Photoresist composition and pattern formation method

Abstract

The present invention provides a photoresist composition and a pattern formation method. [Solution] A polymer having repeating units derived from the first monomer of formula (I). This polymer can be used in photoresist compositions. TIFF2026054452000046.tif44166 (R1-R6 are independently H, a linear / branched / alicyclic substituted / unsubstituted alkyl group having 1-20 carbon atoms, or a substituted / unsubstituted aromatic group having 5-20 carbon atoms; R2 is selected from null, a linear / branched or alicyclic substituted / unsubstituted alkylene group having 1 to a maximum of 20 carbon atoms, up to a maximum of 15 carbon atoms, or a substituted / unsubstituted aromatic group having 5-20 carbon atoms; n is an integer from 0 to 3, or R1 and R2 or R1 and R6 together with the carbon atoms in the ring structure to which they are bonded to form a cyclic structure.)

Description

[Technical Field]

[0001] The present invention relates to a photoresist composition and a patterning method using such a photoresist composition. The present invention finds particular applicability to lithography applications in the semiconductor manufacturing industry. [Background technology]

[0002] Photoresist materials are photosensitive compositions typically used to transfer images onto one or more underlying layers, such as metal, semiconductor, or dielectric layers, placed on a semiconductor substrate. High-resolution photoresists and photolithography tools have been and continue to be developed to increase the integration density of semiconductor devices and enable the formation of structures with dimensions in the nanometer range.

[0003] The latest lithography pattern formation processes currently use ArF (193nm) immersion scanners to process wafers to dimensions of less than 60 nanometers (nm). Pushing ArF lithography to the limit dimensions of less than 60nm presents several challenges regarding photoresist capabilities in terms of process window, linewidth roughness (LWR), and other critically important parameters for the mass production of integrated circuits. For example, as the semiconductor industry continues to pursue smaller and more advanced device nodes, the linewidth roughness (LWR) of photoresist becomes more critically important because linewidth variations along the gate length are determinants of its threshold voltage and leakage current, and therefore directly affect device performance. However, as pattern dimensions decrease at more advanced nodes, LWR values ​​do not decrease simultaneously at the same rate, becoming a significant source of variation during processing at those cutting-edge nodes. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Patent No. 8,431,325 [Patent Document 2] U.S. Patent No. 4,189,323 [Overview of the project] [Problems that the invention aims to solve]

[0005] There is a continuous need for photoresist compositions that address one or more problems associated with photolithography patterning at limit dimensions of less than 60 nm. In particular, there is a continuous need for photoresist compositions that can achieve improved resolution and reduced low-weight tolerance (LWR). Process window improvements are also useful for achieving high yields in integrated circuit manufacturing. [Means for solving the problem]

[0006] Equation (I) [ka] [In the formula, R1, R3, R4, R5, and R6 are independently H, a linear, branched, or alicyclic substituted or unsubstituted alkyl group having 1 to 2, or 3 to a maximum of 20, or up to 15, or up to 10 carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms; R2 is selected from null (i.e., directly bonded), a linear, branched, or alicyclic substituted or unsubstituted alkylene group having 1 to 2, or 3 to a maximum of 20, or up to 15, or up to 10 carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms; n is an integer from 0 to 3, or R1 and R2 or R1 and R6 together with the carbon atoms in the ring structure to which they are bonded to form a cyclic structure.] A polymer is provided comprising a first repeating unit derived from a first monomer of formula (II): The polymer optionally comprises a monomer of formula (II): [ka] (wherein, R7 is a hydrogen atom or a methyl group; R8 is a direct bond or a divalent linking group, and R9 is a lactone or a sultone) one or more ethylenically unsaturated monomers containing a monomer; a monomer (III) containing an acid-labile group, or formula (IV) (wherein each R 12 is a halogen, substituted or unsubstituted C 1~30 alkyl, substituted or unsubstituted C 1~30 heteroalkyl, substituted or unsubstituted C 3~30 cycloalkyl, substituted or unsubstituted C 2~20 heterocycloalkyl, substituted or unsubstituted C 2~20 alkenyl, substituted or unsubstituted C 3~20 cycloalkenyl, substituted or unsubstituted C 3~20 heterocycloalkenyl, C 6~30 aryl, substituted or unsubstituted C 7~30 arylalkyl, substituted or unsubstituted C 7~30 alkylaryl, substituted or unsubstituted C 3~30 heteroaryl, substituted or unsubstituted C 4~30 heteroarylalkyl, or substituted or unsubstituted C 4~30 alkylheteroaryl, wherein each R 12 optionally further contains a divalent linking group as part of its structure; R 13 and R 14 are each independently hydrogen, a halogen, substituted or unsubstituted C 1~30 alkyl, substituted or unsubstituted C 1~30 heteroalkyl, substituted or unsubstituted C 3~30 cycloalkyl, substituted or unsubstituted C 2~20 heterocycloalkyl, C 6~30 aryl, substituted or unsubstituted C 7~30 arylalkyl, substituted or unsubstituted C 7~30 alkylaryl, substituted or unsubstituted C 3~30 heteroaryl, substituted or unsubstituted C 4~30 heteroarylalkyl, or substituted or unsubstituted C 4~30 alkylheteroaryl, wherein R 13 and R 14Each of them independently optionally further includes a divalent linking group as part of its structure; or R 12 , R 13 , and R 14 Any two or more of these may together form a ring via single bonds or divalent linking groups; p is 1 or 2; n is an integer from 1 to 6) and may contain one or more additional repeating units derived from the monomer.

[0007] Photoresist compositions comprising the above-mentioned polymer, a photoacid generator, and a solvent are also provided herein. Methods for forming patterns are also provided herein, comprising: coating a layer of such photoresist composition onto a substrate to provide a photoresist composition layer; pattern-exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer to provide a photoresist pattern. [Modes for carrying out the invention]

[0008] Hereafter, exemplary embodiments will be described in detail, and examples thereof will be illustrated in this description. In this regard, these exemplary embodiments may take different forms and should not be construed as being limited to the descriptions expressed herein. Accordingly, exemplary embodiments are described below only by reference to the figures in order to illustrate aspects of this description.

[0009] The present invention relates to polymers useful for photoresist compositions and such photoresist compositions. A photoresist composition comprises a polymer; a photoacid generator (PAG); a solvent; and may contain additional, optional components. The inventors have discovered that using certain photoresist compositions of the present invention, photoresist films having improved lithographic properties, such as improved linewidth roughness (LWR), can be prepared.

[0010] The polymer of the photoresist composition contains a first repeating unit derived from a first monomer of formula I, which includes a lactone ring and an -OC(R4R5)-O- group such as an acetal or ketal group. In the resulting polymer structure, carbon atoms from the lactone ring form part of the polymer main chain.

[0011] It should be understood that the lactone ring of the first repeating unit is not detached from the polymer backchain or linked to it via a linking group. Rather, the lactone ring of the first repeating unit shares a tertiary carbon atom with the polymer backchain, and as a result, the lactone ring is directly incorporated into the polymer backchain. Without wishing to be bound by theory, the incorporation of the lactone ring into the polymer backchain provides a more rigid structure.

[0012] The first repeating unit is given by Equation 1 [ka] [wherein R1, R3, R4, R5, R6 are independently H, a linear, branched, or alicyclic substituted or unsubstituted alkylene group having 1, 2, or 3 to a maximum of 20, a maximum of 15, or a maximum of 10 carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms; R2 is selected from null (i.e., directly bonded), a linear, branched, or alicyclic substituted or unsubstituted alkyl group having 1, 2, or 3 to a maximum of 20, a maximum of 15, or a maximum of 10 carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms; n is an integer from 0 to 3, or R1 and R2 or R1 and R6 together with the carbon atoms in the ring structure to which they are bonded to form a cyclic structure (e.g., aliphatic, aromatic, heteroaliphatic, or heteroaromatic)] derived from monomers (i.e., polymerization products of monomers). Substitutive alkyl groups or aromatic groups may include halogen (e.g., fluorine), ether, carbonyl, ester, carboxylic acid, sulfoxide, sulfone, sulfonamide, or carboxamide groups. If the alkyl group is branched or includes an alicyclic structure, it contains at least three carbon atoms. For example, R1 may be H, methyl, or ethyl, preferably methyl. For example, R2 may be an alkylene group with 1, 2, 3, 4, or 5 carbon atoms, preferably 1 carbon atom. For example, R3 may be an alkyl group with 2, 3, 4, 5, 6, 7, 8, or 9 carbon atoms, which can be linear or branched, or may include a cycloalkyl group. For example, R4 and R5 may independently be H or an alkyl group with 1, 2, 3, or 4 carbon atoms. For example, n may be 1 or 2, preferably 1.

[0013] A non-restrictive example of the first monomer in formula (I) is: [ka] These are some examples.

[0014] A polymer typically contains a first repeating unit in an amount ranging from 1, 5, 10 to a maximum of 100, up to a maximum of 99, up to a maximum of 97, up to a maximum of 90, up to a maximum of 80, up to a maximum of 70, up to a maximum of 60, up to a maximum of 50, up to a maximum of 40, up to a maximum of 30, up to a maximum of 25, or up to 20 mol% (mol percent), based on the total moles of repeating units in the polymer.

[0015] The monomer of formula I can be copolymerized with one or more additional monomers that form one or more additional repeating units. The one or more additional monomers include ethylenically unsaturated carbon-carbon groups (e.g., vinyl groups). Examples of such ethylenically unsaturated groups include substituted or unsubstituted C2~ 20 Examples include alkenyl groups, substituted or unsubstituted norbornyl groups, substituted or unsubstituted (meth)acrylic groups, substituted or unsubstituted vinyl ether groups, substituted or unsubstituted vinyl ketone groups, substituted or unsubstituted vinyl ester groups, or substituted or unsubstituted vinyl aromatic groups. Typically, polymerizable groups are substituted or unsubstituted C2~ 20 The compounds are alkenyls, substituted or unsubstituted norbornyls, substituted or unsubstituted (meth)acrylics, or substituted or unsubstituted vinyl aromatics. Additional repeating units may be one or more additional units for the purpose of modifying the properties of the photoresist composition, such as etch rate and solubility. The additional repeating units may optionally provide functional groups, such as acid-unstable groups, polar groups, or base-soluble groups.

[0016] If one or more additional repeating units are present in the polymer, they may be used in amounts from 1, 3, 10, 20, 30, 40, 50, 60, or 70 up to a maximum of 99, 95, or 90 mol%, based on the total molar repeating units of the polymer (total amount of all additional repeating units of different structures).

[0017] For example, additional repeating units may include polar groups pendanted to the polymer's main chain. Exemplary polar groups include base-soluble repeating units (e.g., base-soluble repeating units having a pKa of 12 or less), other repeating units containing heteroatom-containing moieties, and repeating units containing substituents further substituted by heteroatom-containing moieties. Exemplary heteroatom-containing moieties that may be polar groups of the present invention include nitro(-NO2), cyano(-CN), and amino(-NR2, where R2 is hydrogen, C) 1~10 Alkyl, C 6~12 Ariel, C 3~12 Examples include, but are not limited to, heteroaryls (or combinations thereof), hydroxyl (-OH), alkoxys, carboxyls, aryloxys, thiols (-SH), arylthios, and sulfonyls. Such repeating units can be derived from ethylenically unsaturated monomers having polar functional groups.

[0018] For example, the additional repeating unit may contain a lactone-containing repeating unit, but without the acetal or ketal functional group of formula I, where the lactone ring is pendanted to the main chain of the polymer, and it is of formula (II): [ka] It may be derived from the monomer.

[0019] In formula (II), R7 is hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1~10 It may be alkyl or fluoroalkyl. R8 may be a single bond or a divalent linking group. R9 may be a substituted or unsubstituted C 4~20 Lactone-containing group or substituted or unsubstituted polycyclic C 4~20 These may be sultone-containing groups, each of which may be a monocyclic, non-condensed polycyclic, or condensed polycyclic group.

[0020] Non-restrictive examples of monomers in formula (II) include: [ka] (In the formula, R f (This is the same as the one defined for R7 in equation (II).) These are some examples.

[0021] Repeating units derived from the monomer of formula II may be present in amounts ranging from 0, 1, 5, 10, 20, 25, or 30 to a maximum of 80, 70, 60, 50, or 40 mol%, based on the total number of moles of repeating units in the polymer.

[0022] The polymer may further contain repeating units having acid-unstable groups, which can be cleaved by photo-generated acids under post-exposure bake conditions. Such repeating units may be derived, for example, from monomer III having ethylenically unsaturated and acid-unstable groups. For example, repeating units having acid-unstable groups have structures (III-a), (III-b), or (III-c): [ka] It can be derived from monomers that have [a certain characteristic].

[0023] In formulas (III-a) and (III-b), Re and Rf can independently be hydrogen, fluorine, cyano, or substituted or unsubstituted C1-10 alkyl or fluoroalkyl. Preferably, R e and R f Each of these can independently be hydrogen, fluorine, fluoroalkyl, or substituted or unsubstituted C1-5 alkyl, typically methyl.

[0024] In equation (III-a), L 6 L is a divalent linking group. For example, L 6 It may contain 1 to 10 carbon atoms and at least one heteroatom. In a typical example, L 6 is -OCH2-, -OCH2CH2O-, or -N(R a )- which is possible, and here, R a is hydrogen or C1~6 It is alkyl.

[0025] In equations (III-a) and (III-b), R 17 ~R 22 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 It is a heteroaryl, however, R 17 ~R 19 Only one of them can be hydrogen, R 20 ~R 22 The condition is that only one of them can be hydrogen, and R 17 ~R 19 If one of them is hydrogen, then R 17 ~R 19 At least one other is a substitution or non-substitution C 6~20 Aryl or substituted or unsubstituted C 3~20 It is a heteroaryl, and R 20 ~R 22 If one of them is hydrogen, then R 20 ~R 22 At least one other is a substitution or non-substitution C 6~20 Aryl or substituted or unsubstituted C 3~20 It is required that it be a heteroaryl compound. Preferably, R 17 ~R 22 These are, independently, substituted or non-substituted C 1~6 Alkyl or substituted or unsubstituted C 3~10 It is a cycloalkyl group. 17 ~R 22 Each of these may optionally further include a divalent linking group as part of their structure.

[0026] In formula (III-a), R 17 ~R 19 Any two of may optionally form a ring together via a single bond or a divalent linking group, where the ring may be substituted or unsubstituted. In formula (III-b), R 20 ~R 22 Any two of may optionally form a ring together via a single bond or a divalent linking group, where the ring may be substituted or unsubstituted.

[0027] For example, any one or more of R 17 ~R 22 may independently be a group of the formula -CH2C(=O)CH (3-n) Y n where each Y is independently a substituted or unsubstituted C 2~10 heterocycloalkyl, and n is 1 or 2. For example, each Y may independently be a substituted or unsubstituted C a1 )(C a2 )O- containing heterocycloalkyl of the formula O(C 2~10 where C a1 and C a2 are each independently hydrogen or substituted or unsubstituted alkyl, where C a1 and C a2 may optionally form a ring together.

[0028] In formula (III-c), R 23 ~R 25 may each independently be substituted or unsubstituted C 1~20 alkyl, substituted or unsubstituted C 3~20 cycloalkyl, substituted or unsubstituted C 3~20 heterocycloalkyl, substituted or unsubstituted C 6~20 aryl, or substituted or unsubstituted C 3~20 heteroaryl, provided that only one of R 23 ~R 25 may be hydrogen, and when one of R 23 ~R 25 is hydrogen, R 23 ~R 25At least one other is a substitution or non-substitution C 6~20 Aryl or substituted or unsubstituted C 3~20 The condition is that it is a heteroaryl compound. 23 ~R 25 Each of these may optionally further include a divalent linking group as part of its structure. 23 ~R 25 Any two of them may optionally form a ring together, and the ring may further contain divalent linking groups as part of its structure.

[0029] In equation (III-c), X d is either substituted or non-substituted C2~ 20 It is a polymerizable group selected from alkenyls or substituted or unsubstituted norbornyls.

[0030] In equation (III-c), L 7 X can be a single bond or a divalent linking group, however, d is substituted or unsubstituted C2~ 20 If it is an alkenyl, L 7 The condition is that it is not a single bond. Preferably, L 7 is a substitution or non-substitution C 6~30 Arylene, or substituted or unsubstituted C 6~30 It is a cycloalkylene.

[0031] In equation (III-c), n1 is either 0 or 1. If n1 is 0, L 7 It should be understood that the group is directly bonded to the oxygen atom.

[0032] As another example, the acid-unstable group may be a tertiary alkyl ester. For example, a repeating unit containing a tertiary alkyl ester group may be derived from one or more monomers of formula (III-a), (III-b), or (III-c), where R 17 ~R 22 None of them are hydrogen, so n1 is 1.

[0033] Non-restrictive examples of monomers represented by formula (III-a) include: [ka] These are some examples.

[0034] Non-restrictive examples of monomers represented by formula (III-b) include: [ka] [ka] (In the formula, R d In equation (III-b), R f As defined herein; R ’ and R ’’ These are, independently, substituted or non-substituted C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 (It is a heteroaryl) These are some examples.

[0035] Non-restrictive examples of monomers represented by formula (III-c) include: [ka] These are some examples.

[0036] Repeating units containing acid-unstable groups have tertiary alkoxy groups, for example, formula: [ka] It may be derived from one or more monomers.

[0037] The polymer may contain repeating units containing acid-unstable groups in amounts ranging from 0, 1, 5, 10, 20, or 30 to a maximum of 80, 70, 60, 50, or up to 40 mol%, based on the total repeating units in the polymer.

[0038] A polymer may contain two or more different repeating units, each containing an acid-unstable group. If a polymer contains two or more different repeating units, each containing an acid-unstable group, the total amount of repeating units containing acid-unstable groups in the polymer may be 1 to 80 mol%, more typically 5 to 75 mol%, and even more typically 5 to 50 mol%, based on the total number of repeating units in the polymer.

[0039] The polymer is, Formula IV: [ka] (In the formula, each R 12 This is halogen, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 4~30 It is an alkyl heteroaryl, where each R 12 It optionally further includes a divalent linking group as part of its structure; R 13 and R 14 These are, independently, hydrogen, halogen, substituted or unsubstituted C. 1~30Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 2~20 Heterocycloalkyl, C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 4~30 It is an alkyl heteroaryl, where R 13 and R 14 Each of them independently optionally further includes a divalent linking group as part of their structure; R 12 , R 13 , and R 14 Any two or more of these elements can be optionally joined together to form a ring via single bonds or divalent linking groups; m is 1 or 2; p is an integer from 1 to 6. The polymer may contain repeating units derived from the monomer. The polymer may contain repeating units of structure IV in amounts ranging from 0, 1, 5, or 10 to a maximum of 50, a maximum of 40, or a maximum of 30 mol%, based on the total repeating units in the polymer.

[0040] The polymer may contain base-soluble repeating units having a pKa of 12 or less. For example, the base-soluble repeating units may be monomers of formulas (V), (VI), (VII), or combinations thereof: [ka] It can be derived from

[0041] In equations (V) to (VII), R h This is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R h is hydrogen, fluorine, or substituted or unsubstituted C 1~5Alkyl (for example, substituted alkyls can be fluoroalkyls), typically methyl.

[0042] In equation (V), R 27 is a substitution or non-substitution C 1~100 Or C 1~20 Alkyl, typically C 1~12 Alkyl; substituted or unsubstituted C 3~30 Or C 3~20 Cycloalkyl; or substituted or unsubstituted poly(C) 1~3 It may be an alkylene oxide. Preferably, a substituted C 1~100 or C 1~20 Alkyl, substituted C 3~30 or C 3~20 Cycloalkyl and substituted poly(C) 1~3 Alkylene oxide is a halogen, C 1~4 Fluoroalkyl groups such as fluoroalkyl groups, typically fluoromethyl groups, and sulfonamide groups -NH-S(O)2-Y 1 (Here, Y 1 is F or C 1~4 It is substituted with one or more perfluoroalkyl groups (e.g., -NHSO2CF3) or fluoroalcohol groups (e.g., -C(CF3)2OH).

[0043] In equation (VI), L 9 is a single bond or, for example, C 1~6 Alkylene or C 3~20 This represents polyvalent linking groups selected from optionally substituted aliphatic and aromatic hydrocarbons, such as cycloalkylenes, and combinations thereof, wherein one or more linking groups are optionally -O-, -S-, -C(O)-, and -NR. 102 -(Here, R 102 C is composed of hydrogen and optionally substituted C 1~10 Selected from alkyl groups, and n2 is an integer from 1 to 5, typically 1. For example, the polymer is of formula (VI) (wherein L 9 C is a single bond or a substituted or unsubstituted C 1~20 Alkylene, typically C 1~6Alkylene; substituted or unsubstituted C 3~20 Cycloalkylene; typically, C 3~10 Cycloalkylenes; and substituted or unsubstituted C 6~24 The repeating unit may further comprise a polyvalent linking group selected from allerenes, and n2 is 1, 2, or 3, derived from one or more monomers.

[0044] In equation (VII), n3 is either 0 or 1, and L 10 This can be a single bond or a divalent linking group. Preferably, L 10 C is a single bond, substituted or unsubstituted C 6~30 Arylene or substituted or non-substituted C 6~30 It could be a cycloalkylene.

[0045] In equation (VII), Ar 1 This is a substituted carbon atom that optionally contains one or more aromatic ring heteroatoms selected from N, O, S, or combinations thereof. 5~60 It is an aromatic group, which can be monocyclic, non-condensed polycyclic, or condensed polycyclic. C 5~60 When an aromatic group is polycyclic, the ring or ring group can be condensed (e.g., naphthyl), uncondensed, or a combination thereof. Polycyclic C 5~60 When the aromatic group is uncondensed, the ring or ring group can be directly linked (e.g., biaryl, biphenyl, etc.) or bridged by a heteroatom (e.g., triphenylamino or diphenylene ether, etc.). Polycyclic C 5~60 Aromatic groups can include combinations of fused rings and directly linked rings (e.g., binaphthyl).

[0046] In equation (VII), y can be an integer between 1 and 12, preferably between 1 and 6, typically between 1 and 3. Each R x These can independently be hydrogen or methyl.

[0047] Non-limiting examples of monomers that may be used to provide base-soluble repeating units include: [ka] [ka] (In the formula, Y 1 As stated above, R i In each of equations (8) to (10), R h , R i , and R j (As defined below) These are some examples.

[0048] If present, the polymer typically contains base-soluble repeating units in amounts of 1–60 mol%, typically 5–50 mol%, and more typically 5–40 mol%, based on the total repeating units in the polymer.

[0049] The polymer typically has a weight-average molecular weight (M) of 1,000 to 50,000 Datons (Da), preferably 2,000 to 30,000 Da, more preferably 4,000 to 20,000 Da, and even more preferably 5,000 to 15,000 Da. w ) has. The number average molecular weight (M) of the polymer. n M divided by ) w The polydispersion index (PDI) is typically 1.1–3, more typically 1.1–2. The molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.

[0050] Polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein may be combined or supplied separately using a suitable solvent and initiator and polymerized in a reactor. For example, polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays of an effective wavelength, or a combination thereof.

[0051] The photoresist composition further comprises a photoacid generator (PAG). A suitable PAG can generate an acid during post-exposure baking (PEB) that causes cleavage of acid-unstable groups present on the polymer of the photoresist composition. The PAG may be ionic or nonionic.

[0052] For example, photoacid generators contain an oxime structure that generates photoacids by Norrish-1 type cleavage. The Norrish-1 reaction is the photochemical cleavage or homolysis of aldehydes and ketones to two free radical intermediates. The carbonyl group accepts a photon and is excited to a photochemical singlet state. Some representative examples of nonionic photoacid generators have the following structures: [ka] This is shown.

[0053] PAG can be in nonpolymeric or polymeric form, and may exist, for example, in polymerized repeating units of the polymer described above, or as part of a different polymer. A suitable nonpolymeric PAG compound is given by formula G + A - (In the formula, G + A is an organic cation selected from iodonium cations substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; and sulfonium cations substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups. - PAG may have (a non-polymerizable organic anion). In some embodiments, PAG may be included as an unpolymerized PAG compound, as a repeating unit of a polymer having a PAG moiety derived from a polymerizable PAG monomer, or as a combination thereof.

[0054] Particularly preferred nonpolymeric organic anions include those whose conjugate acid has a pKa of -15 to 1. Particularly preferred anions are fluorinated alkyl sulfonates and fluorinated sulfonimides.

[0055] Suitable nonpolymeric PAG compounds are known in the art of chemically amplified photoresists and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate and di-t-butylphenyliodonium camphorsulfonate. Nonionic sulfonates and sulfonyl compounds, e.g., nitrobenzyl derivatives, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, e.g. Furthermore, bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimodomethanesulfonic acid and N-hydroxysuccinimodotrifluoromethanesulfonic acid; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine are also known to function as photoacid generators. Suitable non-polymerized photoacid generators are further described in Hashimoto et al. (Patent Document 1), column 37, rows 11-47 and columns 41-91.Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, nitrobenzyl esters, s-triazine derivatives, benzointosylates, t-butylphenyl α-(p-toluenesulfonyloxy)-acetate, and t-butyl α-(p-toluenesulfonyloxy)-acetate, as described in (Patent Document 2) and (Patent Document 1).

[0056] Typically, if the photoresist composition contains a nonpolymer photoacid generator, it is present in the photoresist composition in an amount of 1 to 65 wt%, more typically 2 to 20 wt%, based on the total solids content of the photoresist.

[0057] In some embodiments, G + The formula is shown as follows: [ka] (In the formula, each R aa These are independently substituted or non-substituted C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 6~30 Iodoaryl, substituted or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 7~20 Arylalkyl, or substituted or unsubstituted C 4~20 It may be a sulfonium cation or iodonium cation (which is a heteroarylalkyl). aa These are either individual or connected to another group R via a single bond or divalent linking group. aa They may be connected to each other to form a ring. Each R aa Each R may optionally include a divalent linking group as part of its structure. aaIt may independently contain, optionally, an acid-unstable group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group. aa Suitable divalent linking groups for linking groups include, for example, -O-, -S-, -Te-, -Se-, -C(O)-, -C(S)-, -C(Te)- or -C(Se)-, substituted or unsubstituted C 1~5 Contains alkylenes or combinations thereof.

[0058] Examples of sulfonium cations include: [ka] These are some examples.

[0059] Examples of iodonium cations in formula (12B) include: [ka] These are some examples.

[0060] PAGs, which are onium salts, typically contain organic anions having a sulfonate group or a non-sulfonate type group, such as a sulfonamide, sulfonimidate, methide, or borate.

[0061] Examples of organic anions having a sulfonate group include: [ka] These are some examples.

[0062] Examples of non-sulfonated anions include: [ka] These are some examples.

[0063] The photoresist composition may optionally contain multiple PAGs. The multiple PAGs may be polymers, nonpolymers, or may contain both polymer and nonpolymer PAGs. Preferably, each of the multiple PAGs is nonpolymer.

[0064] For example, the photoresist composition may include a first photoacid generator having a fluorinated sulfonate group on an anion, and the photoresist composition may include a second photoacid generator which is a nonpolymer, wherein the second photoacid generator may include an anion that is either a sulfonate group or does not contain a sulfonate group.

[0065] In some embodiments, the polymer optionally comprises repeating units including a PAG moiety, e.g., formula (13): [ka] It may further contain repeating units derived from one or more monomers.

[0066] In equation (13), R m This is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R m is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl. Q 1 Q may be a single bond or a divalent linking group. Preferably, 1 It may contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0067] In equation (13), A 1 is a substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 2~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, or substituted or unsubstituted C 3~30 It may be one or more heteroarylenes. Preferably, A1 This is a divalent C that is optionally substituted. 1~30 It may be a perfluoroalkylene group.

[0068] In equation (13), Z - The anionic moiety is the anionic portion, and its conjugate acid typically has a pKa of -15 to 5. - The anion can be a sulfonate, carboxylate, sulfonamide anion, sulfonimide anion, or methide anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonates and fluorinated sulfonimides.

[0069] In equation (13), G + is an organic cation as defined above. In some embodiments, G + This is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups. In both cases, the substituents may, if applicable, be linked together to form a ring.

[0070] Examples of monomers in formula (14) are as follows: [ka] (In the formula, G + (It is an organic cation.) These are some examples.

[0071] The polymer may contain repeating units with PAG moieties in an amount of 1 to 15 mol%, typically 1 to 8 mol%, and more typically 2 to 6 mol%, based on the total repeating units in the polymer and / or acid-unstable polymer.

[0072] The photoresist composition further comprises a solvent for dissolving the components of the composition and facilitating its coating on a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, iso-propanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2- These solvents include ketones such as heptanone and cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and acetate acetate; lactones such as gamma-butyrolactone (GBL) and epsilon-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or acyclic carbonate esters such as dimethyl carbonate, ethylene carbonate, propylene carbonate, and diphenyl carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Of these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof. The total solvent content in a photoresist composition (i.e., the cumulative solvent content for all solvents) is typically 40–99% by weight, for example, 70–99% by weight, or 85–99% by weight, based on the total solids content of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the coated photoresist layer and the coating conditions.

[0073] The polymer is typically present in the photoresist composition in amounts of 10–99.9% by weight, typically 25–99% by weight, and more typically 50–95% by weight, based on the total solids content of the photoresist composition. “Total solids” will be understood to include the polymer, PAG, and other non-solvent components.

[0074] A photoresist composition may further comprise a material containing one or more base-unstable groups ("base-unstable material"). As referred to herein, a base-unstable group is a functional group that can undergo a cleavage reaction in the presence of an aqueous alkaline developer after the exposure step and the post-exposure baking step to provide polar groups such as hydroxyls, carboxylic acids, sulfonic acids, etc. A base-unstable group will not react significantly before the development step of a photoresist composition containing a base-unstable group (e.g., it will not undergo a bond cleavage reaction). Therefore, for example, a base-unstable group will be substantially inert during the pre-exposure soft bake, exposure, and post-exposure bake steps. "Substantially inert" means that 5% or less, typically 1% or less, of the base-unstable group (or portion) decomposes, cleaves, or reacts during the pre-exposure soft bake, exposure, and post-exposure bake steps. A base-unstable group is highly reactive under typical photoresist development conditions using an aqueous alkaline photoresist developer, such as an aqueous solution of 0.26 N (N) tetramethylammonium hydroxide (TMAH). For example, a 0.26N aqueous solution of TMAH can be used for single-paddle development or dynamic development, where, for example, a 0.26N TMAH developer is distributed onto the imaging photoresist layer for a suitable time, such as 10 to 120 seconds (s). Exemplary base-unstable groups are ester groups, typically fluorinated ester groups. Preferably, the base-unstable material is substantially miscible with the polymer and other solid components of the photoresist composition and has a lower surface energy than them. When coated onto a substrate, the base-unstable material can thereby separate from the other solid components of the resist composition to the upper surface of the formed photoresist layer.

[0075] A base-unstable material can be a polymer material, also referred to herein as a base-unstable polymer, and may comprise one or more repeating units, each containing one or more base-unstable groups. For example, a base-unstable polymer may comprise two or more repeating units, each containing two or more identical or different base-unstable groups. A preferred base-unstable polymer comprises at least one repeating unit, each containing two or more base-unstable groups, for example, a repeating unit containing two or three base-unstable groups.

[0076] Base-unstable polymers are given by formula (14A): [ka] (In the formula, X e is a substitution or non-substitution C 2~20 A polymerizable group selected from alkenyls or substituted or unsubstituted (meth)acrylics, L 12 R is a divalent linking group; n is a substitution or non-substitution C 1~20 It is a fluoroalkyl compound, provided that the carbon atom bonded to the carbonyl (C=O) in formula (14A) is substituted with at least one fluorine atom. It may be a polymer containing repeating units derived from one or more monomers.

[0077] Examples of monomers in formula (14A) are as follows: [ka] These are some examples.

[0078] Base-unstable polymers may contain repeating units that include two or more base-unstable groups. For example, a base-unstable polymer is given by formula (14B): [ka] (In the formula, X f and R p In equation (14A), X e and R n As defined, L13 is a substitution or non-substitution C 1~20 Alkylene, substituted or unsubstituted C 3~20 A polyvalent linking group containing one or more cycloulkilenes, -C(O)-, or -C(O)O-, where n4 is an integer of 2 or more, for example, 2 or 3. It may contain repeating units derived from one or more monomers.

[0079] Examples of monomers for the monomers in formula (14B) are as follows: [ka] These are some examples.

[0080] Base-unstable polymers may contain repeating units that include one or more base-unstable groups. For example, a base-unstable polymer may have the formula (14C): [ka] (In the formula, X g and R q In equation (14A), X e and R n As defined for; L 14 is a divalent linking group, L 15 is a substitution or non-substitution C 1~20 It is a fluoroalkylene, where the carbon atom bonded to the carbonyl (C=O) in formula (14C) is substituted with at least one fluorine atom. It may contain repeating units derived from one or more monomers.

[0081] Examples of monomers in formula (14C) are as follows: [ka] These are some examples.

[0082] In a more preferred embodiment of the present invention, the base-unstable polymer may comprise one or more base-unstable groups and one or more acid-unstable groups, such as one or more acid-unstable ester moieties (e.g., t-butyl esters) or acid-unstable acetal groups. For example, the base-unstable polymer may comprise repeating units comprising base-unstable groups and acid-unstable groups, i.e., repeating units on which both base-unstable groups and acid-unstable groups reside. In another example, the base-unstable polymer may comprise a first repeating unit comprising base-unstable groups and a second repeating unit comprising acid-unstable groups. The preferred photoresist of the present invention can exhibit a reduction in defects associated with the resist relief image formed from the photoresist composition.

[0083] Base-unstable polymers can be prepared using any suitable method in the art, including those described herein for the first and second polymers. For example, base-unstable polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with a chemical beam at an effective wavelength, or a combination thereof. In addition, or instead, one or more base-unstable groups can be grafted onto the polymer backbone using a suitable method.

[0084] A base-unstable material can be a single molecule containing one or more base-unstable ester groups, preferably one or more fluorinated ester groups. A base-unstable material that is a single molecule typically has a molecular weight in the range of 50 to 1,500 Da. W It has the following characteristics. Examples of base-unstable materials include: [ka] These are some examples.

[0085] If present, the base-unstable material is typically present in the photoresist composition in an amount of 0.01 to 10% by weight, or 1 to 5% by weight, based on the total solids content of the photoresist composition.

[0086] In addition to, or instead of, the base-unstable polymer, the photoresist composition may further include one or more polymers in addition to, and different from, the above-mentioned photoresist polymer. For example, the photoresist composition may include additional polymers as described above, but with different compositions, or polymers similar to those described above, but without each of the essential repeating units. Furthermore, or instead, the one or more additional polymers may be selected from those well known in photoresist technology, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene-based polymers, polyvinyl alcohols, or combinations thereof.

[0087] The photoresist composition may further contain one or more additional, optional additives. For example, optional additives may include chemical laser dyes and contrast agents, striation inhibitors, plasticizers, rate accelerators, sensitizers, photodegradable deactivators (PDQ) (also known as photodegradable bases), basic deactivators, thermoacid generators, surfactants, etc., or combinations thereof. If present, the optional additives are typically present in the photoresist composition in an amount of 0.01 to 10% by weight, based on the total solids content of the photoresist composition.

[0088] PDQ generates a weak acid upon irradiation. The acid generated from the photodegradable inactivator is not strong enough to react rapidly with the acid-unstable groups present in the resist matrix. Exemplary photodegradable inactivators include, for example, photodegradable cations, preferably, for example, C 1~20 Carboxylic acid or C 1~20Examples of compounds useful for preparing strong acid-generating compounds paired with anions of weak acids (pKa>1), such as sulfonic acid anions, include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, and salicylic acid. Examples of sulfonic acids include p-toluenesulfonic acid and camphorsulfonic acid. In preferred embodiments, the photodegradable deactivator is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0089] The photodegradable inactivator may be in a non-polymeric or polymer-bound form. In the polymeric form, the photodegradable inactivator is present in polymerization units on the first or second polymer. Polymerization units containing the photodegradable inactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0090] Examples of basic inactivators include, for example: tributylamine, trioctylamine, triisopropanolamine, tetrakis(2-hydroxypropyl)ethylenediamine, n-tert-butyldiethanolamine, tris(2-acetoxyethyl)amine, 2,2',2'',2'''-(ethane-1,2-diyrbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and linear aliphatic amines such as 2,2',2''-nitrilotriethanol; 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidine carboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butyl Cyclic aliphatic amines such as piperazine-1,4-dicarboxylate and N-(2-acetoxy-ethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3Examples include linear and cyclic amides and their derivatives such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines such as primary and secondary aldimines and ketimines; diazines such as optionally substituted pyrazines, piperazines, and phenazines; diazoles such as optionally substituted pyrazoles, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidines.

[0091] Basic deactivators can exist in a non-polymeric or polymer-bound form. When in a polymeric form, the deactivator may be present within the repeating units of the polymer. Repeating units containing the deactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0092] Exemplary surfactants include fluorinated and non-fluorinated surfactants, which may be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In one embodiment, the photoresist composition further comprises a surfactant polymer containing fluorine-containing repeating units.

[0093] A method for forming patterns using the photoresist composition of the present invention is described below. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates, such as semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multi-chip modules; flat panel display substrates; substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), are used in the present invention, with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), but wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that optionally contain the effective or operable portion of the device to be formed.

[0094] Typically, one or more lithography layers, such as a hard mask layer (e.g., spin-on carbon (SOC), amorphous carbon, or metallic hard mask layer), a CVD layer (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer), an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of the substrate before coating with the photoresist composition of the present invention. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0095] Optionally, a layer of adhesion promoter may be applied to the substrate surface before coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, and hexamethyldisilazane, or aminosilane coupling agents such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from DuPont Electronics & Imaging (Marlborough, Massachusetts) under the names AP 3000, AP 8000, and AP 9000S.

[0096] The photoresist composition can be coated onto a substrate by any preferred method, such as spin coating, spray coating, dip coating, doctor blading, etc. For example, the application of a photoresist layer can be achieved by spin coating the photoresist in a solvent using a coating track, in which case the photoresist is distributed onto a rotating wafer. During distribution, the wafer is typically rotated for a period of 15 to 120 seconds at a speed of, for example, 200 to 3,000 rpm, or 1,000 to 2,500 rpm, up to a maximum of 4,000 revolutions per minute (rpm), to obtain a layer of the photoresist composition on the substrate. It will be well understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and / or the total solid content of the composition. The photoresist layer formed from the composition of the present invention typically has a dry layer thickness of 10 to 500 nanometers (nm), preferably 15 to 200 nm, more preferably 20 to 120 nm.

[0097] The photoresist composition is typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft-bake temperature and time will depend, for example, on the photoresist composition and thickness. The soft-bake temperature is typically 80–170°C, more typically 90–150°C. The soft-bake time is typically 10 seconds–20 minutes, more typically 1 minute–10 minutes, and even more typically 1 minute–2 minutes. The heating time can be easily determined by those skilled in the art based on the composition's components.

[0098] The photoresist layer is then pattern-exposed to activating radiation to create a difference in solubility between exposed and unexposed areas. References herein to exposure of a photoresist composition to activating radiation indicate that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions, corresponding to the exposed and unexposed areas of the resist layer, respectively. Such exposure may instead be performed without a photomask using direct writing methods, which are typically used for e-beam lithography. Activating radiation typically has wavelengths less than 400 nm, less than 300 nm, or less than 200 nm, with 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV) wavelengths, or e-beam lithography being preferred. Preferably, the activating radiation is 193 nm radiation or EUV radiation. This method is utilized in immersion or dry (non-immersion) lithography techniques. The exposure energy depends on the components of the exposure tool and photoresist composition, and is typically 1 to 200 millijoules (mJ / cm²) per square centimeter. 2 ), preferably 10 to 100 mJ / cm² 2 More preferably 20-50 mJ / cm² 2 That is the case.

[0099] After exposure of the photoresist layer, post-exposure baking (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for PEB will depend, for example, on the photoresist composition and layer thickness. PEB is typically performed at a temperature of 70-150°C, preferably 75-120°C, for a time of 30-120 seconds. A latent image is formed in the photoresist, defined by polarity switching regions (exposed regions) and non-switching regions (unexposed regions).

[0100] The exposed photoresist layer is then developed with a developer suitable for selectively removing the soluble regions of the layer, while the remaining insoluble regions form the resulting photoresist pattern relief image. In a positive development (PTD) process, the exposed regions of the photoresist layer are removed during development, leaving the unexposed regions. Conversely, in a negative development (NTD) process, the exposed regions of the photoresist layer remain, and the unexposed regions are removed during development. The application of the developer can be achieved by any preferred method as described above for applying the photoresist composition, with spin coating being a typical example. The development time is an effective time for removing the soluble regions of the photoresist, typically 5 to 60 seconds. Development is typically carried out at room temperature.

[0101] Suitable developers for the PTD process include aqueous base developers, such as tetramethylammonium hydroxide (TMAH), preferably 0.26 N (N) TMAH, quaternary ammonium hydroxide solutions such as tetraethylammonium hydroxide and tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent systems, meaning that the cumulative content of organic solvents in the developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0102] A coated substrate may be formed from the photoresist composition of the present invention. Such a coated substrate comprises (a) a substrate having one or more layers patterned on its surface; and (b) a layer of the photoresist composition on one or more patterned layers.

[0103] A photoresist pattern can be used, for example, as an etching mask, thereby enabling the transfer of the pattern to one or more consecutive underlying layers by known etching techniques, typically by dry etching such as reactive ion etching. A photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, and it can subsequently be used as an etching mask for pattern transfer to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such patterning processes, photoresist compositions can be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0104] definition As used herein, the terms "and / or" include any and all combinations of one or more of the enumerated items relating to them. Expressions such as "at least one of" qualify the entire list of elements, but not the individual elements of the list, when preceding a list of elements.

[0105] As used herein, the terms “a,” “an,” and “the” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically stated herein or clearly contradicted by the context. “Or” means “and / or” unless otherwise specified. The modifying phrase “about” used in relation to quantity includes the expressed value and has meaning determined by the context (e.g., the degree of error associated with the measurement of a particular quantity). All scopes disclosed herein include endpoints, which are independently combinable with one another. The suffix “(s)” includes both singular and plural forms of the term it modifies and is intended to include at least one of those terms. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes both the cases in which the event occurs and the cases in which the event does not occur. The terms “first,” “second,” etc., used herein do not imply order, quantity, or importance, but rather are used to distinguish one element from another. When an element is said to be “on” another element, it may be in direct contact with the other element, or an intervening element may exist between them. In contrast, when an element is said to be “directly on” another element, no intervening element is present. It should be understood that the components, elements, limitations, and / or features described in the embodiments may be combined in any preferred manner in various embodiments.

[0106] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which the invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning as those defined in the relevant art and in relation to this disclosure, and it will be further understood that unless explicitly defined herein, they should not be interpreted in an ideal or overly formal sense.

[0107] As used herein, "chemical beam" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, electron beams and ion beams, and other particle beams. Furthermore, in this invention, "light" means chemical beam or radiation.

[0108] Argon fluoride lasers (ArF lasers) are a specific type of excimer laser, sometimes referred to as exciplex lasers. "Excimer" is short for "excited dimer," while "exciplex" is short for "excited complex." Excimer lasers use a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine) to emit coherent stimulating radiation (laser light) in the ultraviolet range under suitable conditions of electrical stimulation and high pressure.

[0109] Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using far ultraviolet light such as mercury lamps and excimer lasers, X-rays, and extreme ultraviolet (EUV) light, but also writing using particle beams such as electron beams and ion beams.

[0110] As used herein, the term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight-chain or branched-chain saturated hydrocarbon group having the specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence of 2; "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid group" refer to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a straight-chain or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond; "cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least 3 carbon atoms and at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic ring system that satisfies the Hückel rule, contains carbon atoms in the ring, and optionally may contain one or more heteroatoms selected from N, O, and S in place of carbon atoms in the ring; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system that may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring in which all ring members are carbon; "arylene" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group substituted with an alkyl group; "arylalkyl" refers to an alkyl group substituted with an aryl group; "aryloxy" refers to "aryl-O-"; "arylthio" refers to "aryl-S-".

[0111] The prefix "hetero" means that a compound or group contains at least one constituent atom that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) instead of a carbon atom, where each heteroatom is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent containing at least one heteroatom; "heteroalkyl" refers to an alkyl group having at least one heteroatom instead of carbon; "heterocycloalkyl" refers to a cycloalkyl group having at least one heteroatom as a ring constituent atom instead of carbon; and "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of 2.

[0112] The term "heteroaryl" refers to aromatic 4-8 member monocyclic, 8-12 member bicyclic, or 11-14 member tricyclic ring systems having 1-4 heteroatoms (for monocyclics), 1-6 heteroatoms (for bicyclics), or 1-9 heteroatoms (for tricyclics) independently selected from N, O, S, Si, or P (for example, a carbon atom and 1-3, 1-6, or 1-9 N, O, or S heteroatoms, respectively). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, and thiazolyl.

[0113] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one or more fluoro, chloro, bromo, or iodo substituents instead of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or a fluoro group alone may exist. For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C 1~8 "Haloalkyl" refers to C substituted with at least one halogen. 1~8Refers to an alkyl group, which is further substituted with one or more other substituents that are not halogen. It should be understood that since a halogen atom does not replace a carbon atom, substitution of a group with a halogen atom is not considered a heteroatom-containing group.

[0114] "Fluorinated" is understood to mean having one or more fluorine atoms incorporated into the group. For example, C 1~18 When a fluoroalkyl group is shown, the fluoroalkyl group can contain one or more fluorine atoms, such as a single fluorine atom, two fluorine atoms (e.g., 1,1-difluoroethyl group, etc.), three fluorine atoms (e.g., 2,2,2-trifluoroethyl group, etc.), or fluorine atoms at each free valence of carbon (e.g., perfluoro groups such as -CF3, -C2F5, -C3F7, or -C4F9, etc.). "Substituted fluoroalkyl group" is understood to mean a fluoroalkyl group further substituted with another substituent.

[0115] Each of the substituents described above can be optionally substituted unless otherwise explicitly indicated. The term "optionally substituted" refers to being either substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of the chemical structure is replaced with another terminal substituent, typically monovalent, provided that it does not exceed the normal valence of the specified atom. When the substituent is oxo (i.e., =O), two geminal hydrogen atoms on the carbon atom are replaced with the terminal oxo group. Combinations of substituents or variables are allowed. Exemplary substituents that can be present at the "substituted" position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2, mono- or di-(C 1~6 )alkylamino, alkanoyl (such as C 2~6 alkanoyl group, etc.), formyl (-C(=O)H), carboxylic acid or its alkali metal or ammonium salt; ester (including acrylate, methacrylate, and lactone), for example C 2-6-alkyl) and C7-13 aryl esters (-C(=O)O-aryl or -OR); carboxamide (-CH2C(=O)NR2 (wherein R is hydrogen or C) 1~6 Alkyl, halogen, thiol (-SH), C 1~6 Alkylthio(-S-alkyl), thiocyano(-SCN), C 1~6 Alkyl, C 2~6 Alkenil, C 2~6 Alkinyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, a C2 molecule having at least one aromatic ring. 6~12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is either substituted or unsubstituted aromatic), 1 to 3 separate rings or fused rings, and C having 6 to 18 ring carbon atoms. 7~19 Arylalkyl, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Examples include, but are not limited to, arylsulfonyl (-S(=O)2-aryl) or tosyl (CH3C6H4SO2-). When a group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding the carbon atoms of any substituents. For example, the group -CH2CH2CN is a cyanosubstituted C2 alkyl group.

[0116] As used herein, “acid-unstable group” means a group whose bond is cleaved by the catalytic action of an acid, optionally and typically accompanied by heat treatment, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group, which is formed on a polymer and whose portion connected to the cleaved bond is optionally and typically cleaved from the polymer. In other systems, nonpolymer compounds may contain acid-unstable groups that can be cleaved by the catalytic action of an acid, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group on the cleaved portion of the nonpolymer compound. Such acids are typically photo-generated acids in which bond cleavage occurs during post-exposure baking, however, embodiments are not limited thereto, and such acids may be thermally generated, for example. Preferred acid-unstable groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. In this technical field, acid-unstable groups are generally referred to as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-unstable protecting groups," "acid-leaving groups," "acid-degradable groups," and "acid-sensitive groups."

[0117] As used herein, unless otherwise defined, "divalent linking group" refers to -O-, -S-, -Te-, -Se-, -C(O)-, -N(R a -, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 R refers to a divalent group containing one or more heteroarylenes or combinations thereof. a C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30This refers to heteroaryl compounds. Typically, the divalent linking groups are -O-, -S-, -C(O)-, and -N(R a )-, -S(O)-, -S(O)2-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 It contains one or more heteroarylenes or combinations thereof, R a C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It contains one or more heteroaryl groups. More typically, the divalent linking groups are -O-, -C(O)-, -C(O)O-, -N(R a )-,-C(O)N(R a )-, substitution or non-substitution C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 It includes at least one heteroarylene or a combination thereof, R a C is hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted, or unsubstituted C 1~10 Heteroalkyl, substituted, or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 It contains at least one heteroaryl compound.

[0118] The present invention is further illustrated by the following embodiments. [Examples]

[0119] Monomer synthesis. The synthesis reaction was carried out under normal atmospheric conditions. All chemicals were used as received from the suppliers and without further purification.

[0120] Example 1. Preparation of CHOMMBL [ka] Zinc powder (20.9 g) was placed in a dry three-necked round-bottom flask (RBF) equipped with a dropping funnel and condenser under nitrogen (N2) gas, and tetrahydrofuran (THF) (280 mL) was added. Trimethylsilanchloride (4.4 g) was added, and the mixture was stirred at 20°C to 25°C for 10 minutes. Tert-butyl acetoacetate (31.6 g) was added to the reaction mixture and stirred for 5 minutes. A solution prepared by dissolving ethyl (2-bromomethyl)acrylate (46.3 g) in 20 mL of THF was added via a dropping funnel at 25°C. During the addition, the reaction temperature was maintained in the range of 30°C to 35°C. After the addition, the mixture was stirred at 35°C for 1 hour. The reaction solution was cooled to 2°C, poured into 1 N (N) hydrochloric acid (HCl) (200 mL), and the product was extracted with ethyl acetate. The resulting organic layer was dried, concentrated under reduced pressure, and purified by column chromatography to obtain 40.0 g of oil (73.7% yield). 33.9 g of tert-butyl 2-(2-methyl-4-methylene-5-oxotetrahydrofuran-2-yl)acetate and 34.0 g of trifluoroacetic acid were added to 250 mL of RBF, and the reaction mixture was stirred overnight at room temperature. Trifluoroacetic acid was removed under reduced pressure to obtain the oil, which was used directly in the next step without purification.

[0121] Chloromethoxycyclopentane (12.6 g) and heptane (100 mL) were added to 500 mL of RBF. The resulting mixture was cooled in a water bath. Triethylamine (10.3 g) was added dropwise to the resulting solution using a dropping funnel, followed by the dropwise addition of 2-(2-methyl-4-methylene-5-oxotetrahydrofuran-2-yl)acetic acid (17.4 g) in 20 mL of THF. The resulting reaction solution was stirred overnight at room temperature. After the reaction, water (150 mL) was added to the mixture. The resulting solution was transferred to a separatory funnel, the aqueous layer was separated, and the resulting solution was washed three times with water and saturated sodium bicarbonate aqueous solution (100 mL). The resulting product was further washed with 200 mL of saturated sodium chloride aqueous solution. The resulting organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and purified by column chromatography to obtain the product as oil, 18.2 g (71.3% yield).

[0122] Example 2. Preparation of BOMMBL [ka] Zinc powder (8.63 g), THF (183 mL), and a stirring bar were placed in a dry round-bottom flask. The mixture was stirred and purged with N2 for 15 minutes. Trimethylsilan chloride (0.48 g) was added dropwise via syringe under nitrogen, and the mixture was stirred for a further 15 minutes at 22°C. Tert-butyl acetoacetate (17.4 g) was added to the reaction mixture and stirred for 5 minutes. Ethyl (2-bromomethyl)acrylate (21.2 g) was added dropwise via syringe over 30 minutes. The reaction mixture was kept in a water bath during the addition. After the addition, the mixture was warmed to 22°C and stirred for 1 hour. After the reaction, the mixture was diluted with ethyl acetate and filtered to remove the solid. The organic layer was washed with 1N HCl, saturated NaHCO3, and saturated NaCl. The resulting organic layer was dried and concentrated under reduced pressure to obtain the crude product as oil (26.0 g).

[0123] 165 mL of 1N HCl was added to the crude oil, and the reaction mixture was stirred overnight at 50°C. The mixture was extracted five times with dichloromethane. The combined organic layer was basicized with saturated NaHCO3. The aqueous layer was then neutralized with 1N HCl and extracted five times with ethyl acetate. The combined organic layer was dried and concentrated to obtain 2-(2-methyl-4-methylene-5-oxotetrahydrofuran-2-yl)acetic acid as a pale yellow oil (10.2 g).

[0124] Chloromethyl butyl ether (3.65 g) was dissolved in THF (20 mL) and heptane (40 mL). Triethylamine (Et3N) (9.0 g) was added dropwise in an ice bath with stirring. 2-(2-methyl-4-methylene-5-oxotetrahydrofuran-2-yl)acetic acid (5.58 g) in 20 mL of THF was added dropwise to the reaction mixture in an ice bath. The reaction mixture was heated to 22°C and stirred for 3 hours. After the reaction, the salt was filtered. The organic solution was diluted with heptane and washed with H2O, saturated NaHCO3, and saturated NaCl. The combined organic layers were dried and concentrated to obtain the final product BOMMBL as oil (7.63 g).

[0125] Example 3. Preparation of ECPMMBL [ka] Zinc powder (18.5 g) was loaded into a dry three-necked RBF equipped with a dropping funnel and condenser under N2 conditions, and THF (240 mL) was added. Trimethylsilanchloride (4.8 g) was added, and the mixture was stirred at 20°C to 25°C for 10 minutes. 1-ethylcyclopentyl 3-oxobutanoate (34.7 g) was added to the reaction mixture and stirred for 5 minutes. A solution prepared by dissolving ethyl (2-bromomethyl)acrylate (40.5 g) in 20 mL of THF was added via a dropping funnel at 25°C. During the addition, the reaction temperature was maintained in the range of 30°C to 35°C. After the addition, the mixture was stirred at 35°C for 1 hour. The reaction solution was cooled to 25°C, poured into 1N HCl (200 mL), and the product was extracted with ethyl acetate. The resulting organic layer was dried, concentrated under reduced pressure, and purified by column chromatography to obtain 28.0 g of oil (yield 50.1%).

[0126] Synthesis of polymers. The additional monomers used to prepare the polymers of the present invention and the comparative polymers have the following structures: [Chemical formula] have

[0127] Example 4. Synthesis of Polymer P1 13.17 g of propylene glycol methyl ether acetate (PGMEA), 6.85 g of 1-ethylcyclopentyl methacrylate (ECPMA), 6.40 g of 2-oxotetrahydrofuran-3-yl methacrylate (aGBLMA), 4.21 g of β-methyl-α-methylene-γ-butyrolactone (MMBL), and 3.54 g of (cyclohexyloxy)methyl 2-(2-methyl-4-methylene-5-oxotetrahydrofuran-2-yl)acetate (CHOMMBL) were combined in a container, and a monomer feed solution was prepared by stirring the mixture to dissolve the monomers. The initiator feed solution was prepared by combining 2.11 g of V-601 free radical initiator (Wako Pure Chemical Industries, Ltd.) and 19.01 g of PGMEA in a container and stirring the mixture to dissolve the initiator. 14.70 g of PGMEA was introduced into the reaction vessel, and the vessel was purged with nitrogen gas for 30 minutes. Next, the reaction vessel was heated to 80 °C with stirring. The introduction of the monomer feed solution and the initiator feed solution into the reaction vessel was started simultaneously. The monomer feed solution was supplied over a period of 4 hours, and the initiator feed solution was supplied over a period of 3.5 hours. The reaction vessel was maintained at 80 °C for an additional 1 hour with stirring and then cooled to room temperature. The polymer was precipitated in 10×(v / v) methanol to obtain a white solid. The solid was dried under vacuum to obtain the polymer. The weight average molecular weight (Mw) and polydispersity (PDI = Mw / Mn) were determined by polystyrene equivalent values as measured by gel permeation chromatography (GPC): Mw = 7405, PDI = 1.6.

[0128] Example 5. Synthesis of Polymer P2 A feed solution was prepared by combining 10.52 g of propylene glycol methyl ether acetate (PGMEA), 0.69 g of V-601 free radical initiator (Wako Pure Chemical Industries, Ltd.), 2.23 g of 1-ethylcyclopentyl methacrylate (ECPMA), 2.09 g of 2-oxotetrahydrofuran-3-yl methacrylate (aGBLMA), 0.79 g of β-methyl-α-methylene-γ-butyrolactone (MMBL), and 0.90 g of butoxymethyl 2-(2-methyl-4-methylene-5-oxotetrahydrofuran-2-yl) acetate in a container and stirring the mixture to dissolve the initiator and monomers. The feed solution was purged with nitrogen gas for 15 minutes. 2.80 g of PGMEA was introduced into the reaction vessel, and the vessel was purged with nitrogen gas for 15 minutes. Next, the reaction vessel was heated to 80°C with stirring. The feed solution was supplied over 4 hours. The reaction vessel was maintained at 80°C for a further 0.5 hours with stirring, and then cooled to room temperature. The polymer was precipitated in 10 × (v / v) methanol to obtain a white solid. The solid was dried under vacuum to obtain the polymer. The weight-average molecular weight (Mw) and polydispersity (PDI = Mw / Mn) were determined by polystyrene equivalent values ​​measured by gel permeation chromatography (GPC): Mw = 6649, PDI = 1.36.

[0129] Example 6. Synthesis of polymer CP1 A monomer supply solution was prepared by combining 20.75 g of propylene glycol methyl ether acetate (PGMEA), 11.37 g of 1-ethylcyclopentyl methacrylate (ECPMA), 10.60 g of 2-oxotetrahydrofuran-3-yl methacrylate (aGBLMA), 6.99 g of β-methyl-α-methylene-γ-butyrolactone (MMBL), and 4.13 g of (cyclohexyloxy)methyl methacrylate (CHOMMA) in a container and stirring the mixture to dissolve the monomers. The initiator supply solution was prepared by combining 3.02 g of V-601 free radical initiator (Wako Pure Chemical Industries, Ltd.) and 27.16 g of PGMEA in a container and stirring the mixture to dissolve the initiator. 21.00 g of PGMEA was introduced into the reaction vessel, and the reaction vessel was purged with nitrogen gas for 30 minutes. Next, the reaction vessel was heated to 80°C with stirring. The introduction of the monomer feed solution and the initiator feed solution into the reaction vessel was started simultaneously. The monomer feed solution was supplied over a period of 4 hours, and the initiator feed solution was supplied over a period of 3.5 hours. The reaction vessel was maintained at 80°C for a further hour with stirring, and then cooled to room temperature. The polymer was precipitated in 10 × (v / v) methanol to obtain a white solid. The solid was dried under vacuum to obtain the polymer. The weight-average molecular weight (Mw) and polydispersity (PDI = Mw / Mn) were determined by polystyrene equivalent values ​​measured by gel permeation chromatography (GPC): Mw = 7517, PDI = 1.84.

[0130] Example 7. Synthesis of polymer CP2 A monomer supply solution was prepared by combining 11.87 g of propylene glycol methyl ether acetate (PGMEA), 8.46 g of 1-ethylcyclopentyl 2-(2-methyl-4-methylene-5-oxotetrahydrofuran-2-yl) acetate (ECPMMBL), 7.72 g of 2-oxotetrahydrofuran-3-yl methacrylate (aGBLMA), and 2.70 g of (cyclohexyloxy)methyl methacrylate (CHOMMA) in a container and stirring the mixture to dissolve the monomers. The initiator supply solution was prepared by combining 2.31 g of V-601 free radical initiator (Wako Pure Chemical Industries, Ltd.) and 20.80 g of PGMEA in a container and stirring the mixture to dissolve the initiator. 12.60 g of PGMEA was introduced into the reaction vessel, and the vessel was purged with nitrogen gas for 30 minutes. Next, the reaction vessel was heated to 80°C with stirring. The introduction of the monomer feed solution and initiator feed solution into the reaction vessel was started simultaneously. The monomer feed solution was supplied over a period of 4 hours, and the initiator feed solution was supplied over a period of 3.5 hours. The reaction vessel was maintained at 80°C for a further 1 hour with stirring, and then cooled to room temperature. The polymer was precipitated in 10 × (v / v) methanol to obtain a white solid. The solid was dried under vacuum to obtain the polymer. The weight-average molecular weight (Mw) and polydispersity (PDI = Mw / Mn) were determined by polystyrene equivalent values ​​measured by gel permeation chromatography (GPC): Mw = 6581, PDI = 1.7.

[0131] Example 8. Synthesis of polymer CP3 A monomer supply solution was prepared by combining 16.43 g of propylene glycol methyl ether acetate (PGMEA), 10.57 g of 1-ethylcyclopentyl methacrylate (ECPMA), 9.86 g of 2-oxotetrahydrofuran-3-yl methacrylate (aGBLMA), 6.49 g of β-methyl-α-methylene-γ-butyrolactone (MMBL), and 3.32 g of (butyloxy)methyl methacrylate (BOMMA) in a container and stirring the mixture to dissolve the monomers. The initiator supply solution was prepared by combining 3.57 g of V-601 free radical initiator (Wako Pure Chemical Industries, Ltd.) and 32.16 g of PGMEA in a container and stirring the mixture to dissolve the initiator. 12.60 g of PGMEA was introduced into the reaction vessel, and the vessel was purged with nitrogen gas for 30 minutes. Next, the reaction vessel was heated to 80°C with stirring. The introduction of the monomer feed solution and the initiator feed solution into the reaction vessel was started simultaneously. The monomer feed solution was supplied over a period of 4 hours, and the initiator feed solution was supplied over a period of 3.5 hours. The reaction vessel was maintained at 80°C for a further 1 hour with stirring, and then cooled to room temperature. The polymer was precipitated in 10 × (v / v) methanol to obtain a white solid. The solid was dried under vacuum to obtain the polymer. The weight-average molecular weight (Mw) and polydispersity (PDI = Mw / Mn) were determined by polystyrene equivalent values ​​measured by gel permeation chromatography (GPC): Mw = 6649, PDI = 1.59.

[0132] Example 9. Preparation of photoresist formulations The photoresist formulations were prepared by mixing the individual components (polymer, photoacid generator (PAG), diphenyliodonium-2-carboxylate (DPIC) as a deactivator, and additive A1) in the amounts listed in Table 1 in a solvent. The solvent was a blend of 35% PGMEA (propylene glycol methyl ether acetate) and 65% HBM (hydroxyisobutyrate methyl ester). The chemical structures of PAG, DPIC, and base-unstable additive A1 are as follows: [ka]

[0133] The weight percentages of polymers, PAGs, deactivators, and additives listed in Table 1 are weight percentages based on the total weight of solids (i.e., polymers, PAGs, deactivators, and additives). The total amount of solids is 3.1% by weight based on the total weight of solids and solvent. The chemical structures of each photoresist component are reported below. Each mixture was mixed by shaking overnight and further filtered through a 0.2 μm PTFE disk.

[0134] [Table 1]

[0135] Example 10 - Testing of Photoresist Composition Immersion lithography was performed using a TEL Lithius 300mm wafer track and an ASML 1900i immersion scanner. Wafers for photolithography testing were coated with 800 angstroms (Å) of AR® 40A bottom anti-reflective coating (BARC) material (DuPont Electronic Materials International, LLC, Marlborough, MA USA) using a curing time of 205°C / 60 seconds. One side of the AR® 40A BARC material (DuPont Electronic Materials International, LLC, Marlborough, MA USA) was coated with 400 Å of AR104 BARC using a curing time of 175°C / 60 seconds. One side of the BARC stack was coated with 900 Å of photoresist using a soft bake (SB) at 90°C / 60 seconds. For line patterning at 38 nm / 76 pb, exposure was performed with a 1.35 NA (numerical aperture), 0.988 / 0.90 internal / external sigma, and 35 Y polarized dipole illumination. For trench patterning at 46 nm / 92 pb, exposure was performed with a 1.35 NA, 0.80 / 0.40 internal / external sigma, and XY polarized annular illumination. After exposure with increasing focus and increasing dose in 20 nm increment steps, the films were subjected to post-exposure bake (PEB) at 85°C / 60 sec or / and 95°C / 60 sec or / and 105°C / 60 sec. After PEB, the wafers were developed with 0.26 N aqueous TMAH developer for 12 seconds, rinsed with distilled water, and tumble-dried.

[0136] Measurements were performed using a Hitachi CG4000 CD-SEM. Linewidth roughness (LWR) was determined as a 3-sigma value from the distribution of 100 arbitrary points in the linewidth measurement. Esize is defined as the irradiation dose at which the pattern limit dimension equals the mask limit dimension. While this disclosure has been described in relation to what is currently considered to be a practical and exemplary embodiment, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to encompass various modifications and equivalent arrangements that fall within the spirit and scope of the appended claims.

[0137] The results for line patterning are shown in Table 2. The results for trench patterning are shown in Table 3. With respect to line patterning, the data shows that, under comparable lithography conditions, formulations produced using polymers as disclosed herein had similar or better Esize and LWR than comparable formulations having the same components except that they were produced using comparative polymers. With respect to trench patterning, the data shows that, under comparable lithography conditions, formulations produced using polymers as disclosed herein had better Esize and LWR than comparable formulations having the same components except that they were produced using comparative polymers.

[0138] [Table 2]

[0139] [Table 3]

[0140] This disclosure further encompasses the following aspects:

[0141] Appearance 1: Equation (1) [ka] (In the formula, R1, R3, R4, R5, and R6 are independently H, a linear, branched, or alicyclic substituted or unsubstituted alkyl group having 1, 2, or 3 to a maximum of 20, up to 15, or up to 20, up to 15, or up to 10 carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms; R2 is selected from null (i.e., directly bonded), a linear, branched, or alicyclic substituted or unsubstituted alkylene group having 1, 2, or 3 to a maximum of 20, up to 15, or up to 10 carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms; n is an integer from 0 to 3, or R1 and R2 or R1 and R6 together with the carbon atoms in the ring structure to which they are bonded to form a cyclic structure.) A polymer comprising a first repeating unit derived from a first monomer.

[0142] Embodiment 2: The polymer according to Embodiment 1, wherein R1 is an alkyl group with 1, 2, or 3 carbon atoms.

[0143] Embodiment 3: The polymer according to Embodiment 1 or 2, wherein R2 is an alkylene group having 1 to 3 carbon atoms.

[0144] Embodiment 4: The polymer according to any one of Embodiments 1 to 3, wherein R3 is an alkyl group having 3 to 10 carbon atoms.

[0145] Embodiment 5: The polymer according to any one of Embodiments 1 to 4, wherein R4 and R5 are H.

[0146] Embodiment 6: The polymer according to any one of Embodiments 1 to 5, wherein n is 1.

[0147] Appearance 7: Equation (II) [ka] The polymer according to any one of embodiments 1 to 6, further comprising one or more additional repeating units derived from one or more ethylenically unsaturated monomers of the formula (wherein R7 is a hydrogen atom or a methyl group; R8 is a direct bond or a divalent linking group; and R9 is a lactone or a sultone).

[0148] Appearance 9: One or more ethylenically unsaturated monomers of the formula (IV) (wherein each R 12 This is halogen, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 4~30 It is an alkyl heteroaryl, where each R 12 It optionally further includes a divalent linking group as part of its structure; R 13 and R 14 These are, independently, hydrogen, halogen, substituted or unsubstituted C. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 2~20 Heterocycloalkyl, C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30Heteroarylalkyl, or substituted or unsubstituted C 4~30 It is an alkyl heteroaryl, where R 13 and R 14 Each of them independently may optionally further include a divalent linking group as part of their structure; or R 12 , R 13 , and R 14 The polymer according to any one of embodiments 1 to 7, further comprising one or more additional repeating units derived from monomers (where any two or more of the monomers together form a ring via single bonds or divalent linking groups; where p is 1 or 2; and n is an integer from 1 to 6).

[0149] Embodiment 10: The polymer according to any one of Embodiments 1 to 9, further comprising one or more additional repeating units derived from one or more ethylenically unsaturated monomers (III) containing an acid-unstable group.

[0150] Embodiment 11: Monomer (III) containing an acid-unstable group is of the formula [ka] (In the formula, R 10 This is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It is alkyl, R 11 The polymer according to embodiment 10, wherein (is an acid-unstable group).

[0151] Embodiment 12: The polymer according to any one of Embodiments 1 to 11, comprising the first repeating units in an amount of 5 to 25 mole percent based on the total moles of the first repeating units and additional repeating units in the polymer.

[0152] Embodiment 13: A polymer according to any one of Embodiments 10 to 13, wherein, based on the total moles of the first repeating units and additional repeating units in the polymer, the repeating units derived from the monomer of formula II are present in an amount of 10 to 60 mol%, the repeating units derived from the monomer of formula III are present in an amount of 20 to 70 mol%, and the repeating units derived from the monomer of formula IV are present in an amount of 5 to 30 mol%.

[0153] Embodiment 14: A photoresist composition comprising a polymer; a photoacid generator; and a solvent according to any one of Embodiments 1 to 13.

[0154] Embodiment 15: A photoresist composition according to Embodiment 14, further comprising a deactivator selected from a photodegradable deactivator or a basic deactivator; a basic unstable material, or a mixture thereof.

[0155] Embodiment 16: A method for forming a pattern, comprising: coating a layer of the photoresist composition described in either Embodiment 14 or 15 onto a substrate to provide a photoresist composition layer; pattern-exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer to provide a photoresist pattern.

[0156] Embodiment 17: The method according to Embodiment 16, wherein the photoresist composition layer is exposed to 193 nm radiation or EUV radiation, and the photoresist pattern includes features having dimensions of less than 60 nm.

Claims

1. Formula (1) 【Chemistry 1】 (wherein, R １ , R ３ , R ４ , R ５ , R ６ are independently H, a linear, branched or alicyclic substituted or unsubstituted alkyl group having from 1 to a maximum of 20 carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms; R ２ is selected from null, a linear, branched or alicyclic substituted or unsubstituted alkylene group having from 1 to a maximum of 20 carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms; n is an integer from 0 to 3, or R １ and R ２ or R １ and R ６ together with the carbon atoms in the ring structure to which they are attached form a cyclic structure), a polymer containing a first repeating unit derived from a first monomer.

2. R １ is an alkyl group with 1, 2, or 3 carbon atoms, and R ２ R is an alkylene group with 1 to 3 carbon atoms. ３ R is an alkyl group consisting of 3 to 10 carbon atoms. ４ and R ５ The polymer according to claim 1, wherein is H and n is 1.

3. The polymer according to claim 1, further comprising one or more additional repeating units derived from one or more ethylenically unsaturated monomers.

4. The one or more ethylenically unsaturated monomers mentioned above are: Formula (II) 【Chemistry 2】 (In the formula, R ７ R is a hydrogen atom or a methyl group, ８ R is a direct bond or a divalent linking group. ９ (These are monomers of lactones or sultones) Monomers containing acid-unstable groups (III), Formula (IV) (In the formula, each R １２ C is a halogen, substituted, or unsubstituted C １～３０ Alkyl, substituted, or unsubstituted C １～３０ Heteroalkyl, substituted, or unsubstituted C ３～３０ Cycloalkyl, substituted, or unsubstituted C ２～２０ Heterocycloalkyl, substituted or unsubstituted C ２～２０ Alkenyl, substituted, or unsubstituted C ３～２０ Cycloalkenyl, substituted or unsubstituted C ３～２０ Heterocycloalkenyl, C ６～３０ Aryl, substituted, or unsubstituted C ７～３０ Arylalkyl, substituted, or unsubstituted C ７～３０ Alkylaryl, substituted, or unsubstituted C ３～３０ Heteroaryl, substituted, or unsubstituted C ４～３０ Heteroarylalkyl, or substituted or unsubstituted C ４～３０ It is an alkyl heteroaryl, where each R １２ It optionally further includes a divalent linking group as part of its structure; R １３ and R １４ These are, independently, hydrogen, halogen, substituted or unsubstituted C. １～３０ Alkyl, substituted, or unsubstituted C １～３０ Heteroalkyl, substituted, or unsubstituted C ３～３０ Cycloalkyl, substituted, or unsubstituted C ２～２０ Heterocycloalkyl, C ６～３０ Aryl, substituted, or unsubstituted C ７～３０ Arylalkyl, substituted, or unsubstituted C ７～３０ Alkylaryl, substituted, or unsubstituted C ３～３０ Heteroaryl, substituted, or unsubstituted C ４～３０ Heteroarylalkyl, or substituted or unsubstituted C ４～３０ It is an alkyl heteroaryl, where R １３ and R １４ Each of them independently optionally further includes a divalent linking group as part of its structure; or R １２ , R １３ , and R １４ Any two or more monomers together form a ring via single or divalent linking groups; p is 1 or 2; n is an integer from 1 to 6. Alternatively, the polymer according to claim 3, comprising a mixture of two or more of those.

5. The monomer (III) containing the acid-unstable group is, 【Transformation 3】 (In the formula, R １０ This is hydrogen, fluorine, cyano, or substituted or unsubstituted C １～１０ It is alkyl, R １１ (It is an acid-unstable group.) The polymer according to claim 4, having the following characteristics.

6. The polymer according to claim 4, comprising the first repeating units in an amount of 5 to 25 mole percent based on the total moles of the first repeating units and additional repeating units in the polymer.

7. The polymer according to claim 6, wherein, based on the total moles of the first repeating units and additional repeating units in the polymer, repeating units derived from the monomer of formula II are present in an amount of 10 to 60 mol%, repeating units derived from monomer III are present in an amount of 20 to 70 mol%, and repeating units derived from the monomer of formula IV are present in an amount of 5 to 30 mol%.

8. A photoresist composition comprising the polymer according to claim 1; a photoacid generator; and a solvent.

9. The photoresist composition according to claim 8, further comprising: a deactivator selected from a photodegradable deactivator or a basic deactivator; a basic unstable material; or both.

10. A method for forming a pattern, A photoresist composition layer is provided by coating a layer of the photoresist composition described in claim 8 onto a substrate; To provide the exposed photoresist composition layer by pattern-like exposure of the photoresist composition layer with activating radiation; and The exposed photoresist composition layer is developed to provide a photoresist pattern. A method that includes this.

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