Fused ring aromatic hydrocarbon derivatives, methods for their preparation and use in photolithography

Abstract

This invention belongs to the field of photoresist technology, specifically relating to chemically amplified positive photoresists of fused-ring aromatic hydrocarbon derivatives, their preparation methods, and applications. The matrix component of the photoresist is a fused-ring aromatic hydrocarbon derivative represented by general formula (I), which can be dissolved in commonly used organic solvents for photoresists. The photoresist composition of this invention can prepare uniform thin films, and during the film preparation process, the molecular glass, as the matrix component, does not precipitate particulate matter. The thin films prepared from the photoresist composition of this invention have good resolution, photosensitivity, adhesion, and are easy to store.

Description

Technical Field

[0001] This invention belongs to the field of photoresist technology, specifically relating to a class of fused-ring aromatic hydrocarbon derivatives, their preparation methods, and their applications in photolithography. Background Technology

[0002] Integrated circuits (ICs) are the foundation of modern equipment manufacturing, produced through large-scale and very-large-scale IC manufacturing processes. With the rapid development of the semiconductor industry, electronic devices demand increasingly smaller IC (chip) sizes and higher integration densities. Photolithography is the most critical process in IC manufacturing, as the wavelength used in its exposure process affects the resolution of the IC. Since the 1980s, photolithography has evolved from the initial G-line (436nm) and I-line (365nm) lithography to deep ultraviolet (248nm, 193nm) lithography, and then to the next-generation extreme ultraviolet (EUV) lithography (13.5nm). With decreasing wavelengths, the minimum achievable size of ICs has also become increasingly smaller. Furthermore, advanced lithography technologies such as nanoimprint lithography and electron beam lithography have been developed. The minimum feature size of ICs has also progressed from the micrometer and sub-micrometer levels to the nanometer level.

[0003] Photoresist, as a core material in photolithography, is constantly evolving. Traditional high-molecular-weight chemical amplification photoresists, due to their large molecular weight and uneven distribution, struggle to achieve high-resolution line patterns with low edge roughness. Molecular glass materials are small-molecule organic compounds with high glass transition temperatures (Tg), exhibiting monodisperse molecular weight and an amorphous morphology. They possess high melting points and thermal stability, and with the introduction of acid-sensitive groups, they can meet the requirements of EUV lithography. In traditional chemical amplification photoresists, the relatively small molecular weight of the host material leads to low photoresist contrast and poor stripe steepness; therefore, it is necessary to develop molecular glass photoresists with larger molecular weights. Etching is a key patterning process associated with photolithography. It selectively removes materials not covered by the photoresist on the silicon wafer surface using chemical or physical methods. This requires the photoresist to possess etching resistance; increasing the content of benzene rings (fused rings) in the host material structure can improve the photoresist's etching resistance.

[0004] This invention develops a novel molecular glass photoresist, which is expected to achieve a positive chemical amplification photoresist with higher resolution and contrast and high etching resistance. Summary of the Invention

[0005] The purpose of this invention is to provide a fused-ring aromatic hydrocarbon derivative and its preparation method.

[0006] Another object of the present invention is to provide the application of the above-mentioned polycyclic aromatic hydrocarbon derivatives in photolithography and a positive photoresist composition.

[0007] This invention provides compounds represented by formula (Ⅰ):

[0008]

[0009] Wherein, A is selected from polycyclic aromatic hydrocarbons;

[0010] R a R b R c R d Same or different, selected independently from H or The condition is R a R b R c R d At least one of them is

[0011] The This is the connection point;

[0012] Each R is either the same or different, and is independently selected from H and C. 1-20 Alkyl or acid-sensitive group, provided that at least one R is selected from an acid-sensitive group.

[0013] According to an embodiment of the present invention, the fused ring aromatic hydrocarbon is selected from C 9-40 Aromatics, preferably C 10-16 Aromatic hydrocarbons;

[0014] According to an embodiment of the present invention, the fused ring aromatic hydrocarbon is selected from naphthalene, anthracene, phenanthrene, or pyrene.

[0015] According to an embodiment of the present invention, R a R b R c R d Same or different, selected independently from H or The condition is R a R b R c R d One, two, three or four

[0016] According to an embodiment of the present invention, R a R b R c R d Selected from At that time, among them In the group, when there is only one R, it is preferably connected at position 4; when there are two R, it is preferably connected at positions 3 and 4, or positions 4 and 5; when there are three R, it is preferably connected at positions 3, 4 and 5.

[0017] According to an embodiment of the invention, each R may be the same or different, and is independently selected from H and C. 1-6 Alkyl or acid-sensitive group, provided that at least one R is selected from an acid-sensitive group.

[0018] According to an embodiment of the present invention, the acid-sensitive group is -OR2; R2 is selected from -COOC. 1-20 Alkyl, -COC 1-20 Alkyl, -COC 3-20 Cycloalkyl, -(CH2) q -COOC 3-20 Cycloalkyl, where q is an integer from 0 to 6; or the C 1-20 Alkyl, C 3-20 The cycloalkyl group is further optionally surrounded by one, two or more halogens or C. 1-20 Alkyl substitution.

[0019] According to an embodiment of the present invention, the acid-sensitive group is -OR2; R2 is selected from -COOC. 1-6 Alkyl, -COC 1-6 Alkyl, -COC 3-12 Cycloalkyl, -(CH2) q -COOC 3-12 Cycloalkyl, q is selected from 0, 1, 2 or 3; or the C 1-6 Alkyl, C 3-12 The cycloalkyl group is further optionally surrounded by one, two or more Cs. 1-6 Alkyl substitution.

[0020] According to a preferred embodiment of the present invention, the acid-sensitive group is selected from the following structures:

[0021]

[0022] The The location is the connection point.

[0023] According to an embodiment of the present invention, the compound represented by formula (I) preferably has the structure represented by formula (A) or formula (B):

[0024]

[0025] R and A have the definitions described above.

[0026] According to a preferred embodiment of the present invention, the compound represented by formula (Ⅰ) is selected from the following structures:

[0027]

[0028] The present invention also provides a method for preparing the compound shown in formula (I), comprising the following steps:

[0029]

[0030] (i) The compound shown in formula (V) reacts with the compound shown in formula (IV) to give the compound shown in formula (III);

[0031] (ii) The compound represented by formula (III) reacts to give the compound represented by formula (II);

[0032] (iii) The compound shown in formula (II) reacts with a compound that provides an acid-sensitive group to give the compound shown in formula (I);

[0033] Among them, A and R a R b R c R d It has the definition described above;

[0034] R' a 、R' b 、R' c 、R' d Selected from Or H, provided that not all of them are H; each R' is the same or different, and is independently selected from OH or H, provided that not all of them are H;

[0035] R” a 、R” b 、R” c 、R” d Selected from Or H, provided that not all of them are H; each R is either the same or different, and is independently selected from H, -C 1-20 Alkyl, -OC 1-20 Alkyl group, provided that at least one of the R's is -OC 1-20 alkyl;

[0036] L1 represents -B(OH)2, -B(OC)2 1-20 Alkyl)2, Where Y1 is C 1-20 Alkylenes, Y2, are independently selected from -H or C. 1-20 Alkyl; L2, L3, L4, L5 may be the same or different, and are independently selected from halogens or H, provided that they are not all H;

[0037] The compound providing the acid-sensitive group is selected from acid anhydrides containing the acid-sensitive group or from compounds composed of a leaving group L6 and an acid-sensitive group; L6 is a leaving group, such as F, Cl, Br or I.

[0038] According to an embodiment of the present invention, the reaction in step i) is heated under reflux in an organic solvent, such as 1,4-dioxane or tetrahydrofuran.

[0039] According to an embodiment of the invention, the reaction in step i) is carried out in the presence of an alkaline reagent, for example, in the presence of sodium carbonate.

[0040] According to an embodiment of the invention, the reaction in step i) is carried out in the presence of a palladium-containing catalyst, for example, in the presence of tetra(triphenylphosphine)palladium.

[0041] According to an embodiment of the invention, the reaction in step i) is carried out in an inert gas atmosphere, such as in argon.

[0042] According to an embodiment of the invention, the reaction in step ii) is carried out in the presence of a Lewis acid, for example in boron tribromide.

[0043] According to an embodiment of the invention, the reaction in step iii) is carried out in the presence of an acid-binding agent, for example, in the presence of 4-dimethylaminopyridine (DMAP).

[0044] According to an embodiment of the invention, the reaction in step iii) is carried out in an inert gas atmosphere, such as in argon.

[0045] According to an embodiment of the present invention, the compound represented by formula (C-4) is prepared by the following method:

[0046]

[0047] (c1) The compound shown in formula (C-1) reacts with 1,3,6,8-tetrabromopyrene to give the compound shown in formula (C-2);

[0048] (c2) The compound shown in formula (C-2) reacts to give the compound shown in formula (C-3);

[0049] (c3) The compound shown in formula (C-3) reacts with an acid anhydride containing an acid-sensitive group, or with a compound consisting of a leaving group L6 and an acid-sensitive group, to obtain the compound shown in formula (C-4);

[0050] Among them, R and L6 have the definitions described above.

[0051] According to an embodiment of the present invention, the compound represented by formula (D-4) is prepared by the following method:

[0052]

[0053] (d1) The compound shown in formula (D-1) reacts with 9,10-dibromoanthracene to give the compound shown in formula (D-2);

[0054] (d2) The compound shown in formula (D-2) reacts to give the compound shown in formula (D-3);

[0055] (d3) The compound shown in formula (D-3) reacts with an acid anhydride containing an acid-sensitive group, or with a compound consisting of a leaving group L6 and an acid-sensitive group, to obtain the compound shown in formula (D-4).

[0056] Among them, R and L6 have the definitions described above.

[0057] The present invention also provides the use of the compound shown in formula (I) in photolithography, such as in photoresist, preferably in the preparation of positive photoresist.

[0058] The present invention also provides a positive photoresist composition, comprising: a substrate; said substrate being selected from at least one compound represented by formula (I);

[0059] According to an embodiment of the present invention, the composition further includes a photoacid-producing agent, such as a bis(trichloromethyl)triazine derivative, ononium salts, sulfonyl lactones, or sulfonate esters, and preferably at least one of the following:

[0060]

[0061] Among them, R1'-R 10 'Same or different, selected independently from H, C 1-20 Alkyl, ester, amide, carboxyl, aldehyde, hydroxyl.

[0062] According to an embodiment of the present invention, the photoacid-producing agent is selected from...

[0063] According to an embodiment of the present invention, the composition further includes an organic base, such as at least one selected from various nitrogen-containing organic amine compounds, such as methylamine, dimethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, hexamethylenediamine, benzylamine, and cyclohexylamine.

[0064] According to an embodiment of the present invention, the composition further includes an organic solvent, such as selected from alkanes, esters, ethers, and haloalkanes; the organic solvent is preferably at least one selected from 1,2,3-trichloropropane, anisole, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, ethyl lactate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, neopentyl acetate, butyl acetate, diethylene glycol ethyl ether, dichloromethane, and tetrahydrofuran.

[0065] According to an embodiment of the present invention, in the photoresist composition, the mass of the substrate accounts for 2%-30% of the total mass of the positive photoresist composition, preferably 4-20%.

[0066] According to an embodiment of the present invention, in the photoresist composition, the photoacid generator accounts for 2%-30% of the mass of the substrate, preferably 5%-20%.

[0067] According to an embodiment of the present invention, in the photoresist composition, the organic base accounts for 0.02%-8% of the mass of the substrate.

[0068] According to an embodiment of the present invention, in the photoresist composition, the organic solvent accounts for 70%-96% of the total mass of the photoresist composition.

[0069] According to an embodiment of the present invention, the photoresist composition further includes other additives, such as sensitizers, surfactants, dyes, stabilizers, etc.

[0070] The present invention also provides the application of the photoresist composition in deep ultraviolet (248nm, 193nm) lithography, extreme ultraviolet (13.5nm, EUV) lithography, nanoimprint lithography (NIL) and electron beam lithography (EBL).

[0071] Beneficial effects

[0072] The matrix component of the positive photoresist composition of the present invention has a condensed ring aromatic hydrocarbon as the central core structure shown in formula (I), thus having a high melting point, which can meet the requirements of photolithography technology, and the structure is stable, with no change in the film structure during high-temperature baking.

[0073] The matrix component of the positive photoresist composition of the present invention is a stereoasymmetric amorphous small molecule compound, which can be dissolved in commonly used organic solvents for photoresists. The photoresist composition of the present invention can prepare uniform thin films, and the molecular glass compound serving as the matrix component does not precipitate during the film-forming process. Therefore, the thin films prepared from the photoresist composition of the present invention have good resolution, photosensitivity, adhesion, and are easy to store. Attached Figure Description

[0074] Figure 1 The image shows the thermogravimetric analysis result of compound C prepared in Example 1.

[0075] Figure 2 The image shows an X-ray diffraction test image of compound C prepared in Example 1.

[0076] Figure 3 Electron micrograph of the deep ultraviolet lithographic pattern of the photoresist composition prepared in Example 3.

[0077] Figure 4 Electron beam lithography image of the photoresist composition prepared in Example 3.

[0078] Figure 5 Electron beam lithography image of the photoresist composition prepared in Example 4.

[0079] Terminology Definitions and Explanations

[0080] 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.

[0081] "More than three" means three or more.

[0082] The term "halogen" includes F, Cl, Br, or I.

[0083] Term "C" 1-20 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 20 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.

[0084] Term "C" 3-20 "Cycloalkyl" should be understood as representing a saturated monovalent monocyclic, bicyclic, or polycyclic hydrocarbon ring (also called a fused ring hydrocarbon ring) with 3-20 carbon atoms. Bicyclic or polycyclic cycloalkyl includes fused cycloalkyl, bridged cycloalkyl, and spirocyclic cycloalkyl; fused ring refers to a fused ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing a bond). Bridged ring refers to a fused ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. Spirocyclic refers to a fused ring structure formed by two or more cyclic structures sharing a single ring atom. For example, the C 3-20 Cycloalkyl groups can be C 3-8 Monocyclic cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C 7-12 Circoalkyl, such as decahydronaphthalene ring; or C7-12 Bridged cycloalkyl groups, such as norbornene, adamantane, and bicyclo[2,2,2]octane.

[0085] Term "C" 9-40 "Aromatic hydrocarbon" should be understood to preferably refer to a fused ring having aromatic or partially aromatic properties with 9 to 40 carbon atoms. It can be a monoaromatic ring or a polyaromatic ring fused together, preferably "C". 9-20 Aromatic hydrocarbons. The term "C" 9-20 "Aromatic hydrocarbon" should be understood to preferably represent an aromatic or partially aromatic fused ring having 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, particularly a ring having 10-16 carbon atoms ("C"). 10-16 Aromatic hydrocarbons (“C9 aromatics”). Examples include rings with 9 carbon atoms (“C9 aromatics”), such as indene or indene, or rings with 10 carbon atoms (“C9 aromatics”). 10 Aromatic hydrocarbons, such as tetrahydronaphthalene, dihydronaphthalene, or naphthalene, or rings with 13 carbon atoms (“C”). 13 Aromatic hydrocarbons, such as fluorene, or rings with 14 carbon atoms (“C”). 14 Aromatic hydrocarbons, such as anthracene; or rings with 16 carbon atoms (“C”). 16 Aromatic hydrocarbons), such as pyrene. When the C 9-40 When aromatic hydrocarbons are substituted, they can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, they can be ortho-, para-, or meta-substituted. Detailed Implementation

[0086] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0087] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0088] Example 1: Preparation of compound C

[0089] Synthetic route of compound C:

[0090]

[0091] Synthesis of compound C1:

[0092] 15.2 g of 4-methoxyphenylboronic acid, 0.92 g of tetraphenylphosphine palladium, 17 g of Na₂CO₃, and a magnetic flask were placed in a three-necked flask (the three-necked flask was connected to a gas delivery tube, a constant pressure dropping funnel, and a rubber stopper). The flask was evacuated and purged with argon gas three times to ensure the reaction was carried out under argon protection. 150 mL of 1,4-dioxane and 100 mL of ultrapure water were added to the three-necked flask. 12.6 g of 1,3,5-tribromobenzene was dissolved in 50 mL of 1,4-dioxane, and the solution was added to the dropping funnel. The reaction system was heated to 80 °C and stirred. The solution in the dropping funnel was added dropwise. After the addition was complete, the system was heated to 100 °C and stirred for 24 hours. After the reaction was completed, the reaction solution was washed with a large amount of saturated brine and dichloromethane, dried over anhydrous Na₂SO₄ for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and separated by column chromatography to obtain 6.49 g of compound C1.

[0093] Synthesis of compound C2:

[0094] 4.57 g of pinacol diboronic acid ester, 4.42 g of KOAc, 327 mg of Pd(dppf)Cl2, and a magnetic buoy were placed in a three-necked flask (the three-necked flask was connected to a gas delivery tube, a constant pressure dropping funnel, and a rubber stopper). The flask was evacuated and purged with argon gas three times to ensure the reaction was carried out under argon protection. 35 mL of 1,4-dioxane was added to the three-necked flask. 5.54 g of compound C2 was dissolved in 30 mL of 1,4-dioxane, and the solution was poured into the dropping funnel. The reaction system was heated to 80 °C and stirred, and the solution in the dropping funnel was added dropwise. The reaction was allowed to proceed for 24 h. After the reaction was complete, the reaction solution was washed with a large amount of saturated saline and dichloromethane, dried over anhydrous Na2SO4 for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and a large amount of n-hexane was added to precipitate the product. The product was then sonicated and filtered to obtain 5.71 g of compound C2.

[0095] Synthesis of compound C3:

[0096] 1.04 g of 1,3,6,8-tetrabromopyrene, 2.21 g of Na₂CO₃, 0.277 g of tetraphenylphosphine palladium, and a magnetic flask were placed in a three-necked flask (the three-necked flask was connected to a gas delivery tube, a constant-pressure dropping funnel, and a rubber stopper). The flask was evacuated and purged with argon gas three times to ensure the reaction was carried out under argon protection. 10 mL of 1,4-dioxane and 8 mL of ultrapure water were added to the three-necked flask. 4.16 g of compound C2 was dissolved in 40 mL of 1,4-dioxane, and the solution was added to the dropping funnel. The reaction system was heated to 80 °C and stirred. The solution in the dropping funnel was added dropwise. After the addition was complete, the system was heated to 100 °C and stirred for 24 hours. After the reaction was complete, the reaction solution was washed with a large amount of saturated brine and dichloromethane, dried over anhydrous Na₂SO₄ for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and separated by column chromatography to obtain 1.63 g of compound C3.

[0097] Synthesis of compound C4:

[0098] 1.36 g of compound C3 was dissolved in 70 mL of dichloromethane and added to a three-necked flask equipped with a magnetic inlet (the three-necked flask was connected to a gas delivery tube, a constant-pressure dropping funnel, and a rubber stopper). The system was placed in an ice-water bath, and 4.64 mL of BBr3 was added to the dropping funnel with stirring. After the addition was complete, the mixture was allowed to return to room temperature and reacted for 24 hours. After the reaction was complete, the reaction solution was transferred to another three-necked flask connected to a constant-pressure dropping funnel. 100 mL of ice water was added to the three-necked flask and added slowly in an ice-water bath with stirring for 2 hours. After the reaction was complete, the reaction solution was washed with a large amount of saturated brine and ethyl acetate, dried over anhydrous Na2SO4 for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and a large amount of n-hexane was added to precipitate the product. The product was then sonicated and filtered to obtain 1.24 g of compound C4.

[0099] Synthesis of compound C:

[0100] 1.24 g of compound C4 and 97.6 mg of 4-dimethylaminopyridine (DMAP) were placed in a three-necked flask (the flask was connected to a gas delivery tube, a constant pressure dropping funnel, and a rubber stopper). 10 mL of THF was added. 2.62 g of Boc anhydride was dissolved in 10 mL of THF, and the solution was added to the dropping funnel. The reaction system was placed in an ice-water bath and stirred. The solution in the dropping funnel was added dropwise, and after the addition was complete, the mixture was slowly brought to room temperature and reacted for 12 hours. After the reaction was completed, the reaction solution was evaporated to dryness, washed with a large amount of saturated brine and ethyl acetate, dried over anhydrous Na2SO4 for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and separated by column chromatography to obtain 1.0 g of compound C.

[0101] Thermogravimetric analysis of compound C is shown in Figure 1 The decomposition temperature is around 180℃; XRD analysis is shown below. Figure 2 This indicates that compound C is an amorphous compound and will not crystallize out.

[0102] 1 ¹H NMR (400MHz, DMSO) δ 8.47 (d, J = 7.7Hz, 6H), 8.05 (d, J = 21.2Hz, 12H), 7.97 (d, J = 8.5Hz, 16H), 7.33 (d, J = 8.5Hz, 16H), 1.54 (s, 72H). HRMS (MALDI): Theoretical value [M+H] + : 2043.84; Experimental value: 2043.834.

[0103] Example 2: Preparation of compound F

[0104] Synthetic route of compound F:

[0105]

[0106] Synthesis of compound F3:

[0107] 1.08 g of 1,6-dibromopyrene, 2.86 g of Na₂CO₃, 0.208 g of tetraphenylphosphine palladium, and a magnetic buoy were placed in a three-necked flask (the three-necked flask was connected to a gas delivery tube, a constant-pressure dropping funnel, and a rubber stopper). The flask was evacuated and purged with argon gas three times to ensure the reaction was carried out under argon protection. 10 mL of 1,4-dioxane and 15 mL of ultrapure water were added to the three-necked flask. 3.12 g of compound C₂ was dissolved in 20 mL of 1,4-dioxane, and the solution was poured into the dropping funnel. The reaction system was heated to 80 °C and stirred. The solution in the dropping funnel was added dropwise. After the addition was complete, the system was heated to 100 °C and the reaction was stirred for 24 hours. After the reaction was completed, the reaction solution was washed with a large amount of saturated saline and dichloromethane, dried with anhydrous Na2SO4 for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and a large amount of petroleum ether was added to precipitate the product. The product was then sonicated and filtered to obtain 2.34 g of compound F3.

[0108] Synthesis of compound F4:

[0109] 2.34 g of compound F3 was dissolved in 30 mL of dichloromethane and added to a three-necked flask equipped with a magnetic inlet (the three-necked flask was connected to a gas delivery tube, a constant-pressure dropping funnel, and a rubber stopper). The system was placed in an ice-water bath, and 1.74 mL of BBr3 was added to the dropping funnel with stirring. After the addition was complete, the mixture was allowed to return to room temperature and reacted for 24 hours. After the reaction was complete, the reaction solution was transferred to another three-necked flask connected to a constant-pressure dropping funnel. 50 mL of ice water was added to the three-necked flask, and the mixture was slowly added dropwise under an ice-water bath with stirring for 2 hours. After the reaction was complete, the reaction solution was washed with a large amount of saturated brine and ethyl acetate, dried over anhydrous Na2SO4 for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and a large amount of n-hexane was added to precipitate the product. The product was then sonicated and filtered to obtain 2.16 g of compound F4.

[0110] Synthesis of compound F:

[0111] 723 mg of compound F4 and 4.89 mg of 4-dimethylaminopyridine (DMAP) were placed in a three-necked flask (the three-necked flask was connected to a gas delivery tube, a constant pressure dropping funnel, and a rubber stopper). 10 mL of THF was added. 1.31 g of Boc anhydride was dissolved in 5 mL of THF, and the solution was added to the dropping funnel. The reaction system was placed in an ice-water bath and stirred. The solution in the dropping funnel was added dropwise, and after the addition was complete, the mixture was slowly brought to room temperature and reacted for 12 hours. After the reaction was completed, the reaction solution was evaporated to dryness, washed with a large amount of saturated brine and ethyl acetate, dried over anhydrous Na2SO4 for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and separated by column chromatography to obtain 724 mg of compound F. 1¹H NMR (300MHz, CDCl₃) δ 8.29 (dd, J = 15.3, 8.6Hz, 4H), 8.09 (d, J = 7.7Hz, 4H), 7.80 (dd, J = 31.8, 8.7Hz, 14H), 7.29 (t, J = 8.3Hz, 8H), 1.58 (s, 36H). HRMS (MALDI): Theoretical value [M+H] + : 1122.46; Experimental value: 1122.45.

[0112] Example 3: Photoresist composition containing compound C

[0113] Photoresist composition:

[0114] (1) Matrix: (Compound C) 50mg;

[0115] (2) Photoacid-producing agents: 2.5mg;

[0116] (3) Organic base: Trioctylamine 0.125 mg;

[0117] (4) Organic solvent: 2 mL of propylene glycol methyl ether acetate (PGMEA).

[0118] Example 4: Photoresist composition containing compound F

[0119] Photoresist composition:

[0120] (1) Matrix: (Compound F) 50mg;

[0121] (2) Photoacid-producing agents: 2.5mg;

[0122] (3) Organic base: Trioctylamine 0.125 mg;

[0123] (4) Organic solvent: 2 mL of propylene glycol methyl ether acetate (PGMEA).

[0124] Example 5: Photoresist composition containing compound D

[0125] Photoresist composition:

[0126] (1) Matrix: (Compound D) 50mg;

[0127] (2) Photoacid-producing agents: 2.5mg;

[0128] (3) Organic base: Trioctylamine 0.125 mg;

[0129] (4) Organic solvent: 2 mL of propylene glycol methyl ether acetate (PGMEA).

[0130] Compound D was prepared using a method similar to that in Examples 1 and 2. HRMS(MALDI)[M+H] + 1098.45.

[0131] Example 6: Photoresist composition containing compound G

[0132] Photoresist composition:

[0133] (1) Matrix: (Compound G) 50mg;

[0134] (2) Photoacid-producing agents: 2.5mg;

[0135] (3) Organic base: Trioctylamine 0.125 mg;

[0136] (4) Organic solvent: 2 mL of propylene glycol methyl ether acetate (PGMEA).

[0137] Compound G was prepared using a method similar to that in Examples 1 and 2. HRMS(MALDI)[M+H] + : 1048.43.

[0138] Test Example 1

[0139] Using the photoresist composition containing compound C from Example 3, and PGMEA as the solvent, a 50-100 nm photoresist film was spin-coated onto a silicon wafer. This photoresist composition exhibits good film-forming properties, and the resulting film has uniform thickness. Deep ultraviolet electron beam lithography was then performed to obtain micron-scale lithographic patterns, as shown in [reference needed]. Figure 3 Electron beam lithography was performed at the National Center for Nanoscience and Technology at 35 μC / cm. 2 At the specified dosage, a line lithography pattern with an 80nm period and a 40nm linewidth was obtained, as shown in [reference needed]. Figure 4 This demonstrates that the photoresist composition prepared from the compounds of this invention has good resolution and photosensitivity.

[0140] Test Example 2

[0141] Using the photoresist composition containing compound F from Example 4, and PGMEA as the solvent, a 50-100 nm photoresist film was spin-coated onto a silicon wafer. This photoresist composition exhibited good film-forming properties, resulting in a uniform film thickness. Electron beam lithography was performed at the National Center for Nanoscience and Technology to obtain a line lithography pattern with a 60 nm period and a 30 nm linewidth, as shown in [reference needed]. Figure 5 .

[0142] The embodiments of the technical solution of the present invention have been described above by way of example. It should be understood that the protection scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the protection scope of the claims of this application.

Claims

1. The compound represented by formula (Ⅰ): in, A is selected from anthracene, phenanthrene, or pyrene; R a R b R c R d Same or different, selected independently from H or The condition is R a R b R c R d Two, three, or four of them are ; The " The location marked with a "" is the connection point. Each R is either the same or different, and is independently selected from H and C. 1-20 An alkyl or acid-sensitive group, wherein at least one R is selected from an acid-sensitive group, and the acid-sensitive group is selected from the following structures: 。 2. The compound according to claim 1, characterized in that, R a R b R c R d Selected from At that time, among them In the group, when there is only one R that is an acid-sensitive group, it is attached at position 4; when there are two R that are acid-sensitive groups, they are attached at positions 3 and 4, or positions 4 and 5; when there are three R that are acid-sensitive groups, they are attached at positions 3, 4, and 5.

3. The compound according to claim 1, characterized in that, Each R is either the same or different, and is independently selected from H and C. 1-6 Alkyl or acid-sensitive group, provided that at least one R is selected from an acid-sensitive group; The acid-sensitive group is selected from the following structures: The " The location marked with a "" is the connection point.

4. The compound according to any one of claims 1-3, characterized in that, The compound has the structure shown in formula (A) or formula (B): Wherein, R and A have the definitions described in any one of claims 1-3.

5. The compound according to claim 1, characterized in that, The compound is selected from the following structures: 。 6. A method for preparing the compound according to any one of claims 1-5, comprising the following steps: (i) The compound shown in formula (V) reacts with the compound shown in formula (IV) to give the compound shown in formula (III); (ii) The compound represented by formula (III) reacts to give the compound represented by formula (II); (iii) The compound shown in formula (II) reacts with a compound that provides an acid-sensitive group to give the compound shown in formula (I); in, A, R a R b R c R d It has the definition as described in any one of claims 1-5; R ’ a R ’ b R ’ c R ’ d Same or different, selected independently from each other Or H, provided that R ’ a R ’ b R ’ c R ’ d Two, three, or four of them are Each R' may be the same or different, and each R' is independently selected from OH or H, provided that they are not all H. R ’’ a R ’’ b R ’’ c R ’’ d Same or different, selected independently from each other Or H, provided that R ’’ a R ’’ b R ’’ c R ’’ d Two, three, or four of them are ; Each R ’’ Whether the two are the same or different, they are independently selected from H and -OC. 1-20 Alkyl group, provided that it has at least one R ’’ -OC 1-20 alkyl; L1 represents -B(OH)2, -B(OC)2 1-20 Alkyl)2, or Y2 is selected independently from -H or C. 1-20 Alkyl; L2, L3, L4, L5 may be the same or different, and are independently selected from halogens or H, provided that two, three or four of L2, L3, L4, L5 are halogens; The compound providing the acid-sensitive group is selected from acid anhydrides of the acid-sensitive group, or from compounds composed of a leaving group L6 and an acid-sensitive group, wherein L6 is selected from F, Cl, Br or I.

7. The use of the compound according to any one of claims 1-5 in the preparation of positive photoresist.

8. A positive photoresist composition, comprising: Matrix; The matrix is ​​selected from at least one of the compounds described in any one of claims 1-5.

9. The positive photoresist composition according to claim 8, characterized in that, The composition further includes a photoacid-producing agent, wherein the photoacid-producing agent is selected from at least one of the following: Among them, R1 ’ -R 10 ’ They are either the same or different, and are independently selected from H and C. 1-20 Alkyl, carboxyl, aldehyde, hydroxyl.

10. The positive photoresist composition according to claim 9, characterized in that, The photo-induced acid-producing agent is selected from... ; Alternatively, the composition may further include an organic base selected from at least one of methylamine, dimethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, hexamethylenediamine, benzylamine, and cyclohexylamine; Alternatively, the composition may further include an organic solvent selected from at least one of 1,2,3-trichloropropane, anisole, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, ethyl lactate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, neopentyl acetate, butyl acetate, diethylene glycol ethyl ether, dichloromethane, and tetrahydrofuran.

11. The positive photoresist composition according to claim 8, characterized in that, In the positive photoresist composition, the substrate accounts for 2%-30% of the total mass of the positive photoresist composition.

12. The positive photoresist composition according to claim 9, characterized in that, In the positive photoresist composition, the photoacid generator accounts for 2%-30% of the mass of the substrate.

13. The positive photoresist composition according to claim 10, characterized in that, In the positive photoresist composition, the organic base accounts for 0.02%-8% of the mass of the matrix; Alternatively, in the positive photoresist composition, the organic solvent accounts for 70%-96% of the total mass of the positive photoresist composition.

14. The positive photoresist composition according to claim 8, characterized in that, In the positive photoresist composition, the mass of the substrate accounts for 4-20% of the total mass of the positive photoresist composition.

15. The positive photoresist composition according to claim 9, characterized in that, In the positive photoresist composition, the photoacid generator accounts for 5%-20% of the mass of the substrate.

16. The use of the positive photoresist composition according to any one of claims 8-15 in deep ultraviolet 248nm lithography, deep ultraviolet 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography and electron beam lithography.

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