Non-chemically amplified multi-phenyl substituted adamantane derivative monomolecular resin photoresist, preparation method and application thereof

Abstract

The application discloses a polyphenyl-substituted adamantane derivative monomolecular resin represented by formula IA and a preparation method and application thereof. The polyphenyl-substituted adamantane derivative monomolecular resin has good solubility in various polar solvents, is suitable for being made into a film, has a high decomposition temperature, and can well meet the requirements of a photoetching process.

Description

Technical Field

[0001] This invention belongs to the field of materials technology, and more specifically, relates to a polyphenyl-substituted adamantane derivative monomolecular resin and a non-chemically amplified photoresist composition. Background Technology

[0002] Photoresist, also known as photoresist, is a type of etch-resistant thin film material whose solubility changes upon exposure to energy radiation such as ultraviolet light, electron beams, or ion beams. It is widely used in the microfabrication of integrated circuits and discrete semiconductor devices. By coating photoresist onto the surface of a semiconductor, conductor, or insulator, the remaining portion after exposure and development protects the underlying substrate. Then, an etchant is used to transfer the desired micro-pattern from the photomask to the substrate. Therefore, photoresist is a key material in device microfabrication technology.

[0003] With the rapid development of the semiconductor industry, the requirements for resolution in photolithography technology are becoming increasingly stringent. The resolution of photolithography is not only related to the photolithography equipment but also closely related to the performance of the photoresist material. High-performance photoresists can achieve higher resolution. Traditional photoresists are typically chemically amplified photoresists, mainly composed of an acid-sensitive polymer host material, an acid-generating agent, and additives. Due to their multi-component and chemically amplified characteristics, while they possess high sensitivity, they also suffer from problems such as uneven distribution of components, acid diffusion, and delayed post-baking. In contrast, non-chemically amplified photoresists are usually composed only of a photosensitive host material, undergoing a direct solubility change before and after exposure, thus avoiding the problems associated with chemically amplified photoresists. Non-chemically amplified photoresists also typically exhibit higher resolution and lower line edge roughness.

[0004] In addition, traditional photoresist substrates use polymer resins with molecular weights of 5,000 to 15,000 Daltons. These polymer resins are often affected by factors such as large molecular volume, highly dispersed molecular weight, and entangled molecular chains, which affect the resolution and edge roughness of the photolithography pattern and cannot meet the requirements of high-resolution photolithography.

[0005] Therefore, there is a need to provide a non-chemically amplified monomolecular resin with the smallest possible molecular size, as well as a photoresist material with good film-forming properties and thermal stability, in order to meet the requirements of high-resolution photolithography. Summary of the Invention

[0006] One object of the present invention is to provide a polyphenyl-substituted adamantane derivative monomolecular resin.

[0007] Another object of the present invention is to provide a photoresist composition comprising the polyphenyl-substituted adamantane derivative monomolecular resin.

[0008] To achieve the above objectives, the present invention adopts the following technical solution:

[0009] The following compound is shown in formula IA:

[0010]

[0011] Among them, R1, R2, R3, and R4 may be the same or different, and are independently selected from H or

[0012] Ra is selected from H, OH, -OS(O)2-C n C n Selected from C 1-12 Alkyl, Halogenated C 1-12 Alkyl, -C 6-20 aryl-Rb, -5-20 quinone heteroaryl-Rb, where Rb is selected from nitro, cyano, halogen, C 1-12 Alkyl, C 1-12 alkoxy or halogenated C 1-12 alkyl;

[0013] m is 1, 2, 3, 4 or 5;

[0014] The condition is that at least one of R1, R2, R3, and R4 is selected from... and At least one Ra is -OS(O)2-C n .

[0015] According to an embodiment of the present invention, Ra is selected from H, OH, -OS(O)2-C n C n Selected from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, -C 6-12 aryl-Rb, -5-12-membered heteroaryl-Rb, where Rb is selected from nitro, cyano, halogen, C 1-6 Alkyl, C 1-6 alkoxy or halogenated C 1-6 alkyl;

[0016] m is 1, 2, 3, 4 or 5;

[0017] and At least two Ra are -OS(O)2-C n .

[0018] According to some specific embodiments of the present invention, formula IA is selected from the structure shown in formula I, formula II or formula III:

[0019]

[0020] In Formula I, Formula II, or Formula III, Ra may be the same or different, and each independently represents a hydrogen atom, a hydroxyl group, or -OS(O)2-C. n The condition is that each 1 At least one of the multiple Ra substituents is -OS(O)2-C n And C n Selected from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, -C 6-12 aryl-Rb, -5-12-membered heteroaryl-Rb, where Rb is selected from nitro, cyano, halogen, C 1-6 Alkyl, C 1-6 alkoxy or halogenated C 1-6 alkyl.

[0021] In some specific implementation plans, each 1 of In this case, one Ra substituent is -OS(O)2-C. n The others are H; or there are 2 Ra substituents that are -OS(O)2-C n The others are H; or all three are -OS(O)2-C n And C n Selected from C 1-3 Alkyl, Halogenated C 1-3 Alkyl groups (e.g., perfluorinated C-substituted alkyl groups) 1-3 Alkyl), -C 6-12 Aryl-C 1-3 Alkyl, -5-12-membered heteroaryl-C 1-3 alkyl.

[0022] In some specific implementations, -OS(O)2-C n Selected from OTf,

[0023] In one embodiment, the compound represented by Formula I is prepared by the following method:

[0024]

[0025] Compound Ia reacts with compounds Cn-(O)2S-OS(O)2-Cn or LS(O)2-Cn to give the compound shown in formula I;

[0026] Where Ra' is H or OH, and At least one Ra' is OH; Cn, Ra has the definition as described above;

[0027] L represents a leaving group, such as halogens.

[0028] In one embodiment, the compound represented by Formula II is prepared by the following method:

[0029]

[0030] Compound IIa reacts with compounds Cn-(O)2S-OS(O)2-Cn or LS(O)2-Cn to give the compound shown in formula II;

[0031] Where Ra' is H or OH, and At least one Ra' is OH; Cn, Ra has the definition as described above;

[0032] L represents a leaving group, such as halogens.

[0033] In one embodiment, the compound represented by Formula III is prepared by the following method:

[0034]

[0035] Compound IIIa reacts with compounds Cn-(O)2S-OS(O)2-Cn or LS(O)2-Cn to give the compound shown in formula III;

[0036] Where Ra' is H or OH, and At least one Ra' is OH; Cn, Ra has the definition as described above;

[0037] L represents a leaving group, such as halogens.

[0038] In some more specific implementation plans, Selected from

[0039] This invention directly uses adamantane as the core to chemically modify and synthesize polyphenyl-substituted adamantane derivative monomolecular resins as shown in Formula IA, fully utilizing the advantages of the adamantane structure. The adamantane structure itself possesses excellent etching resistance; its tetrahedral geometric framework effectively inhibits intermolecular crystallization, facilitating film formation; it also exhibits a certain degree of rigidity, a high glass transition temperature, and good thermal stability. The adamantane structures synthesized in this invention, with their different substituents, not only possess the inherent advantages of adamantane in terms of etching resistance, film formation, and thermal stability, but also form monomolecular resins with small molecular sizes, suitable for high-resolution photolithography. The polyphenyl-substituted adamantane derivative monomolecular resins of this invention exhibit excellent solubility in various organic solvents, making them suitable for thin film fabrication, while also possessing a high decomposition temperature, which well meets the requirements of photolithography processes.

[0040] The -OS(O)2-C described in this invention nSubstituents can all undergo rapid decomposition reactions under ultraviolet light, electron beam, and extreme ultraviolet light conditions, causing the compound shown in Formula IA to form a new compound, resulting in a significant change in the solubility of the illuminated and unilluminated regions, thereby achieving photolithography.

[0041] As an example, the compound shown in formula IA is selected from the following:

[0042]

[0043]

[0044] In III-4, R represents... Substituents or hydrogen atoms.

[0045] The monomolecular resin of the adamantane derivative shown in Formula IA, synthesized by esterification reaction in this invention, has a simple synthesis process. The synthesized monomolecular resin exhibits excellent solubility in a variety of polar solvents.

[0046] The present invention also provides the use of the compound represented by Formula IA above for the preparation of photoresists.

[0047] According to an embodiment of the present invention, the photoresist is a single-component photoresist, containing only the compound represented by formula IA in addition to the solvent.

[0048] The present invention also provides a photoresist composition comprising a compound represented by formula IA.

[0049] According to an embodiment of the present invention, the photoresist composition is a positive or negative photoresist composition, comprising the compound represented by formula IA and a photoresist solvent.

[0050] Preferably, in the photoresist composition, when the polyphenyl-substituted adamantane derivative monomer resin is of formula (I), the sulfonate substituent -OS(O)2-C is one of its 28 substituents Ra. n The number is at least four; in the photoresist composition, when the polyphenyl-substituted adamantane derivative monomeric resin is of formula (II), the sulfonate substituent -OS(O)2-C in its 21 substituents Ra is... n The number is three or more; in the photoresist composition, when the polyphenyl-substituted adamantane derivative monomer resin is of formula (III), the sulfonate substituent -OS(O)2-C in its 14 substituents Ra n The number is two or more. In the photoresist composition of the present invention, the sulfonate substituents of the polyphenyl-substituted adamantane derivative monomer resin account for a certain proportion, and the solubility of the host material changes significantly before and after exposure, resulting in better photoresist performance.

[0051] Preferably, in the photoresist composition, the mass of the polyphenyl-substituted adamantane derivative monomolecular resin of formula IA accounts for 1 to 10 wt% of the total mass of the photoresist composition.

[0052] Preferably, the photoresist composition comprises, by weight percentage:

[0053] 1-10 wt% of polyphenyl-substituted adamantane derivative monomolecular resins as shown in Formula IA

[0054] Photoresist solvent 90-99 wt%.

[0055] Preferably, the photoresist solvent in the photoresist composition is selected from one or more of methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, acetonitrile, acetone, ethylene glycol monomethyl ether, and cyclohexanone.

[0056] The present invention also provides a photoresist coating, which is obtained by applying the above-described photoresist composition onto a substrate to form a film.

[0057] Preferably, the application method is spin coating. This invention uses spin coating to obtain good thin films, and the compound has a high decomposition temperature (greater than 200°C), which is suitable for the requirements of photolithography processes.

[0058] The present invention also provides the application of the above-mentioned photoresist composition or photoresist coating in modern photolithography technologies such as 248nm photolithography, 254nm photolithography, 193nm photolithography, extreme ultraviolet (EUV) photolithography, nanoimprint lithography or electron beam lithography.

[0059] The beneficial effects of this invention are as follows:

[0060] (1) In this invention, the synthesis process of the monomolecular resin with the adamantane structure as the core is simple and suitable for industrial production;

[0061] (2) This invention makes full use of the characteristics of adamantane having a three-dimensional geometric framework, which can effectively suppress molecular crystallization. Photoresist with polyphenyl-substituted adamantane derivative monomolecular resin as the main material is easy to form a film.

[0062] (3) The present invention introduces sulfonate functional groups around the adamantyl group, which can undergo decomposition reaction under conditions such as ultraviolet light, electron beam and extreme ultraviolet light to achieve solubility transformation.

[0063] (4) In this invention, the polyphenyl-substituted adamantane derivative monomolecular resin has a definite molecular structure, and the molecular size is small and uniform, which can well meet the requirements of high-resolution photolithography.

[0064] Terms and Definitions

[0065] Unless otherwise defined, all technical terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains.

[0066] Partial substituents marked with an asterisk (*) indicate connection sites.

[0067] Term "C" 1-12 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms. Preferably, "C" is used. 1-6 Alkyl", "C" 1-6 "Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers.

[0068] Term "C" 1-12 "Alkoxy" should be understood as -OC 1-12 Alkyl, wherein C 1-12 Alkyl groups have the above definition.

[0069] Term "C" 6-20 "Aryl" should be understood as representing a monocyclic, bicyclic, or tricyclic hydrocarbon ring with 6 to 20 carbon atoms that is monovalent and partially aromatic, preferably "C". 6-14 Aryl. The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20 When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0070] The term "5-20-membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, such as "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and, in each case, may be benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc.

[0071] The term "C" above 1-12 The definition of "alkyl" also applies to other C-containing compounds. 1-12 Alkyl groups, such as halogenated C 1-12 Alkyl. Halogenation indicates substitution by fluorine, chlorine, bromine, or iodine.

[0072] "Halogen" refers to fluorine, chlorine, bromine, or iodine.

[0073] Similarly, C 6-20 Aryl and 5-20 heteroaryl compounds have the same definition throughout the text. Attached Figure Description

[0074] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0075] Figure 1 The thermogravimetric curve of III-1 in Embodiment 3 of the present invention is shown.

[0076] Figure 2 The image shows an AFM image of the photoresist film prepared by spin coating in Example 3-1 of the present invention.

[0077] Figure 3The image shows a scanning electron microscope (SEM) image of the positive photoresist stripes obtained by 254nm photolithography in Example 3 of the present invention, III-1.

[0078] Figure 4 The image shows a scanning electron microscope (SEM) image of the negative photoresist stripes obtained by 254nm photolithography in Example 3 of the present invention, III-1.

[0079] Figure 5 The image shows a scanning electron microscope (SEM) image of the positive photoresist stripes obtained by electron beam lithography in Embodiment 3-1 of the present invention.

[0080] Figure 6 The image shows a scanning electron microscope (SEM) image of the negative photoresist stripes obtained by electron beam lithography in Embodiment 3-1 of the present invention.

[0081] Figure 7 The image shows a scanning electron microscope (SEM) image of the positive photoresist stripes obtained by 254nm photolithography in Example 1 of the present invention.

[0082] Figure 8 The image shows a scanning electron microscope (SEM) image of the negative photoresist stripes obtained by electron beam lithography in Embodiment 2 of the present invention, II-1.

[0083] Figure 9 The image shows a scanning electron microscope (SEM) image of the positive photoresist stripes obtained by 254nm photolithography in Example 4 of the present invention, III-2.

[0084] Figure 10 The image shows a scanning electron microscope (SEM) image of the negative photoresist stripes obtained by electron beam lithography in Example 5 of the present invention, III-3.

[0085] Figure 11 The image shows a scanning electron microscope (SEM) image of the positive photoresist stripes obtained by electron beam lithography in Example 6 of the present invention, III-4.

[0086] Figure 12 The image shows a scanning electron microscope (SEM) image of the negative photoresist stripes obtained by EUV lithography in Example 3-1 of the present invention. Detailed Implementation

[0087] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further clarifies the invention. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0088] The polyphenolic raw materials shown in I-1, II-1, and III-1 of this invention are known compounds. Trifluoromethanesulfonic anhydride (Tf₂O), methanesulfonic anhydride, p-toluenesulfonic anhydride, and pyridine are commercial products.

[0089] Example 1

[0090] The synthetic route for the preparation of I-1 is as follows:

[0091]

[0092] In the formula, Tf represents Substituents, It represents the bond connecting to oxygen in the main structure.

[0093] The specific steps are as follows:

[0094] 1.3 g (1.0 mmol) of 1,3,5,7-tetra-[3,5-bis(3,4-dihydroxyphenyl)-phenyl]adamantane was added to a 100 mL three-necked flask and dissolved in 20 mL of pyridine. After stirring, 9.03 g (32.0 mmol) of trifluoromethanesulfonic anhydride (Tf₂O) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 h. The reaction solution was poured into water to give a white solid, which was filtered, washed repeatedly with water and 5% aqueous ethanol solution, and then recrystallized in an ethyl acetate / n-hexane mixture to give 2.86 g of a white solid, with a yield of 75%. 1 ¹H NMR (600MHz, CDCl₃) δ (ppm) 7.76 (s, 4H, benzene ring), 7.35 (s, 4H, benzene ring), 7.24–7.07 (m, 8H, benzene ring), 6.90 (s, 8H, benzene ring), 2.15 (s, 12H, adamantane). HRMS (MALDI) m / z: [M+Na] + Calculated value C 98 H 48 F 48 O 48 S 16 Na + 3439.60, experimental value 3439.61.

[0095] Example 2

[0096] The synthetic route for preparing II-1 is as follows:

[0097]

[0098] In the formula, Tf represents Substituents, It represents the bond connecting to oxygen in the main structure.

[0099] The specific steps are as follows:

[0100] 965 mg (1.0 mmol) of 1,3,5-tris-[3,5-di(4-hydroxyphenyl)-4-hydroxyphenyl]adamantane was added to a 100 mL three-necked flask, and dissolved in 20 mL of pyridine. After stirring, 5.08 g (18.0 mmol) of trifluoromethanesulfonic anhydride (Tf₂O) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 h. The reaction solution was poured into water to give a white solid, which was filtered, washed repeatedly with water and 5% aqueous ethanol solution, and then recrystallized in an ethyl acetate / n-hexane mixture to give 1.51 g of a white solid, with a yield of 70%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm) 7.88 (s, 6H, benzene ring), 7.25–6.97 (m, 24H, benzene ring), 2.27 (s, 6H, adamantane), 2.22 (d, 6H, adamantane), 1.41 (s, 1H); HRMS (MALDI) m / z: [M+Na] + Calculated value C 73 H 43 F 27 O 27 S9Na + 2174.89, experimental value 2174.88.

[0101] Example 3

[0102] The synthetic route for preparing III-1 is as follows:

[0103]

[0104] In the formula, Tf represents Substituents, It represents the bond connecting to oxygen in the main structure.

[0105] The specific steps are as follows:

[0106] 753 mg (1.0 mmol) of 1,3-bis-[3,5-bis(3,4-dihydroxyphenyl)-4-hydroxyphenyl]adamantane was added to a 100 mL three-necked flask, and dissolved in 20 mL of pyridine. After stirring, 5.64 g (20.0 mmol) of trifluoromethanesulfonic anhydride (Tf₂O) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 h. The reaction solution was poured into water to give a white solid, which was filtered, washed repeatedly with water and 5% aqueous ethanol solution, and then recrystallized in an ethyl acetate / n-hexane mixture to give 1.55 g of a white solid, with a yield of 75%. 1¹H NMR (600MHz, CDCl₃) δ 7.60 (m, 12H, benzene ring), 7.48 (s, 4H, benzene ring), 2.48 (s, 2H, adamantane), 2.12–2.04 (m, 10H, adamantane), 1.86 (s, 2H, adamantane); HRMS (MALDI) m / z: [M+Na] + Calculated value C 56 H 30 F 30 O 30 S 10 Na + 2094.74, experimental value 2094.75. The thermal stability and glass transition temperature of the prepared monomeric resin III-1 were determined, and the thermogravimetric curves are shown below. Figure 1 The results showed that its decomposition temperature reached over 250℃, indicating excellent thermal stability.

[0107] Example 4

[0108] The synthetic route for preparing III-2 is as follows:

[0109]

[0110] The specific steps are as follows:

[0111] 753 mg (1.0 mmol) of 1,3-bis-[3,5-bis(3,4-dihydroxyphenyl)-4-hydroxyphenyl]adamantane was added to a 100 mL three-necked flask, and 20 mL of pyridine was added to dissolve it. After stirring, 3.48 g (20.0 mmol) of methanesulfonic anhydride was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 h. The reaction solution was poured into water to give a white solid, which was filtered, washed repeatedly with water and 5% aqueous ethanol solution, and then recrystallized in an ethyl acetate / n-hexane mixture to give 1.01 g of a white solid, with a yield of 65%. 1 ¹H NMR (600MHz, CDCl₃) δ 7.61 (m, 12H, benzene ring), 7.48 (s, 4H, benzene ring), 3.28 (s, 30H, CH₃), 2.48 (s, 2H, adamantane), 2.12–2.04 (m, 10H, adamantane), 1.86 (s, 2H, adamantane); HRMS (MALDI) m / z: [M+Na] + Calculated value C 56 H 60 O 30 S 10 Na + 1555.03, experimental value 1555.04.

[0112] Example 5

[0113] The synthetic route for preparing III-3 is as follows:

[0114]

[0115] The specific steps are as follows:

[0116] 753 mg (1.0 mmol) of 1,3-bis-[3,5-bis(3,4-dihydroxyphenyl)-4-hydroxyphenyl]adamantane was added to a 100 mL three-necked flask and dissolved in 20 mL of pyridine. After stirring, 4.00 g (20.0 mmol) of p-toluenesulfonyl chloride was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 h. The reaction solution was poured into water to give a white solid, which was filtered, washed repeatedly with water and a 10% aqueous ethanol solution, and then recrystallized in an ethyl acetate / n-hexane mixture to give 1.56 g of a white solid, with a yield of 68%. 1 ¹H NMR (600MHz, CDCl₃) δ 8.04 (d, 20H, benzene ring), 7.61 (m, 12H, benzene ring), 7.48 (s, 4H, benzene ring), 7.05 (d, 20H, benzene ring), 2.48 (s, 2H, adamantane), 2.42 (s, 30H, CH₃), 2.12–2.04 (m, 10H, adamantane), 1.86 (s, 2H, adamantane); HRMS (MALDI) m / z: [M+Na] + Calculated value C 116 H 100 O 30 S 10 Na + 2316.34, experimental value 2316.33.

[0117] Example 6

[0118] The synthetic route for preparing III-4 is as follows:

[0119]

[0120] In the formula, R represents Substituents or hydrogen atoms, It represents the bond connecting to oxygen in the main structure.

[0121] The specific steps are as follows:

[0122] 753 mg (1.0 mmol) of 1,3-bis-[3,5-bis(3,4-dihydroxyphenyl)-4-hydroxyphenyl]adamantane was added to a 100 mL three-necked flask, and 20 mL of pyridine was added to dissolve it. After stirring, 2.256 g (8.0 mmol) of trifluoromethanesulfonic anhydride (Tf₂O) was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 h. The reaction solution was poured into water to obtain a white solid. The solid was filtered, washed repeatedly with water and 5% ethanol aqueous solution, and the product was dissolved in ethyl acetate. The product was then precipitated in n-hexane to obtain 1.34 g of a white solid, with a yield of 80%. Based on NMR data, it was determined that there were approximately three remaining phenolic hydroxyl groups in the molecule, and the remaining phenolic hydroxyl groups were converted into trifluoromethanesulfonate. 1 ¹H NMR (600MHz, CDCl₃) δ 8.71–8.92 (m, 3.21H, Ar-OH), 7.63 (s, 2H, Ar-OH), 7.60 (m, 12H, benzene ring), 7.48 (s, 4H, benzene ring), 2.48 (s, 2H, adamantane), 2.12–2.04 (m, 10H, adamantane), 1.86 (s, 2H, adamantane).

[0123] Example 7

[0124] A photoresist composition comprising III-1 prepared in Example 3 and the solvent methyl isobutyl ketone.

[0125] The specific method is as follows:

[0126] Compound III-1 from Example 3 was dissolved in methyl isobutyl ketone to prepare a 2 wt% solution. This solution was filtered through an organic filter membrane with a pore size of 0.22 μm to obtain a photoresist solution. This solution was then spin-coated onto a silicon substrate and baked at 100°C for 3 minutes. The resulting film was characterized using AFM. Figure 2 As shown, the film surface is very smooth, and the film thickness fluctuates within ±3nm.

[0127] The photoresist compositions of other compounds I-1, II-1, III-2, III-3, and III-4 were prepared using the exact same method.

[0128] Example 8

[0129] Compound III-1 was used as a positive photoresist for 254 nm photolithography. The photoresist film prepared in Example 7 was exposed at 254 nm for 1 min at a dose of 300 mJ / cm². 2 The exposed film was developed with a 25% (w / w) tetramethylammonium hydroxide aqueous solution, yielding a high-quality 1μm line pattern, such as... Figure 3 As shown.

[0130] Example 9

[0131] Compound III-1 was used as a negative photoresist for 254 nm photolithography. The photoresist film prepared in Example 7 was exposed at 254 nm for 1 min at a dose of 300 mJ / cm². 2 The exposed film was developed using a mixture of n-hexane and chlorocyclohexane (volume ratio: n-hexane:chlorocyclohexane = 10:1), which yielded a high-quality 1μm line pattern, such as... Figure 4 As shown.

[0132] Example 10

[0133] Compound III-1 was used as a positive photoresist in electron beam lithography. The photoresist film prepared in Example 7 was subjected to electron beam exposure, and the exposed film was developed with a 25% (w / w) tetramethylammonium hydroxide aqueous solution, yielding a high-quality 40nm line pattern, such as... Figure 5 As shown.

[0134] Example 11

[0135] Compound III-1 was used as a negative photoresist in electron beam lithography. The photoresist film prepared in Example 7 was subjected to electron beam exposure. The exposed film was then developed using a mixture of n-hexane and chlorocyclohexane (volume ratio: n-hexane:chlorocyclohexane = 10:1), yielding a high-quality 25nm line pattern, such as... Figure 6 As shown.

[0136] Example 12

[0137] Compound I-1 was used as a positive photoresist for 254 nm photolithography. The photoresist film prepared in Example 7 was exposed at 254 nm for 1.5 min at a dose of 450 mJ / cm². 2 The exposed film was developed with a 25% (w / w) tetramethylammonium hydroxide aqueous solution, yielding a high-quality 1μm line pattern, such as... Figure 7 As shown.

[0138] Example 13

[0139] Compound II-1 was used as a negative photoresist in electron beam lithography. The photoresist film prepared in Example 7 was subjected to electron beam exposure. The exposed film was then developed with a mixture of n-hexane and chlorocyclohexane (volume ratio: n-hexane:chlorocyclohexane = 5:1), yielding a high-quality 30nm line pattern, such as... Figure 8 As shown.

[0140] Example 14

[0141] Compound III-2 was used as a positive photoresist for 254 nm photolithography. The prepared photoresist film was exposed at 254 nm for 1.5 min at a dose of 400 mJ / cm². 2 The exposed film was developed with a 25% (w / w) tetramethylammonium hydroxide aqueous solution, yielding a high-quality 1μm line pattern, such as... Figure 9 As shown.

[0142] Example 15

[0143] Compound III-3 was used as a negative photoresist in electron beam lithography. The photoresist film prepared in Example 7 was subjected to electron beam exposure. The exposed film was then developed with a mixture of n-hexane and chlorocyclohexane (volume ratio: n-hexane:chlorocyclohexane = 4:1), yielding a high-quality 30nm line pattern, such as... Figure 10 As shown.

[0144] Example 16

[0145] Compound III-4 was used as a positive photoresist in electron beam lithography. The photoresist film prepared in Example 7 was subjected to electron beam exposure, and the exposed film was developed with a 10% (w / w) tetramethylammonium hydroxide aqueous solution, yielding a high-quality 50nm line pattern, such as... Figure 11 As shown.

[0146] Example 12

[0147] Compound III-1 was used as a negative photoresist in EUV lithography. The photoresist film prepared in Example 7 was subjected to EUV exposure. The exposed film was then developed using a mixture of n-hexane and chlorocyclohexane (volume ratio: n-hexane:chlorocyclohexane = 10:1), yielding a high-quality 20nm line pattern, such as... Figure 12 As shown.

[0148] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. The compound represented by formula IA: IA in, R1, R2, R3, and R4 may be the same or different, and are independently selected from H or ; Ra is selected from H, OH, -OS(O)2-C n C n Selected from C 1-12 Alkyl, Halogenated C 1-12 Alkyl, -C 6-20 aryl-Rb, -5-20 heteroaryl-Rb, Rb selected from halogens, C 1-12 Alkyl, C 1-12 alkoxy or halogenated C 1-12 alkyl; m is 1, 2, 3, 4 or 5; The condition is that at least two of R1, R2, R3, and R4 are selected from... ,and At least one Ra is -OS(O)2-C n .

2. The compound according to claim 1, wherein, Ra is selected from H, OH, -OS(O)2-C n C n Selected from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, -C 6-12 aryl-Rb, -5-12 heteroaryl-Rb, where Rb is selected from halogens, C 1-6 Alkyl, C 1-6 alkoxy or halogenated C 1-6 alkyl; m is 1, 2, 3, 4 or 5; and At least two Ra are -OS(O)2-C n .

3. The compound according to claim 2, wherein, Formula IA is selected from the structure shown in Formula I, Formula II, or Formula III: In Formula I, Formula II, or Formula III, Ra may be the same or different, and each independently represents a hydrogen atom, a hydroxyl group, or -OS(O)2-C. n The condition is that each 1 At least one of the multiple Ra substituents is -OS(O)2-C n And C n Selected from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, -C 6-12 aryl-Rb, -5-12 heteroaryl-Rb, where Rb is selected from halogens, C 1-6 Alkyl, C 1-6 alkoxy or halogenated C 1-6 alkyl.

4. The compound according to any one of claims 1-3, wherein, Each 1 of One of the Ra substituents is -OS(O)2-C n The others are H; or there are 2 Ra substituents that are -OS(O)2-C n The others are H; or all three are -OS(O)2-C n And C n Selected from C 1-3 Alkyl, Halogenated C 1-3 Alkyl, -C 6-12 Aryl-C 1-3 Alkyl, -5-12-membered heteroaryl-C 1-3 alkyl.

5. The compound according to any one of claims 1-3, wherein, The compounds are selected from the following: 。 6. A photoresist composition comprising the compound according to any one of claims 1-5.

7. The photoresist composition according to claim 6, wherein, The photoresist composition is a positive or negative photoresist composition, comprising a compound of formula IA and a photoresist solvent.

8. The photoresist composition according to claim 6 or 7, wherein, The photoresist composition comprises, by weight percentage: 1-10 wt% of the compound according to any one of claims 1-5 Photoresist solvent 90~99wt%.

9. The photoresist composition according to claim 8, wherein, The photoresist solvent is selected from one or more of methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, acetonitrile, acetone, ethylene glycol monomethyl ether, and cyclohexanone.

10. The use of the photoresist composition according to any one of claims 6-9 in 248nm lithography, 254nm lithography, 193nm lithography, extreme ultraviolet lithography or electron beam lithography.

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