity of the di-azine structure portion, and carbene tends to be more easily generated by irradiation with an electron beam or EUV light. In other words, the use of a di-azine compound including the structure represented by general formula (b1) tends to further increase sensitivity.

[0057] The two or more structures represented by general formula (b1) present in one molecule of the di-diazine compound may be the same structure or different structures. An example of the latter is compound (B) having, in one molecule, a structure represented by general formula (b1) where n is 0 and a structure represented by general formula (b1) where n is 1.

[0058] Specifically, the di-azine compound can have a structure represented by the following general formula (BB).

[0059]

[0060] In formula (BB), A represents a group represented by formula (b) or (b1), k represents an integer of 2 or more, and L represents a k-valent linking group.

[0061] In general formula (BB), there may be a plurality of A's. The plurality of A's may have the same structure or different structures.

[0062] From the viewpoint of ease of synthesis and availability and the balance of various performances, k is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3.

[0063] When L is a divalent linking group, specific examples of L include a linear or branched alkylene group, a group in which two hydrogen atoms have been removed from an alicyclic group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —NR— (R is a monovalent organic group), —S—, and —SO ２-, a group in which two or more of these groups are linked together, etc. L is preferably a linear or branched alkylene group, an arylene group, -O-, or a group in which two or more of these groups are linked together. When L is a trivalent or higher valent linking group, L can specifically be a group in which one or more hydrogen atoms have been further removed from the above divalent linking group. L is typically a k-valent organic group.

[0064] In terms of ease of synthesis of the di-di-ridine compound, moderate curability, and the like, it is preferable that the "length" of the L moiety is moderate. Here, the "length" of the L moiety is defined as the number of atoms present on the shortest path from an atom in L in the di-ridine compound represented by general formula (BB) to which a certain A is directly covalently bonded as the starting point, tracing only the covalent bonds in L, to an atom to which another A is directly covalently bonded (end point). However, when A in the L moiety is a group represented by general formula (b1), the "length" of the L moiety is determined by including the oxygen atom linked to the benzene ring in general formula (b1) in L. In other words, when A in the L moiety is a group represented by general formula (b1), the oxygen atom in general formula (b1) is used as the starting point or end point. Furthermore, when the di-ridine compound has 3 or more A's, the shortest definable length is used as the "length." For example, if a di-diazine compound has three A's, A1, A2, and A3, and the "length" from A1 to A2 is 10 and the "length" from A1 to A2 is 12, then the "length" of the L moiety in this compound (B) is 10. For example, the "length" of the L moiety in BondLynx GEN-I used in the examples below is 1, the "length" of the L moiety in BondLynx GEN-IIIa is 10, and the "length" of the L moiety in BondLynx GEN-IIIe is 14.

[0065] In terms of ease of synthesis of the diazine compound, appropriate curability, and the like, the "length" of the L moiety is, for example, 1 to 20, preferably 1 to 16. As another example, the "length" of the L moiety is preferably 6 to 20, more preferably 8 to 20. When the L moiety is "appropriately long," the diazine compound (or carbene generated from the diazine compound) in the film formed from the composition is more likely to react with the polymer, which may further improve sensitivity. On the other hand, when the L moiety is "not too long," contact between the diazine compound (or carbene generated from the diazine compound) and the polymer is suppressed, which may improve the stability of the composition over time.

[0066] When L is electron-withdrawing or when L is substituted with an electron-withdrawing group, the stability over time of the composition tends to be improved. For example, by using a di-allylidine compound in which L has a fluorine atom in the general formula (BB), a di-allylidine compound in which L is an organic group substituted with a fluorine atom in the general formula (BB), a di-allylidine compound in which L is a fluorinated alkylene group in the general formula (BB), or the like, the stability over time of the composition tends to be improved. When L is electron-withdrawing or when L is substituted with an electron-withdrawing group, the stability over time of the composition tends to be improved. ２ It is believed that the elimination of L to generate carbene is thermodynamically somewhat unfavorable, that is, carbene generation is somewhat more difficult. For this reason, it is believed that unintended decomposition of the di-azine compound is suppressed, improving sensitivity. Although sensitivity may be somewhat reduced, when importance is attached to the stability over time of the composition, it is preferable to select a di-azine compound in which L is electron-withdrawing or in which L is substituted with an electron-withdrawing group.

[0067] The molecular weight of the di-allylidine compound is typically from 100 to 2000, preferably from 100 to 1000. The di-allylidine compound is typically a low molecular weight compound and is not a polymer.

[0068] Diazine compounds can be purchased from, for example, XlynX Materials Inc., which is based in Canada. Specific examples of diazine compounds include compounds having a diazine structure exemplified in Patent Document 2. Furthermore, diazine compounds having the structure shown below are also preferably used.

[0069]

[0070] When a di-di-idine compound is used, only one di-di-idine compound may be used, or two or more di-di-idine compounds may be used in combination. From the viewpoint of the balance of various properties, when a di-di-idine compound is used, the amount thereof is usually 5 to 50 parts by mass, preferably 8 to 40 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of the polymer.

[0071] [Other Optional Components] The resin composition of the present embodiment may contain optional components other than those described above. Examples of the optional components include a developing aid, a plasticizer, an antioxidant, a leveling agent, a surfactant, etc.

[0072] In particular, from the viewpoint of obtaining a resin film with good in-plane uniformity upon application, it is preferable to use one or more surfactants. The type of surfactant is not particularly limited. Any surfactant that is appropriately soluble or dispersible in a solvent can be used as appropriate. Examples of surfactants include those described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Other examples include the "F-Top" series from Shin-Akita Chemical Industry Co., Ltd., the "Fluorad" series from 3M, the "Megafac" series from DIC Corporation, and the "Surflon" series from AGC Sei Chemical Co., Ltd. Preferably, fluorine-based surfactants and silicone-based surfactants can be used as surfactants. In particular, nonionic surfactants containing fluorine atoms are preferably used. When a surfactant is used, the amount used can be, for example, 0.01 to 3 parts by mass, specifically 0.1 to 1 part by mass, per 100 parts by mass of the polymer.

[0073] <Method for forming a pattern and method for manufacturing an electronic device> A resin composition whose solubility in an alkaline developer changes due to the action of actinic rays or radiation, that is, a photosensitive resin composition, can be used to form a pattern through the following steps: A first step of applying the resin composition onto a substrate to form a resin film A second step of irradiating the resin film formed in the first step with an electron beam or EUV light A third step of developing the resin film after the second step to obtain a substrate on which a resin pattern has been formed A resin pattern can be formed on a substrate through these steps.

[0074] Furthermore, an electronic device can be manufactured by carrying out steps such as: a fourth step of etching the substrate on which the resin pattern obtained as described above has been formed; and a removal step of removing the resin pattern remaining on the substrate after the fourth step.

[0075] These steps will be specifically described below.

[0076] (First Step: Formation of Resin Film) The substrate on which the resin film is formed is not particularly limited. Examples include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, copper substrates, and copper-plated substrates. The substrate may be an unprocessed substrate or a substrate on which electrodes or elements are formed. An anti-reflective film may be provided on the substrate in advance. As the anti-reflective film, either an inorganic film type made of titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, or the like, or an organic film type made of a light absorber and a polymer material can be used. In addition, commercially available organic anti-reflective films such as the DUV30 series and DUV-40 series manufactured by Brewer Science, and the AR-2, AR-3, and AR-5 manufactured by Shipley, can also be used.

[0077] The method for forming the resin film is not particularly limited. In the field of electronic device manufacturing, spin coating using a spinner is common, but other methods may also be used. For example, spray coating using a spray coater, dipping, printing, roll coating, inkjet method, etc. may also be used.

[0078] The composition coated on the substrate is typically dried by a heat treatment. The heating temperature is usually 50 to 140°C, preferably 60 to 120°C. An appropriate drying temperature may be set from the viewpoints of rapid and sufficient drying of the solvent and suppression of carbene generation from the di-azine compound. The heating time varies depending on the heating device, but when a hot plate is used, it is usually 30 to 300 seconds, preferably about 60 to 180 seconds, and when a hot air oven is used, it is usually 5 to 60 minutes, preferably about 10 to 30 minutes.

[0079] The thickness (dry thickness) of the resin film is not particularly limited and may be adjusted appropriately depending on the size and aspect ratio of the pattern to be finally obtained. The thickness can be adjusted by adjusting the concentration of nonvolatile components in the composition or by changing the application method. The thickness is, for example, 10 to 1000 nm, specifically 20 to 500 nm.

[0080] (Second Step: Irradiation with Actinic Rays or Radiation) The exposure step is usually carried out by irradiating the resin film with actinic rays or radiation. Preferred examples of actinic rays or radiation include far ultraviolet rays, extreme ultraviolet rays (EUV light), and electron beams. When electron beams are used as actinic rays or radiation, the exposure dose is, for example, 10 to 1000 μC / cm ２ , specifically 20 to 500 μC / cm ２ The acceleration voltage of the electron beam can be, for example, 10 to 200 keV, specifically 30 to 150 keV. When irradiating with far ultraviolet or EUV light, the irradiation dose can be, for example, 0.1 to 500 mJ / cm. ２ , specifically 1 to 250 mJ / cm ２ It can be said that:

[0081] When irradiating a resin film with deep ultraviolet or EUV light to "pattern" the film, the deep ultraviolet or EUV light is usually irradiated through a photomask.

[0082] The alkali solubility of the resin composition of this embodiment is appropriately adjusted, and therefore the resin composition of this embodiment is preferably used for forming fine patterns using electron beams or EUV light.

[0083] If necessary, after irradiation with actinic rays or radiation and before the third step (development), the resin film may be heated (post-exposure bake). The temperature is, for example, 70 to 150° C., preferably 70 to 120° C. The time is usually 30 to 300 seconds, preferably 50 to 180 seconds, when using a hot plate, for example.

[0084] Post-exposure baking is usually performed in chemically amplified compositions to promote a chain reaction caused by the action of acid generated by irradiation with actinic rays or radiation. On the other hand, the resin composition of this embodiment is not necessarily chemically amplified. Specifically, resin compositions containing the aforementioned di-allylidine compound are not necessarily chemically amplified. Therefore, in principle, patterning is possible without post-exposure baking. However, post-exposure baking may be effective in some cases to promote decomposition of the di-allylidine compound and / or promote bond formation between the polymer and the di-allylidine compound.

[0085] (Third Step: Development) A pattern can be obtained by developing the resin film irradiated with actinic rays or radiation. Typically, development can be carried out using a developer by a method such as an immersion method, a puddle method, or a rotary spray method. By development, the unexposed areas of the photosensitive resin film are usually dissolved and removed, resulting in a negative pattern.

[0086] As the developer, an alkaline aqueous solution is usually used. Specific examples of the alkaline aqueous solution include (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. As the developer, an aqueous tetramethylammonium hydroxide solution is particularly preferred. The concentration of the tetramethylammonium hydroxide is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

[0087] Furthermore, as the developer, a developer containing an organic solvent, specifically a developer mainly composed of an organic solvent (the developer contains an organic solvent in an amount of 50% by mass or more). As the developer containing an organic solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, a hydrocarbon-based solvent, or the like can be used. For more specific information about developers containing an organic solvent, the descriptions in paragraphs 0299 ​​to 0305 of Patent Document 1 can be referred to.

[0088] By performing the third step, a resin pattern can be obtained on the substrate. After development, it is preferable to wash the resin pattern and the substrate with a rinse liquid. Ultrapure water or alcohol is suitable as the rinse liquid.

[0089] (Fourth Step: Etching) The substrate on which the resin pattern obtained by the first to third steps is formed can be etched to process the substrate. Specifically, by applying an etching gas to the substrate on which the resin pattern is formed, a pattern can be formed in the portions of the substrate on which the resin pattern is not formed. In other words, the resin pattern functions as a "resist pattern" that prevents the substrate from being processed during etching. The etching may be wet etching, but dry etching is usually used in terms of ease of microfabrication. The specific etching conditions and usable etching gases can be appropriately changed and optimized depending on the structure and specifications of the electronic device to be manufactured.

[0090] As described above, the pattern formed using the resin composition of this embodiment functions as a resist pattern during etching. In other words, the resin composition of this embodiment is preferably "for forming a resist pattern during an etching process." In other words, the resin composition of this embodiment is preferably not used for forming a permanent film (a film that remains in the final electronic device) such as an insulating film.

[0091] (Removal step) The resin pattern remaining after the fourth step (etching) is usually removed with a resist stripper. In addition, residues generated by etching can be removed with an etching residue remover. Known resist strippers and etching residue removers can be used as appropriate.

[0092] (Other Steps) In manufacturing the electronic device, various steps other than those described above, such as an ion implantation step, a bump electrode formation step, a rewiring formation step, and the like, may be carried out.

[0093] <Polymer> Up to this point, the description has focused on embodiments of a "resin composition" containing a polymer having a specific structural unit and a solvent. On the other hand, the polymer described in the <Resin composition> section is useful because it has alkali solubility and other desirable properties. In other words, the polymer described in the <Resin composition> section can be applied to various uses by itself and can be used for various purposes other than photosensitive resin compositions. Specific embodiments of the polymer have been described in the [Polymer] section of the <Resin composition> section, so further description will be omitted.

[0094] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0095] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. However, it should be noted that the present invention is not limited to the Examples.

[0096] <Preparation of Monomers> The following monomers were prepared.

[0097]

[0098] <Synthesis (Production) of Polymer> The polymer of Synthesis Example 1 shown in Table 1 below was synthesized (produced) as follows.

[0099] (1) HFANB (9.2 g, 33 mmol), CyMI (6.0 g, 33 mmol), and H-MI (3.2 g, 33.3 mmol) were weighed out. These were added to a polymerization solvent (anisole, 67 g). The solution containing the monomers was heated to 150°C while stirring under a nitrogen atmosphere. (2) VR-110 (0.51 g, 2 mmol), a polymerization initiator manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., was added to a solvent (anisole, 7.5 g). This polymerization initiator solution was added to the monomer polymerization solution heated to 150°C under a nitrogen atmosphere. The amount of polymerization initiator was 0.02 mol per 1 mol of monomer. The amounts of monomer and polymerization solvent were adjusted so that the non-volatile components of the monomer and polymerization initiator were approximately 20% by mass. (3) The polymerization solvent (2) containing the monomer and polymerization initiator was stirred for 1.5 hours at 150°C under a nitrogen atmosphere. (4) After heating and stirring were completed, the mixture was allowed to cool to room temperature. The cooled polymerization solvent was added dropwise to heptane in an amount four times the mass of the polymerization solvent, causing a white to yellow powder to precipitate. The powder was filtered, washed with heptane, and then dried overnight in a vacuum dryer at 80°C, yielding a white to yellow polymer powder.

[0100] The ratio of each structural unit in the obtained polymer was determined by measuring the amount of each remaining monomer in the polymerization solvent after the completion of the above (3) by gas chromatography. In other words, the amount of monomer introduced into the polymer was considered to be the amount of monomer charged minus the amount of remaining monomer.

[0101] The number average molecular weight Mn and weight average molecular weight Mw of the resulting polymer were determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0102] The polymers of Synthesis Example 2 and subsequent examples were synthesized in the same manner as in Synthesis Example 1, except that the types and ratios of the monomers used and the polymerization solvent were changed as shown in Table 1.

[0103] For the polymer of Synthesis Example 2, in a deuterated DMSO solvent １H-NMR measurement was carried out. As a result of the measurement, the following three peaks were confirmed as peaks derived from the functional groups in the monomers used: (i) 11.0-11.8 ppm: H in the NH group in H-MI (ii) 7.4-7.8 ppm: H in the hydroxy group in HFANB (iii) 3.5-3.9 ppm: H bonded to the carbon atom bonded to the N atom in the cyclohexyl group in CyMI

[0104] The incorporation rates of the respective monomers, calculated from the area ratios of the peaks (i), (ii), and (iii), were 28 mol%, 47 mol%, and 25 mol%, respectively, which were in close agreement with the monomer consumption rates measured by gas chromatography.

[0105] <Measurement of Polymer Dissolution Rate> The synthesized polymer was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a concentration of 10% by mass. Each of these solutions was spin-coated onto a silicon wafer, and the solvent was dried to obtain a resin film with a thickness T of approximately 300 nm. This resin film, together with the silicon wafer, was immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C, and the time t until the film thickness reached zero was measured. The dissolution rate was then calculated by calculating T / t.

[0106] <Preparation and Evaluation of Photosensitive Resin Compositions> A polymer listed in Table 2 below and one of the di-allylidine compounds listed below were dissolved in propylene glycol monomethyl ether acetate (PGMEA). Photosensitive resin compositions were prepared using this solution. The amount of the di-allylidine compound was 20 parts by mass per 100 parts by mass of the polymer. The non-volatile component concentration was adjusted to 10% by mass for the evaluation of [Alkali Solubility] (Table 2) and [Electron Beam Irradiation Dose and Film Remaining Rate] (Table 3) described below. Furthermore, the amount of PGMEA was adjusted to 3% by mass for the evaluation of [Line and Space (L / S) Pattern Formation] (Table 4).

[0107]

[0108] The resulting photosensitive resin composition was subjected to the following measurements and evaluations.

[0109] [Alkali Solubility] The resin composition was applied to a silicon wafer by spin coating, and the solvent was dried to obtain a resin film with a film thickness T of approximately 70 nm. This resin film, together with the silicon wafer, was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25° C. The time t until the film thickness became zero was measured, and the dissolution rate was calculated by calculating T / t.

[0110] [Electron Beam Irradiation Dose and Film Retention Rate] First, a composition was applied to a silicon wafer by spin coating, and a resin film was formed by drying the solvent. The thickness of the resin film at this time was as shown in Table 3. Next, the resin film was irradiated with an electron beam at an acceleration voltage of 130 keV. In order to understand the relationship between the electron beam irradiation dose and the film retention rate, the electron beam irradiation dose was set to 20 to 300 μC / cm in one resin film. ２ A plurality of regions were irradiated with electron beams at different doses between the silicon wafer and the resin film. After irradiation with the electron beam, the resin film was immersed together with the silicon wafer in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. The development time (the time the resin film was immersed in the developer) was as shown in Table 3.

[0111] [Line and space (L / S) pattern formation] First, a composition was applied to a silicon wafer by spin coating, and a resin film was formed by drying the solvent. The thickness of the resin film at this time was as shown in Table 3. Next, the resin film was irradiated with an electron beam at an acceleration voltage of 130 keV. The electron beam irradiation was selectively performed so as to form a 50 nm line and space (L / S) pattern, a 100 nm L / S pattern, or a 200 nm L / S pattern. The electron beam irradiation dose to the line portion was set as follows, taking into account the results of the above [Electron beam irradiation dose and film remaining rate]. Example 1 200 nm L / S: 150 μC / cm ２ , 100nm L / S: 150μC / cm ２ , 50nm L / S: 150μC / cm ２ Example 2 200 nm L / S: 150 μC / cm ２(100 nm L / S or less was not satisfactorily resolved) Example 3 200 nm L / S: 150 μC / cm ２ , 100nm L / S: 200μC / cm ２ , 50nm L / S: 250μC / cm ２ After irradiation with the electron beam, the resin film was immersed together with the silicon wafer in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide or an aqueous solution diluted with pure water to a tetramethylammonium hydroxide concentration of 1.19% by mass. The development time (the time the resin film was immersed in the developer) was as shown in Table 4. The surface of the silicon wafer after development was observed with an electron microscope to evaluate the resolution of the L / S pattern. Furthermore, if the pattern was resolved, the degree of swelling of the pattern was observed.

[0112] Table 1 summarizes information mainly related to the polymer. Tables 2 to 4 also summarize information mainly related to the composition and evaluation results of the photosensitive resin composition. In Table 1, "GBL" for the solvent means γ-butyrolactone. In Table 1, the mixing ratio of the polymerization solvent is a mass ratio. In Table 1, the "%" for the ratio of the structural unit derived from each monomer in the polymer means mol%.

[0113]

[0114]

[0115]

[0116]

[0117] As shown in Table 1, it was confirmed that the polymers of Synthesis Examples 1 to 12 had appropriate solubility in an alkaline developer. Furthermore, as shown in Table 2, it was confirmed that the resin compositions prepared using the polymers obtained in the Synthesis Examples and the diazine compound also had appropriate solubility in an alkaline developer.

[0118] Furthermore, by irradiating a resin film formed from a resin composition shown in Table 3 with an electron beam, the resin film became insoluble in an alkaline developer. Specifically, the residual film rate increased with increasing electron beam irradiation dose. In other words, it was demonstrated that the resin compositions shown in Table 3 can be preferably used as photosensitive resin compositions.

[0119] In addition, fine patterns could be formed by irradiating a resin film formed from the resin composition shown in Table 4 with an electron beam. In particular, when the resin compositions of Examples 1 and 3 were used, extremely fine patterns of 50 nm L / S could be formed. Incidentally, as far as observation under an electron microscope is concerned, swelling of the L / S patterns obtained in Examples 1 to 3 due to the developer was sufficiently suppressed.

[0120] This application claims priority based on Japanese Patent Application No. 2023-053506, filed March 29, 2023, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A polymer having a structural unit represented by general formula (NB) below, a structural unit represented by general formula (MI-1) below, and a structural unit represented by general formula (MI-2) below, A solvent; A resin composition comprising: 【Chemistry 1】 In the general formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that R １ , R ２ , R ３ and R ４ At least one of the groups is -C(CF ３ ) ２ is a group having an OH group, a １ is 0, 1 or 2. 【Chemistry 2】 In general formula (MI-1), X is a monovalent organic group containing a cyclic skeleton. 【Chemistry 3】 In general formula (MI-2), A is a group containing a phenolic hydroxy group.

2. A polymer having a structural unit represented by general formula (NB) below and a structural unit represented by general formula (MI-1) below, A solvent; The resin composition is used for forming a negative resin pattern by exposure to actinic rays or radiation and development treatment. 【Chemistry 1】 In the general formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that R １ , R ２ , R ３ and R ４ At least one of the groups is -C(CF ３ ) ２ is a group having an OH group, a １ is 0, 1 or 2. 【Chemistry 2】 In general formula (MI-1), X is a monovalent organic group containing a cyclic skeleton.

3. The resin composition according to claim 2, The resin composition, wherein the polymer further has a structural unit represented by the following general formula (MI-2): 【Chemistry 3】 In general formula (MI-2), A is a hydrogen atom or a group containing an alkali-soluble group.

4. The resin composition according to claim 3, A resin composition, wherein A in the general formula (MI-2) is a group containing a phenolic hydroxy group.

5. The resin composition according to any one of claims 1 to 4, In the general formula (NB), R １ , R ２ , R ３ and R ４ At least one of the above is a group represented by general formula (fa): -L-C(CF ３ ) ２ OH (fa) In general formula (fa), L is a single bond or an alkylene group having 1 to 6 carbon atoms.

6. The resin composition according to any one of claims 1 to 4, A resin composition, wherein X in the general formula (MI-1) contains a cyclic aliphatic group.

7. The resin composition according to any one of claims 1 to 4, The content ratio of the structural unit represented by general formula (NB) in the polymer is 1 to 50 mol %, The resin composition, wherein the content ratio of the structural unit represented by general formula (MI-1) in the polymer is 10 to 80 mol %.

8. The resin composition according to any one of claims 1 to 4, A resin composition whose solubility in an alkaline developer changes due to the action of actinic rays or radiation.

9. A first step of applying the resin composition according to claim 8 onto a substrate to form a resin film; a second step of irradiating the resin film with actinic rays or radiation; a third step of developing the resin film after the second step to obtain a substrate having a resin pattern formed thereon; A pattern forming method comprising:

10. A fourth step of etching the substrate on which the resin pattern is formed, the substrate being obtained by the pattern forming method according to claim 9 ; a removing step of removing the resin pattern remaining on the substrate after the fourth step; A method for manufacturing an electronic device, comprising:

11. A polymer having a structural unit represented by general formula (NB) below, a structural unit represented by general formula (MI-1) below, and a structural unit represented by general formula (MI-2) below. 【Chemistry 4】 In the general formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that R １ , R ２ , R ３ and R ４ At least one of the groups is -C(CF ３ ) ２ is a group having an OH group, a １ is 0, 1 or 2. 【Chemistry 5】 In general formula (MI-1), X is a monovalent organic group containing a cyclic skeleton. 【Chemistry 6】 In general formula (MI-2), A is a group containing a phenolic hydroxy group.

12. A polymer having a structural unit represented by general formula (NB) below and a structural unit represented by general formula (MI-1) below (however, this polymer does not fall under the category of a resin whose solubility in an alkaline developer increases by the action of an acid). 【Chemistry 4】 In the general formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that R １ , R ２ , R ３ and R ４ At least one of the groups is -C(CF ３ ) ２ is a group having an OH group, a １ is 0, 1 or 2. 【Chemistry 5】 In general formula (MI-1), X is a monovalent organic group containing a cyclic skeleton.

13. 13. The polymer of claim 11 or 12, In the general formula (NB), R １ , R ２ , R ３ and R ４ At least one of the above is a group represented by general formula (fa) below: -L-C(CF ３ ) ２ OH (fa) In general formula (fa), L is a single bond or an alkylene group having 1 to 6 carbon atoms.

14. 13. The polymer of claim 11 or 12, In the general formula (MI-1), X is a polymer containing a cyclic aliphatic group.

15. 13. The polymer of claim 11 or 12, The content ratio of the structural unit represented by the general formula (NB) is 1 to 50 mol %, A polymer having a content of the structural unit represented by the general formula (MI-1) of 10 to 80 mol %.

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