Polymer for photoetching medium composition, and photoetching medium composition

Abstract

The present application relates to a polymer for a photoetching medium composition, and a photoetching medium composition. The polymer has a structural unit as represented by general formula (1) below. In the present invention, under the circumstance that the polymer retains a carbon-rich structure (i.e. a multi-benzene-ring structure), a secondary hydroxyl structure is introduced into the structure and can provide a cross-linking site during a film-forming process of a material, thereby improving the overall cross-linking density of the material and further improving the etching resistance of the material. In addition, the secondary hydroxyl structure can serve as a polar acting site and has relatively strong movement ability, thereby prompting an improvement in the ability thereof regarding interaction with a solvent, and ensuring the dissolution performance of the material. The polymer of the present application has both good solubility and good etching resistance, the solubility thereof is maintained while the etching resistance thereof is improved, and the polymer is very suitable as an etching-resistant dielectric layer material.

Description

Polymer for photolithographic dielectric composition and photolithographic dielectric composition Technical Field

[0001] The present application relates to polymers for photolithographic dielectric compositions and photolithographic dielectric compositions. Background Art

[0002] Photolithography is one of the most important processes in the manufacture of semiconductor integrated circuit chips. Specifically, photolithography utilizes the photosensitivity of photoresist (photoresist) to transfer the fine circuit patterns of the integrated circuit from the mask to the photoresist. The final pattern is then formed on the substrate through a subsequent etching process, or ion implantation is performed through ion implantation. With the development of the semiconductor integrated circuit industry, the integrated circuit patterns produced by photolithography have become increasingly fine, from tens of nanometers to several nanometers. In a typical photolithography process, the photoresist forms a photolithographic pattern after exposure and development, and serves as a mask for etching the underlying substrate material. Therefore, the photoresist layer must have a certain degree of etch resistance. With the development of photolithography and the increasing demand for pattern fineness, the thickness of the photoresist layer must be reduced to improve resolution, resulting in the fact that photoresist alone cannot fully fulfill the role of mask. Therefore, a multi-layer stacking process (such as photoresist-antireflective interlayer-etch-resistant interlayer-substrate material layer) must be designed to meet the production requirements of high-aspect ratio patterns. After the photolithography pattern is formed in the photoresist layer, the pattern is transferred layer by layer to the intermediate dielectric layers and the base material layer by taking advantage of the different etching rates of the etching gas for different material layers. Throughout the entire process, the previous layer of material acts as an etching mask for the next layer.

[0003] Furthermore, spin coating is a more cost-effective method for thin-film fabrication than chemical deposition, and the resulting intermediate layer exhibits improved fillability and planarization properties. Therefore, the intermediate dielectric layer material must possess excellent etch resistance, planarization, and anti-reflection properties while also maintaining good solubility. Therefore, there remains a need in the art for a photolithography dielectric layer material with improved etch resistance and balanced solubility.

[0004] Summary of the Invention

[0005] The present application provides a polymer for a photolithographic medium composition, which has a structural unit represented by the following general formula (1):

[0006] Wherein, A is a C6-C30 monocyclic or polycyclic aromatic group,

[0007] R 2 Each is independently selected from hydrogen, halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, -OR 11 、-SR 11、-NR 11 R 12 , ether or ester group;

[0008] Z is selected from a single bond, substituted with 0 to 3 R A C1-C10 alkylene, substituted with 0-3 R A C6-C20 arylene, substituted with 0-3 R A C6-C20 aralkylene, substituted with 0-3 R A C4-C20 heteroarylalkylene or substituted with 0-3 R A C1-C10 heteroalkylene;

[0009] R 1 Selected from substituted with 0 to 3 R A C1-C10 alkyl, substituted with 0-3 R A C6-C20 aryl, substituted with 0-3 R A A heteroaryl group containing 3 to 20 skeleton ring atoms and one or more identical or different heteroatoms, substituted with 0 to 3 R A A heterocyclic group containing 3 to 20 skeleton ring atoms and one or more identical or different heteroatoms, or substituted with 0 to 3 R A A cyclic hydrocarbon group containing 3 to 20 carbon atoms;

[0010] R A Each is independently selected from hydrogen, halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, -OR 11 、-SR 11 、-NR 11 R 12 , ether or ester group;

[0011] R 11 and R 12 are each independently selected from hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl;

[0012] n is 1, 2 or 3.

[0013] In one embodiment, the structural unit represented by general formula (1) is the structural unit represented by general formula (2)

[0014] Among them, R 1 、R 2 , n and Z are as defined above.

[0015] In one embodiment, R 2 is a hydroxyl group, and n is 1 or 2.

[0016] In one embodiment, the structural unit represented by general formula (1) is the structural unit represented by general formula (3)

[0017] Among them, R 1 、R 2 and Z are as defined above.

[0018] In one embodiment, R 1 Selected from substituted with 0 to 3 R A C6~C20 aromatic group.

[0019] In one embodiment, the C6-C20 aryl group is selected from phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl and terphenyl.

[0020] In one embodiment, Z is selected from the following structural formula

[0021] In one embodiment, the polymer further comprises a structural unit represented by formula (4) and / or a structural unit represented by formula (5)

[0022] Among them, R 3 Selected from C8-C20 arylmethylene, C8-C30 arylmethine or C8-C40 arylcarbonyl;

[0023] R 1 、R 2 , Z and n are as defined above.

[0024] In one embodiment, the structural unit represented by general formula (4) is the structural unit represented by general formula (6)

[0025] Among them, R 2 is hydroxyl group, R 3 C8-C20 aryl methylene groups, such as anthrylmethylene, pyrenylmethylene, naphthylmethylene, phenylmethylene, etc., C8-C30 aryl methine groups, such as diphenylmethyl, fluorenyl, etc., C8-C40 aryl carbonyl groups, such as triphenylcarbonyl, phenylfluorenylcarbonyl, etc.;

[0026] The structural unit represented by general formula (5) is the structural unit represented by general formula (7)

[0027] Among them, R 1 Selected from substituted with 0 to 3 R A C6-C20 aryl; preferably, the C6-C20 aryl is selected from phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl and terphenyl;

[0028] R 2is hydroxyl group;

[0029] R 3 It is a C8-C20 aryl methylene group, such as anthracenyl methylene, pyrenyl methylene, naphthyl methylene, phenyl methylene, etc.; or it is a C8-C30 aryl methine group, such as diphenylmethyl, fluorenyl, etc.; or it is a C8-C40 aryl carbonyl group, such as triphenylcarbonyl, phenylfluorenylcarbonyl, etc.

[0030] In one embodiment, the weight average molecular weight of the polymer is 500 to 20,000 Da, preferably 1,000 to 5,000 Da; and the molecular weight distribution is 1.1 to 4.0.

[0031] The present application also relates to a photolithography dielectric composition, comprising an acid generator, a cross-linking agent, and a dielectric material, wherein the dielectric material is the polymer mentioned above.

[0032] In one embodiment, the amount of the dielectric material is 0.1 to 30 wt %, preferably 2 to 15 wt %, more preferably 3 to 10 wt %, based on the total weight of the photolithographic dielectric composition;

[0033] Based on the total weight of the photoresist dielectric composition, the amount of the crosslinking agent is 0 to 10 wt %;

[0034] The amount of the acid generator is 0 to 10 wt % based on the total weight of the photoresist dielectric composition.

[0035] In one embodiment, the acid generator comprises a thermal acid generator and optionally a photoacid generator,

[0036] Wherein, based on the total weight of the photolithographic dielectric composition, the content of the thermal acid generator is 0 to 10 wt %, preferably 0.01 to 5 wt %, and more preferably 0.01 to 3 wt %;

[0037] Based on the total weight of the photoresist dielectric composition, the content of the photoacid generator is 0 to 10 wt %, preferably 0 to 5 wt %, and more preferably 0.01 to 3 wt %.

[0038] In one embodiment, the photolithographic dielectric composition further comprises a surfactant and a solvent.

[0039] In one embodiment, the content of the surfactant is between 0 and 20 wt %, more preferably 0.0001 to 5 wt %, based on the total weight of the photolithographic dielectric composition;

[0040] The solvent is present in an amount of 70 to 99 wt %, more typically 85 to 99 wt %, based on the total weight of the photoresist dielectric composition.

[0041] The present application also relates to a photolithographic medium layer, which is formed from the above-mentioned photolithographic medium composition.

[0042] The polymer of the present invention, while maintaining a carbon-rich structure (i.e., a polyphenyl ring structure), introduces a secondary hydroxyl structure into the structure. The secondary hydroxyl structure can provide a cross-linking site during the film-forming process of the material, thereby increasing the overall cross-linking density of the material and thus improving the etching resistance of the material. In addition, the secondary hydroxyl structure can be used as a polar action site and the structure has a strong mobility, which promotes the interaction ability with the solvent to improve, thereby ensuring the performance of the material in terms of solubility. The polymer of the present application has excellent performance in terms of solubility and etching resistance, and while improving etching resistance, takes into account its solubility, and is very suitable as an etching-resistant dielectric layer material. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 is a graph showing the polymer A-1 obtained in Example 1. 1 H-NMR spectrum. DETAILED DESCRIPTION

[0044] The present application will be further described in detail below through the accompanying drawings and examples, through which the features and advantages of the present application will become more clear and distinct.

[0045] The word "exemplary" is used exclusively herein to mean "serving as an example, example, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are shown in the drawings, the drawings are not necessarily drawn to scale unless otherwise indicated.

[0046] In addition, the technical features involved in different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0047] definition

[0048] It should be understood that the above summary and the following detailed description are exemplary and explanatory only and do not limit the subject matter of the present invention in any way. In this application, it must be noted that unless otherwise clearly indicated, the singular forms used in this specification and claims include the plural forms of the referents. It should also be noted that unless otherwise indicated, the use of "or" and "or" means "and / or". In addition, the use of the term "including" and other forms, such as "comprising", "including" and "containing" are not limiting.

[0049] When a substituent is described by a conventional chemical formula written from left to right, the substituent also includes chemically equivalent substituents that would result if the formula were written from right to left. For example, CH2O is equivalent to OCH2.

[0050] The term "substituted or unsubstituted" includes both "substituted" and "unsubstituted", where "substituted" means that any one or more hydrogen atoms on a specific atom are replaced by a substituent, as long as the valence state of the specific atom is normal and the compound after substitution is stable; "unsubstituted" means that the hydrogen atoms on the specific atom are not replaced by a substituent. For example, "substituted or unsubstituted ethyl" (for example, when the substituent is a halogen) includes unsubstituted (-CH2CH3), monosubstituted (such as -CH2CH2F), polysubstituted (such as -CHFCH2F, -CH2CHF2, etc.) or fully substituted (-CF2CF3). It will be understood by those skilled in the art that for any group containing one or more substituents, no substitution or substitution pattern that is sterically impossible to exist and / or cannot be synthesized will be introduced. When the substituent is oxo (i.e., =O), it means that two hydrogen atoms on the same atom are replaced.

[0051] When any variable (e.g., R) occurs more than once in a compound's composition or structure, its definition is independent on each occurrence. Thus, for example, if a group is represented by 0 to 3 R A substituted, then the group may optionally be replaced by up to three R A is replaced, and in each case R A are all independent options. In addition, combinations of substituents and / or their variants are permissible only if such combinations result in stable compounds. The term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and the description includes both occurrence of the event or circumstance and non-occurrence of the event or circumstance.

[0052] As used herein, Cm-Cn refers to a moiety having m-n carbon atoms. For example, a "C1-C8" group refers to a moiety having 1-8 carbon atoms, i.e., the moiety contains 1 carbon atom, 2 carbon atoms, 3 carbon atoms, ... 8 carbon atoms. Thus, for example, "C1-C8 alkyl" refers to an alkyl group containing 1-8 carbon atoms, i.e., the alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, ... octyl, etc. Numeric ranges herein, such as "1-8," refer to each integer in the given range, such as "1-8 carbon atoms," which means the moiety may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, or 8 carbon atoms.

[0053] The term "alkyl" refers to an optionally substituted straight-chain or optionally substituted branched saturated aliphatic hydrocarbon group that is attached to the rest of the molecule by a single bond. The "alkyl" herein may have 1 to 8 carbon atoms, for example, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples of "alkyl" herein include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, and the like, as well as longer alkyl groups such as heptyl and octyl, and the like. When a group is defined herein, such as "alkyl," a numerical range is included. For example, "C1-C8 alkyl" refers to an alkyl group consisting of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, or 8 carbon atoms. For another example, "C1-C4 alkyl" refers to an alkyl group consisting of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, or 4 carbon atoms. Alkyl groups herein also include groups without a numerical range.

[0054] The term "alkenyl" refers to an optionally substituted straight chain or optionally substituted branched monovalent hydrocarbon group having at least one C=C double bond. The alkenyl group has, but is not limited to, 2 to 8 carbon atoms, such as 2 to 6 carbon atoms, 2 to 4 carbon atoms. The double bonds in these groups can be in cis or trans conformations and should be understood to include the two isomers. Examples of alkenyl groups include, but are not limited to, vinyl (CH=CH2), 1-propenyl (CH2CH=CH2), isopropenyl (C(CH3)=CH2), butenyl and 1,3-butadienyl, etc. When a numerical range appears in the alkenyl group defined herein, for example, "C2 to C8 alkenyl" refers to an alkenyl group that can be composed of 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, or 8 carbon atoms, and the alkenyl group herein also covers the case where a numerical range is not specified.

[0055] The term "alkynyl" refers to an optionally substituted linear or branched monovalent hydrocarbon group having at least one C≡C triple bond. The alkynyl group has, but is not limited to, 2 to 8 carbon atoms, such as 2 to 6 carbon atoms, or 2 to 4 carbon atoms. Examples of alkynyl groups herein include, but are not limited to, ethynyl, 2-propynyl, 2-butynyl, and 1,3-butadiynyl. When a numerical range appears in the alkynyl group defined herein, for example, "C2 to C8 alkynyl" refers to an alkynyl group that can be composed of 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, or 8 carbon atoms. The alkynyl group herein also covers the case where a numerical range is not specified.

[0056] The term "cycloalkyl" refers to a non-aromatic carbon ring, including a saturated carbocyclic ring (such as a cycloalkyl group) or an unsaturated carbocyclic ring (such as a cycloalkenyl group). Carbocyclic rings include monocarbocyclic rings (having one ring), for example, a monocyclic cycloalkyl group; bicarbocyclic rings (having two rings), for example, a bicyclic cycloalkyl group; and polycarbocyclic rings (having more than two rings). The rings may be bridged or spirocyclic. Carbocyclic rings (such as cycloalkyl or cycloalkenyl) may have 3 to 8 carbon atoms, for example, 3 to 6 ring carbon atoms or 3 to 5 ring carbon atoms. Cycloalkyl groups containing 3 to 20 carbon atoms may be cycloalkyl groups containing 3 to 12 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0057] The term "aryl" refers to an optionally substituted aromatic hydrocarbon group having 6 to 20, such as 6 to 12 or 6 to 10, ring-forming carbon atoms, and can be a monocyclic aromatic group, a bicyclic aromatic group, or a polycyclic aromatic group. A bicyclic aromatic group or a polycyclic aromatic group can be a monocyclic aromatic group fused to another independent ring, such as an alicyclic ring, a heterocyclic ring, an aromatic ring, or an aromatic heterocyclic ring. Non-limiting examples of monocyclic aromatic groups include monocyclic aromatic groups having 6 to 12, 6 to 10, or 6 to 8 ring-forming carbon atoms, such as phenyl; bicyclic aromatic groups include naphthyl; and polycyclic aromatic groups include phenanthrenyl, anthracenyl, and azulenyl.

[0058] The term "arylmethylene" refers to a methylene group having an aryl group attached thereto, wherein "aryl" is as explained above.

[0059] The term "arylmethine" refers to a methine group in which one or more aryl groups are linked to the methine group, wherein "aryl" is as explained above.

[0060] The term "arylcarbonyl" refers to a carbon group in which one or more aryl groups are linked, wherein "aryl" has the same meaning as above.

[0061] The term "heteroaryl" refers to an optionally substituted heteroaryl group containing about 5 to 20, such as 5 to 12 or 5 to 10 skeleton ring atoms, wherein at least one (such as 1 to 4, 1 to 3, 1 to 2) ring atoms is a heteroatom, and the heteroatom is independently selected from the heteroatoms of oxygen, nitrogen, sulfur, phosphorus, silicon, selenium and tin, but is not limited thereto. Heteroaryl groups include monocyclic heteroaryl groups (having one ring), bicyclic heteroaryl groups (having two rings) or polycyclic heteroaryl groups (having more than two rings). In embodiments where two or more heteroatoms appear in the ring, the two or more heteroatoms may be the same as each other, or some or all of the two or more heteroatoms may be different from each other. Bicyclic heteroaryl groups or polycyclic heteroaryl groups may be a monocyclic heteroaryl group fused with other independent rings, such as alicyclic rings, heterocyclic rings, aromatic rings, or aromatic heterocyclic rings (collectively referred to as fused ring heteroaryl groups). Non-limiting examples of heteroaryl groups include, but are not limited to, pyrrolyl, furanyl, thienyl, imidazolyl, oxazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, tetrazolyl, triazolyl, triazinyl, benzofuranyl, benzothienyl, indolyl, isoindolyl, and the like.

[0062] The term "heterocyclyl" refers to a non-aromatic heterocycle, including saturated or unsaturated heterocycles (containing unsaturated bonds), that does not have a completely conjugated π-electron system and can be classified as a non-aromatic monocyclic, fused polycyclic, bridged, or spirocyclic system, in which one or more (e.g., 1 to 4, 1 to 3, 1 to 2) of the ring atoms are heteroatoms, such as oxygen, nitrogen, or sulfur atoms. Heterocycles can include monocyclic heterocycles (having one ring), bicyclic heterocycles (having two bridged rings), or polycyclic heterocycles (having more than two bridged rings); spirocycles are also included. A heterocyclyl group can have 3 to 20, such as 3 to 10, 3 to 8, 4 to 8, 4 to 7, 5 to 8, or 5 to 6, ring atoms. Non-limiting examples of heterocyclyl groups include oxiranyl, thioranyl, aziridinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuranyl, pyrrolidinyl, oxazolidinyl, tetrahydropyrazolyl, pyrrolinyl, dihydrofuranyl, dihydrothiophenyl, piperidinyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, piperazinyl, dihydropyridinyl, tetrahydropyridinyl, dihydropyranyl, tetrahydropyranyl, dihydrothiopyranyl, azepanyl, oxepanyl, thiepanyl, oxazabicyclo[2.2.1]heptyl, and azaspiro[3.3]heptyl, and the like.

[0063] Other group terms herein include: "hydroxy" refers to an -OH group, "thiol" refers to a -SH group, "cyano" refers to a -CN group, and "carboxyl" refers to a -COOH group.

[0064] The present application relates to a polymer for a photolithographic medium composition, which has a structural unit represented by the following general formula (1):

[0065] Wherein, A is a C6-C30 monocyclic or polycyclic aromatic group,

[0066] R 2 Each is independently selected from hydrogen, halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, -OR 11 、-SR 11 、-NR 11 R 12 , ether or ester group;

[0067] Z is selected from a single bond, substituted with 0 to 3 R A C1-C10 alkylene, substituted with 0-3 R A C6-C20 arylene, substituted with 0-3 R A C6-C20 aralkylene, substituted with 0-3 R A C4-C20 heteroarylalkylene or substituted with 0-3 R A C1-C10 heteroalkylene;

[0068] R 1 Selected from substituted with 0 to 3 R A C1-C10 alkyl, substituted with 0-3 R A C6-C20 aryl, substituted with 0-3 R A A heteroaryl group containing 3 to 20 skeleton ring atoms and one or more identical or different heteroatoms, substituted with 0 to 3 R A A heterocyclic group containing 3 to 20 skeleton ring atoms and one or more identical or different heteroatoms, or substituted with 0 to 3 R A A cyclic hydrocarbon group containing 3 to 20 carbon atoms;

[0069] R A Each is independently selected from hydrogen, halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, -OR 11 、-SR 11 、-NR 11 R 12 , ether or ester group;

[0070] R 11 and R 12 are each independently selected from hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl;

[0071] n is 1, 2 or 3.

[0072] Preferably, the structural unit represented by general formula (1) is the structural unit represented by general formula (2)

[0073] Among them, R1 、R 2 , n and Z are defined as shown in formula (1). It should be noted that in the structural unit shown in the above general formula (2), n R 2 It can be located on the same benzene ring of the naphthalene ring, or on two different benzene rings of naphthalene. 2 Located on two different benzene rings of naphthalene.

[0074] In one embodiment, R 2 is a hydroxyl group, and n is 1 or 2.

[0075] In one embodiment, the structural unit represented by general formula (1) is the structural unit represented by general formula (3)

[0076] Among them, R 1 、R 2 and Z are defined as shown in formula (1). Preferably, R 2 It is a hydroxyl group, that is, it has two hydroxyl groups, and the two hydroxyl groups are located on two different benzene rings of the naphthalene ring.

[0077] In one embodiment, R 1 Selected from substituted with 0 to 3 R A Preferably, the C6-C20 aryl group is selected from phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl and terphenyl.

[0078] In one embodiment, Z is selected from the following structural formula

[0079] In the above structural formula, * indicates the connection position of the above structural formula.

[0080] The polymer can be 2 The compound is first polymerized with a monomer having cross-linking reactivity to form a polymer chain; then one or more aldehyde compounds are added to the reaction system to modify the side chain of the polymer with a secondary hydroxyl structure.

[0081] For active groups R 2 The compound may be a naphthalene compound, for example substituted with one or more R 2 Naphthalene compounds. For example, the naphthalene compound may be naphthol, dihydroxynaphthalene, dimercaptonaphthalene, naphthylamine, hydroxynaphthylamine, etc. For dihydroxynaphthalene, it may include 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, etc. For dimercaptonaphthalene, it may include 2,7-dimercaptonaphthalene, 2,6-dimercaptonaphthalene, 1,6-dimercaptonaphthalene, 2,3-dimercaptonaphthalene, etc. For hydroxynaphthylamine, it may include 6-hydroxynaphthalene-2-amine, 7-hydroxynaphthalene-2-amine, etc.

[0082] As monomers with cross-linking reactivity, aldehydes such as formaldehyde and paraformaldehyde, or diol compounds such as terephthalene dimethanol, biphenyl dimethanol, naphthalene dimethanol and anthracene dimethanol can be used. 2 The amount of the cross-linking reactive monomer used is 0.5 to 1.5 mol, particularly 0.8 to 1.2 mol.

[0083] The above polymerization reaction process can be carried out in the presence of a catalyst. The catalyst can be an acid catalyst, and inorganic acids or organic acids can be used, such as hydrochloric acid, sulfuric acid and other inorganic acids, and p-toluenesulfonic acid, acetic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and other organic acids. Lewis acids such as aluminum chloride and zinc chloride can also be used. 2 For compounds with a moiety (such as the above-mentioned naphthalene compound), the amount of the acid catalyst used can be 0.0001 to 0.1 mol.

[0084] The polymerization reaction may be carried out using a reaction solvent such as an alcohol solvent (e.g., diethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether, ethylene glycol dimethyl ether), an ester solvent (e.g., propylene glycol methyl ether acetate, ethyl lactate, ethyl acetate, butyl acetate), a halogenated hydrocarbon (e.g., dichloromethane, chloroform, ethylene dichloride), or a combination thereof. The polymerization reaction may be carried out at a temperature of 50 to 160° C.

[0085] In one embodiment, the polymer may further comprise a structural unit represented by general formula (4) and / or a structural unit represented by general formula (5):

[0086] Among them, R 3 Selected from C8-C20 arylmethylene, C8-C30 arylmethine or C8-C40 arylcarbonyl;

[0087] R 1 、R 2 , Z and n are as defined above.

[0088] In one embodiment, the structural unit represented by general formula (4) is the structural unit represented by general formula (6)

[0089] Among them, R 2 is hydroxyl group, R 3is a C8-C20 aryl methylene group, such as anthrylmethylene, pyrenylmethylene, naphthylmethylene, phenylmethylene, etc., is a C8-C30 aryl methine group, such as diphenylmethyl, fluorenyl, etc., is a C8-C40 aryl carbonyl group, such as triphenylcarbonyl, phenylfluorenylcarbonyl, etc. The structural unit represented by the general formula (6) above has two hydroxyl groups, and the two hydroxyl groups are located on two different benzene rings of the naphthalene ring.

[0090] The structural unit represented by general formula (5) is the structural unit represented by general formula (7)

[0091] Among them, R 1 Selected from substituted with 0 to 3 R A Preferably, the C6-C20 aryl group is selected from phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl and terphenyl.

[0092] R 2 is hydroxyl group;

[0093] R 3 is a C8-C20 aryl methylene group, such as anthrylmethylene, pyrenylmethylene, naphthylmethylene, phenylmethylene, etc.; or is a C8-C30 aryl methine group, such as diphenylmethyl, fluorenyl, etc.; or is a C8-C40 aryl carbonyl group, such as triphenylcarbonyl, phenylfluorenylcarbonyl, etc. The structural unit represented by the general formula (7) above has two hydroxyl groups, and the two hydroxyl groups are located on two different benzene rings of the naphthalene ring.

[0094] The polymer of the present application may contain the structural unit represented by the general formula (4) and / or the structural unit represented by the general formula (5) (especially, the structural unit represented by the general formula (6) and / or the structural unit represented by the general formula (7)). Since the structural units represented by the general formulas (4) to (7) above have an R containing an aromatic group, 3 The group can make the polymer of the present application have a higher carbon content, thereby making the polymer have better etching resistance.

[0095] In the above process of preparing the polymer, a compound with a group R can be added to the polymerization raw material. 3 Reactive compounds are used to form random copolymers containing structural units of formula (1) / (2) / (3) and structural units represented by general formula (4) and / or structural units represented by general formula (5) (particularly, structural units represented by general formula (6) and / or structural units represented by general formula (7)). 3 The reactive compounds include pyrene methanol, anthracene methanol, naphthalene methanol, benzyl alcohol, dibenzyl alcohol, fluorenyl methanol, triphenylmethanol, phenylfluorenylmethanol, 1-phenylethanol and the like.

[0096] After the polymerization reaction, or during the polymerization reaction, a certain amount of aldehyde compound is added to the reaction system to introduce a secondary hydroxyl structure on the side chain of the polymer. The aldehyde compound may include one or more aldehyde compounds, such as benzaldehyde, furfural, hydroxybenzaldehyde (including m-hydroxybenzaldehyde and p-hydroxybenzaldehyde), naphthalene formaldehyde, anthracene formaldehyde, biphenyl formaldehyde, pyrene formaldehyde, pyridine formaldehyde, cyclohexyl formaldehyde, etc. 2 The amount of the aldehyde compound used can be 0.1 to 2.0 mol.

[0097] It should be noted that the side chain modification of the polymer in this application is performed after the polymer chain is formed. Therefore, not every polymer chain segment has a secondary hydroxyl structure introduced by the aldehyde compound. The modification rate of the secondary hydroxyl structure is between 20% and 95%.

[0098] It should be noted that, in the prepared polymer, the R 3 The group and the secondary hydroxyl structure can be located in the same structural unit, as shown in the structural unit of general formula (5) / (7); the R 3 The group can also be located in a different structural unit from the secondary hydroxyl structure, that is, with the R 3 The structural unit of the group does not contain the secondary hydroxyl structure, as shown by the structural unit represented by the general formula (4) / (6).

[0099] In one embodiment, the weight average molecular weight of the polymer is 500 to 20,000 Da, preferably 1,000 to 5,000 Da; and the molecular weight distribution (PDI) is 1.1 to 4.0.

[0100] Because the polymers of this application contain secondary hydroxyl structures, their solubility can be improved, increasing the wettability of the material to the substrate, thereby improving the film quality. Furthermore, these secondary hydroxyl structures are reactive groups that can react with crosslinkers to increase the degree of crosslinking in the film layer, thereby improving the film's etch resistance. Therefore, the above-mentioned compounds and polymers of this application have high solubility in solvents, particularly in propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone, and exhibit excellent solubility and superior etch resistance.

[0101] Photolithographic dielectric composition

[0102] Typically, etch-resistant dielectric layer materials are required to exhibit superior etch resistance in industrial applications. In recent years, efforts have been made to develop dielectric layer materials and apply these materials to multilayer stacking processes. However, existing experience shows that improving material etch resistance (e.g., pursuing high carbon content) often comes at the expense of solubility and film-forming properties.

[0103] However, the polymer of the present invention, while maintaining a carbon-rich structure (i.e., a polyphenyl ring structure), introduces a secondary hydroxyl structure into the structure. The secondary hydroxyl structure can provide a cross-linking site during the film-forming process of the material, thereby increasing the overall cross-linking density of the material and thus improving the etching resistance of the material. In addition, the secondary hydroxyl structure can be used as a polar action site and the structure has a strong mobility, which promotes the interaction ability with the solvent to improve, thereby ensuring the performance of the material in terms of dissolution. The polymer of the present application has excellent performance in terms of solubility and etching resistance, and while improving etching resistance, takes into account its solubility, and is very suitable as an etching-resistant dielectric layer material.

[0104] Therefore, the present application also relates to a photolithographic dielectric composition, which includes an acid generator, a cross-linking agent, and a dielectric material, wherein the dielectric material is the above-mentioned polymer of the present application.

[0105] The dielectric material contained in the photolithographic dielectric composition of the present application may be the above-mentioned polymer of the present application, wherein the amount of the dielectric material is 0.1 to 30 wt %, preferably 2 to 15 wt %, and more preferably 3 to 10 wt %, based on the total weight of the photolithographic dielectric composition.

[0106] In addition to the above-mentioned dielectric materials, the photolithographic dielectric composition of the present application may further include an acid generator, a cross-linking agent, a surfactant, a solvent, and the like.

[0107] In one embodiment, the amount of the acid generator is 0 to 10 wt %, such as 0.001 to 10 wt %, preferably 0.01 to 5 wt %, based on the total weight of the photoresist dielectric composition.

[0108] The acid generator may include a thermal acid generator and an optional photoacid generator. In one embodiment, the thermal acid generator may be an ionic thermal acid generator or a non-ionic thermal acid generator. Ionic thermal acid generators include, but are not limited to, sulfonates such as carbocyclic aromatic and heteroaryl sulfonates, aliphatic sulfonates, benzenesulfonates, trifluoromethanesulfonates, triethylamine dodecylsulfonate, and ammonium p-toluenesulfonate. Non-ionic thermal acid generators include, but are not limited to, p-toluenesulfonic acid, methyl trifluoromethanesulfonate, cyclohexyl trifluoromethanesulfonate, cyclohexyl 2,4,6-triisopropylbenzenesulfonate, 2-nitrobenzyl p-toluenesulfonate, organic alkyl sulfonates, benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate, tris(2,3-dibromopropyl)-1,3,5-triazine-trione, dodecylbenzenesulfonic acid, oxalic acid, phthalic acid, phosphoric acid, camphorsulfonic acid, and their salts, as well as those disclosed in US Pat. No. 10,429,737 B2. The content of the thermal acid generator can be 0-10 wt %, for example, 0.001-10 wt %, preferably 0.01-5 wt %, and more preferably 0.01-3 wt %, based on the total weight of the photolithographic dielectric composition.

[0109] Examples of the photoacid generator include onium salts such as (tetra-tert-butylphenyl)-iodonium trifluoromethanesulfonate and triphenyltrifluoromethanesulfonium salt; halogen-containing compound photoacid generators such as phenylbis(trichloromethyl)-s-triazine; benzoin tosylate and N-hydroxysuccinimidyl trifluoromethanesulfonate-type photoacid generators; and disulfonyldiazomethanes. onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives such as bis(benzenesulfonyloxy)benzene; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate; 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. In one embodiment, the content of the photoacid generator is 0 to 10 wt %, preferably 0 to 5 wt %, and more preferably 0.01 to 3 wt %, based on the total weight of the photolithographic dielectric composition.

[0110] The photoresist dielectric composition of the present application may further include a crosslinking agent. In one embodiment, the amount of the crosslinking agent is 0 to 10 wt %, for example, 0.01 to 10 wt %, based on the total weight of the photoresist dielectric composition. The crosslinking agent used in the present application may be a glycoluril derivative, a melamine derivative, a biphenol derivative, etc., for example, hexamethylolmelamine, hexamethoxymethylmelamine, hexamethoxyethylmelamine, etc.; tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, etc.

[0111] The photoresist medium composition formed by the present invention may be added with a surfactant. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene lauryl (dodecyl) ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene and polyoxypropylene block polymers, sorbitan monolaurate, sorbitan monopalmitate (hexadecanoate), and sorbitan monostearate. , sorbitan monooleate (octadecanoic acid), polyoxyethylene sorbitan monolaurate, sorbitan trioleate, sorbitan tristearate; polyoxyethylene sorbitan monopalmitate (hexadecanoic acid), polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate (octadecanoic acid), polyoxyethylene sorbitan tristearate, etc. In one embodiment, the content of the surfactant is between 0 and 20 wt %, more preferably 0.0001 to 5 wt %, based on the total weight of the photolithographic medium composition.

[0112] The solvent of the photolithographic dielectric composition formed by the present invention includes a single solvent or a mixed solvent of the type of alcohol, ester, ether, cyclic ketone, etc. The solvent includes, but is not limited to, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, ethyl 2-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. In one embodiment, the solvent is present in an amount of 70 to 99 wt %, more typically 85 to 99 wt %, based on the total weight of the photolithographic dielectric composition.

[0113] The present application also relates to a photolithographic dielectric layer formed from the photolithographic dielectric composition described above. The method for forming the dielectric layer is not particularly limited and can be applied to a substrate using methods known in the art, such as spin coating, screen printing, or other known coating or printing methods, to volatilize the organic solvent, thereby forming the dielectric layer. After film formation, baking or other methods can be employed to promote the crosslinking reaction. In one embodiment, the baking temperature can be 80 to 400°C, particularly 200 to 400°C.

[0114] The following examples are provided to further illustrate the present invention.

[0115] Synthesis example 1

[0116] To a 200 mL reaction flask equipped with magnetic stirring and reflux, 16 g (0.1 mol) of 2,7-dihydroxynaphthalene, 11.1 g (0.08 mol) of terephthalic acid, 1.9 g (0.01 mol) of p-toluenesulfonic acid monohydrate, and 100 mL of cyclopentyl methyl ether were added. Stirring was continued at 60°C for 10 minutes to dissolve the mixture completely. The mixture was then heated to reflux for 24 hours. The mixture was cooled to room temperature, and 15.9 g (0.15 mol) of benzaldehyde was added. The mixture was again heated to reflux for 6 hours. After the reaction, the product was precipitated in 500 mL of n-hexane and filtered. The mixture was washed with deionized water and then n-hexane, and dried in a vacuum oven at 50°C to obtain polymer A1. Gel chromatography revealed a weight-average molecular weight of 2500 Da and a PDI of 2.5.

[0117] Use 500MHz 1 The chemical structure was confirmed by H-NMR, and its spectrum is shown in Figure 1. δ(A1): (ppm, DMSO, TMS): 9.11-10.00 (-OH), 6.30-8.00 (Ph-H, >CH-OH), 6.12 (>CH-OH), 5.05 (Ph-CH2OH), 4.50 (Ph-CH2-OH), 3.68-4.75 (Ph-CH2-Ph).

[0118] Synthesis example 2

[0119] Naphthaldehyde was used instead of benzaldehyde. Polymer A2 was obtained by the same operation as in Synthesis Example 1, with a weight average molecular weight of 1700 Da and a PDI of 2.2.

[0120] Use 500MHz 1 H-NMR confirmed the chemical structure, δ(A2) (ppm, DMSO, TMS):

[0121] 9.35-00.05(-OH), 6.60-8.59(Ph-H, >CH-OH), 6.30(>CH-OH), 5.05(Ph-CH2OH), 4.50(Ph-CH2-OH), 4.03-4.77(Ph-CH2-Ph).

[0122] Synthesis example 3

[0123] Pyridine-2-carboxaldehyde was used instead of benzaldehyde. The same operation as in Synthesis Example 1 was performed to obtain polymer A3 with a weight average molecular weight of 2200 Da and a PDI of 1.9.

[0124] Use 500MHz 1H-NMR confirmed the chemical structure, δ(A3) (ppm, DMSO, TMS): 9.27-9.92 (-OH), 6.68-8.80 (Ph-H, >CH-OH), 6.31 (>CH-OH), 5.07 (Ph-CH2OH), 4.50 (Ph-CH2-OH), 3.78-4.32 (Ph-CH2-Ph).

[0125] Synthesis example 4

[0126] Cyclohexylcarboxaldehyde was used instead of benzaldehyde. The same operation as in Synthesis Example 1 was performed to obtain polymer A4 having a weight average molecular weight of 2200 Da and a PDI of 2.0.

[0127] Use 500MHz 1 H-NMR confirmed the chemical structure, δ(A4) (ppm, DMSO, TMS): 9.25-9.76 (-OH), 6.60-7.85 (Ph-H, >CH-OH), 4.53 (>CH-OH), 5.07 (Ph-CH2OH), 4.49 (Ph-CH2-OH), 3.78-4.35 (Ph-CH2-Ph), 1.32-1.89 (-CH2-).

[0128] Synthesis example 5

[0129] 1,6-dihydroxynaphthalene was used instead of benzene 2,7-dihydroxynaphthalene. The same operation as in Synthesis Example 1 was performed to obtain polymer A5 with a weight average molecular weight of 4200 Da and a PDI of 2.6.

[0130] Use 500MHz 1 H-NMR confirmed the chemical structure, δ(A6) (ppm, DMSO, TMS): 8.50-9.73 (-OH), 6.21-8.20 (Ph-H, >CH-OH), 6.12 (>CH-OH), 5.07 (Ph-CH2OH), 4.50 (Ph-CH2-OH), 3.64-4.30 (Ph-CH2-Ph).

[0131] Synthesis example 6

[0132] A portion of 2,7-dihydroxynaphthalene (0.04 mol) in Synthesis Example 1 was replaced with 2-hydroxynaphthalene (0.08 mol). The same operation as Synthesis Example 1 was performed to obtain polymer A6 with a weight-average molecular weight of 5000 Da and a PDI of 3.0.

[0133] Use 500MHz 1The chemical structure was confirmed by H-NMR, δ(A6) (ppm, DMSO, TMS): 9.29-9.98 (-OH), 6.56-8.20 (Ph-H, >CH-OH), 6.12 (>CH-OH), 5.07 (Ph-CH2OH), 4.50 (Ph-CH2-OH), 3.80-4.39 (Ph-CH2-Ph).

[0134] Synthesis Example 7

[0135] The same operation as in Synthesis Example 1 was followed except that a portion of the p-phenylenediol (0.02 mol) was replaced with anthracenemethanol (0.02 mol). Polymer A7 was obtained with a weight-average molecular weight of 3100 Da and a PDI of 2.6.

[0136] Use 500MHz 1 H-NMR confirmed the chemical structure, δ(A7) (ppm, DMSO, TMS): 9.18-10.05 (-OH), 6.36-8.77 (Ph-H, >CH-OH), 6.12 (>CH-OH), 5.07 (Ph-CH2OH), 4.50 (Ph-CH2-OH), 3.65-4.63 (Ph-CH2-Ph).

[0137] Comparative Synthesis Example 1

[0138] To a 200 mL reaction flask equipped with magnetic stirring and reflux, add 14.4 g (0.1 mol) of 2-hydroxynaphthalene, 3 g of paraformaldehyde, and 100 mL of cyclopentyl methyl ether. Stir at 60°C for 10 minutes to completely dissolve the mixture. Then, add 0.95 g of p-toluenesulfonic acid and heat to reflux for 24 hours. After the reaction, the product is precipitated in 500 mL of n-hexane and filtered. The product is washed sequentially with deionized water and n-hexane, and dried in a vacuum oven at 50°C to obtain the target polymer B1. Gel chromatography revealed a weight-average molecular weight of 3300 Da and a PDI of 2.5.

[0139] Use 500MHz 1 H-NMR confirmed the chemical structure, δ (ppm, DMSO, TMS): 9.52-9.92 (-OH), 7.00-8.22 (Ph-H), 4.30-4.68 (Ph-CH2-Ph)

[0140] Comparative Synthesis Example 2

[0141] To a 200 mL reaction flask equipped with magnetic stirring and reflux, add 16 g (0.1 mol) of 2,7-dihydroxynaphthalene, 11.1 g (0.08 mol) of terephthalic acid, 1.9 g (0.01 mol) of p-toluenesulfonic acid monohydrate, and 100 mL of cyclopentyl methyl ether. Stir at 60°C for 10 minutes to completely dissolve the mixture. Heat to reflux for 24 hours. After the reaction, the product is precipitated in 500 mL of n-hexane and filtered. Wash with deionized water and then n-hexane, then dry in a vacuum oven at 50°C to obtain the target product B-2. Gel chromatography reveals a weight-average molecular weight of 2300 Da and a PDI of 2.3.

[0142] Use 500MHz 1 H-NMR confirmed the chemical structure, δ(B2): (ppm, DMSO, TMS): 9.11-10.00 (-OH), 6.30-8.00 (Ph-H), 5.05 (Ph-CH2OH), 4.50 (Ph-CH2-OH), 3.60-4.55 (Ph-CH2-Ph).

[0143] Preparation and performance testing of photolithographic dielectric compositions

[0144] Example 1

[0145] (1) Solubility evaluation

[0146] At 25°C, polymer A1 was dissolved in 100g of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. The maximum amount of polymer dissolved was recorded. A maximum amount dissolved greater than 20g was marked as "excellent", between 10g and 20g was marked as "good", and less than 10g was marked as "poor".

[0147] (2) Optical testing

[0148] Dissolve 0.4 g of polymer A1 obtained in Synthesis Example 1 in 10 g of a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether in a volume ratio of 7:3. Add 8 mg of p-toluenesulfonic acid, 0.08 g of the acid-induced crosslinker Powderlink 1174, and 2 mg of the surfactant polyoxyethylene sorbitan trioleate. Mix the solution thoroughly and filter through a 0.22 μm filter to obtain a photolithographic medium composition.

[0149] The composition was spin-coated on a silicon wafer at 1500 rpm and baked at 250°C for 60 seconds to form a thin film. The film thickness was measured using a spectroscopic ellipsometer, and its refractive index n and extinction coefficient k at 193 nm were obtained.

[0150] (3) Etching resistance evaluation

[0151] The obtained thin film was etched in CF4 plasma gas with a power of 300 W, a flow rate of 40 sccm, and a pressure of 8 mtorr for 60 seconds; and etched in O2 plasma gas with a power of 50 W, a flow rate of 8 sccm, and a pressure of 8 mtorr for 30 seconds. The film thickness was measured using a spectroscopic ellipsometer, and the change in film thickness was calculated. The etching rate of the obtained thin film in the two plasma gases was calculated according to Formula 1-1.

[0152] Etching rate (nm / min) = film thickness change (nm) / time (min) Formula 1-1

[0153] All data are summarized in Table 1-1.

[0154] Example 2

[0155] Except that A1 was replaced by A2, the same composition preparation and testing methods as in Example 1 were adopted.

[0156] Example 3

[0157] Except that A1 was replaced by A3, the same composition preparation and testing methods as in Example 1 were adopted.

[0158] Example 4

[0159] Except that A1 was replaced by A4, the same composition preparation and testing methods as in Example 1 were adopted.

[0160] Example 5

[0161] Except that A1 was replaced by A5, the same composition preparation and testing methods as in Example 1 were adopted.

[0162] Example 6

[0163] Except that A1 was replaced by A6, the same composition preparation and testing methods as in Example 1 were adopted.

[0164] Example 7

[0165] Except that A1 was replaced by A7, the same composition preparation and testing methods as in Example 1 were adopted.

[0166] Comparative Example 1

[0167] Except that A1 was replaced by B1, the same composition preparation and testing methods as in Example 1 were adopted.

[0168] Comparative Example 2

[0169] Except that A1 was replaced by B2, the same composition preparation and testing methods as in Example 1 were adopted.

[0170] Table 1-1

[0171] As shown in the statistical results in Table 1-1, under the test conditions of this experiment, the etching rates of Examples 1-7 were superior to those of Comparative Examples 1 and 2. This indicates that polymers A1-A7 used in Examples 1-7 have superior etching resistance compared to the polymers used in the comparative examples. Comparing the structures of polymers A1-A7 and B2 and the etching test results of the corresponding examples demonstrates that the introduction of secondary hydroxyl groups into the polymer composition is beneficial for improving the material's etching resistance.

[0172] Furthermore, the statistical results in Table 1-1 show that the polymers A-1 to A-7 used in Examples 1 to 7 all exhibited excellent solubility under the experimental conditions, comparable to that of the comparative examples. This indicates that the polymer structure has no negative impact on solubility.

[0173] In summary, the polymer having a secondary hydroxyl structure of the present application can improve the etching resistance of the composition while taking into account the solubility.

[0174] The present application has been described above in conjunction with preferred embodiments, but these embodiments are merely exemplary and serve only as an illustrative example. On this basis, various replacements and improvements can be made to the present application, all of which fall within the scope of protection of the present application.

Claims

1. A polymer for a photolithographic medium composition, which has a structural unit represented by the following general formula (1) in, A is a C6-C30 monocyclic or polycyclic aromatic group, R 2 Each is independently selected from hydrogen, halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, -OR 11 、-SR 11 、-NR 11 R 12 , ether group or ester group; Z is selected from a single bond, substituted with 0 to 3 R A C1-C10 alkylene, substituted with 0-3 R A C6-C20 arylene group, substituted with 0-3 R A C6-C20 aralkylene, substituted with 0-3 R A C4-C20 heteroarylalkylene or substituted with 0-3 R A C1-C10 heteroalkylene; R 1 Selected from substituted with 0 to 3 R A C1-C10 alkyl, substituted with 0-3 R A C6-C20 aryl, substituted with 0-3 R A A heteroaryl group containing 3 to 20 skeleton ring atoms and one or more identical or different heteroatoms, substituted with 0 to 3 R A A heterocyclic group containing 3 to 20 skeleton ring atoms and one or more identical or different heteroatoms, or substituted with 0 to 3 R A A cyclic hydrocarbon group containing 3 to 20 carbon atoms; R A Each is independently selected from hydrogen, halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, -OR 11 、-SR 11 、-NR 11 R 12 , ether group or ester group; R 11 and R 12 Each is independently selected from hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl; n is 1, 2 or 3.

2. The polymer according to claim 1, wherein The structural unit represented by the general formula (1) is the structural unit represented by the general formula (2) Among them, R 1 , R 2 , n and Z are as defined in claim 1.

3. The polymer according to claim 1 or 2, wherein R 2 is a hydroxyl group, and n is 1 or 2.

4. The polymer according to claim 1, wherein The structural unit represented by the general formula (1) is the structural unit represented by the general formula (3) Among them, R 1 , R 2 and Z as defined in claim 1.

5. The polymer according to any one of claims 1 to 4, wherein R 1 Selected from substituted with 0 to 3 R A C6~C20 aromatic group.

6. The polymer according to claim 5, wherein The C6-C20 aryl group is selected from phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl and terphenyl.

7. The polymer according to any one of claims 1 to 6, wherein Z is selected from the following structural formulas 8. The polymer according to any one of claims 1 to 7, wherein The polymer further comprises a structural unit represented by general formula (4) and / or a structural unit represented by general formula (5) Among them, R 3 Selected from C8-C20 aryl methylene, C8-C30 aryl methine or C8-C40 aryl carbonyl; R 1 , R 2 , Z and n are as defined in claim 1.

9. The polymer according to claim 8, wherein The structural unit represented by the general formula (4) is the structural unit represented by the general formula (6) Among them, R 2 is hydroxyl group, R 3 C8-C20 aryl methylene, such as anthracenyl methylene, pyrenyl methylene, naphthyl methylene, phenyl methylene, etc., C8-C30 aryl methine, such as diphenylmethyl, fluorenyl, etc., C8-C40 aryl carbonyl, such as triphenylcarbonyl, phenylfluorenylcarbonyl; The structural unit represented by the general formula (5) is the structural unit represented by the general formula (7) Among them, R 1 Selected from substituted with 0 to 3 R A C6-C20 aryl; preferably, the C6-C20 aryl is selected from phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl and terphenyl; R 2 is hydroxyl group; R 3 It is a C8-C20 aryl methylene group, such as anthracenyl methylene, pyrenyl methylene, naphthyl methylene, phenyl methylene, etc.; or it is a C8-C30 aryl methine group, such as diphenylmethyl, fluorenyl, etc.; or it is a C8-C40 aryl carbonyl group, such as triphenylcarbonyl, phenylfluorenylcarbonyl, etc.

10. The polymer according to any one of claims 1 to 9, wherein The weight average molecular weight of the polymer is 500-20000 Da, preferably 1000-5000 Da; the molecular weight distribution is 1.1-4.

0. 11 . A photolithography dielectric composition, comprising an acid generator, a cross-linking agent, and a dielectric material, wherein the dielectric material is the polymer according to claim 1 .

12. The photolithographic dielectric composition according to claim 11, wherein: Based on the total weight of the photolithographic dielectric composition, the amount of the dielectric material is 0.1 to 30 wt%, preferably 2 to 15 wt%, and more preferably 3 to 10 wt%; Based on the total weight of the photolithographic medium composition, the amount of the crosslinking agent is 0 to 10 wt %; The amount of the acid generator is 0 to 10 wt % based on the total weight of the photolithographic dielectric composition.

13. The photolithographic dielectric composition according to claim 11 or 12, wherein: The acid generator includes a thermal acid generator and an optional photoacid generator, Wherein, based on the total weight of the photolithographic medium composition, the content of the thermal acid generator is 0 to 10 wt %, preferably 0.01 to 5 wt %, and more preferably 0.01 to 3 wt %; Based on the total weight of the photolithographic dielectric composition, the content of the photoacid generator is 0 to 10 wt %, preferably 0 to 5 wt %, and more preferably 0.01 to 3 wt %.

14. The photolithographic medium composition according to any one of claims 11 to 13, further comprising a surfactant and a solvent.

15. The photolithographic dielectric composition according to claim 14, wherein: Based on the total weight of the photolithographic medium composition, the content of the surfactant is between 0 and 20 wt %, more preferably 0.0001 to 5 wt %; The solvent is present in an amount of 70 to 99 wt %, more typically 85 to 99 wt %, based on the total weight of the photolithographic dielectric composition.

16. A photolithographic dielectric layer, formed from the photolithographic dielectric composition according to any one of claims 11 to 15.

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