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

Abstract

The present application belongs to the technical field of photoresist, and particularly relates to a chemical amplification negative photoresist of condensed ring aromatic hydrocarbon derivative, a preparation method and application thereof. The base component of the photoresist is a condensed ring aromatic hydrocarbon derivative shown in general formula (I), which can be dissolved in the commonly used organic solvent of photoresist. The photoresist composition of the present application can be prepared into a uniform film, and the molecular glass as the base component does not precipitate during the film preparation process. The film prepared from the photoresist composition of the present application has good resolution, photosensitivity, adhesion, and is 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] In integrated circuit manufacturing, photolithography is a crucial process. It utilizes the chemical reaction that occurs during photoresist exposure to transfer the circuit pattern from the photomask onto the photoresist film. Subsequent etching processes then transfer the pattern onto the silicon substrate. Therefore, photoresist is the most important material in both photolithography and etching processes, and its resolution determines the critical dimensions and integration density of the integrated circuit.

[0003] Photoresist consists of a host material, a photosensitizer (photoacid generator), a solvent, and additives. With the continuous development of integrated circuits, the performance requirements for photoresist are becoming increasingly stringent. Resolution, sensitivity, and line edge roughness or linewidth roughness are three important parameters for evaluating photoresist performance. These three parameters are interdependent, and researchers are currently dedicated to studying how to coordinate the relationship between them to design better photoresist materials. Chemically amplified photoresists can utilize the acid generated by the decomposition of the photoacid generator, causing deprotection or cross-linking reactions of acid-sensitive groups in the material, while releasing new acids, thereby significantly improving the photoresist sensitivity. Traditional polymer chemically amplified photoresists, due to their large molecular weight and uneven distribution, suffer from low resolution and poor line edge roughness. Molecular glass photoresists, on the other hand, use a small-molecule compound as their host material, possessing a high glass transition temperature. Combining the advantages of polymers and small molecules, they have a small and monodisperse molecular weight, and the introduction of acid-sensitive groups allows them to meet the requirements of photolithography.

[0004] Fused-ring aromatic hydrocarbons (FROs) are organic compounds formed by the fusion of two or more benzene rings sharing two adjacent carbon atoms, such as naphthalene, anthracene, phenanthrene, and pyrene. These compounds are characterized by high melting and boiling points, and due to their multiple conjugated benzene rings, they are well-suited as the core structure of molecular glass photoresists. Molecular glass photoresists centered on FROs exhibit high melting points and thermal stability, as well as ideal etching resistance.

[0005] This invention develops a novel molecular glass photoresist centered on polycyclic aromatic hydrocarbons, which is expected to achieve negative chemical amplification photoresist with higher resolution and contrast and high etching resistance. Summary of the Invention

[0006] The purpose of this invention is to provide a fused-ring aromatic hydrocarbon derivative and its preparation method.

[0007] Another object of the present invention is to provide the application of the above-mentioned polycyclic aromatic hydrocarbon derivatives in photolithography and a negative photoresist composition.

[0008] This invention provides compounds represented by formula (Ⅰ):

[0009]

[0010] Wherein, A is selected from polycyclic aromatic hydrocarbons;

[0011] 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

[0012] Each R is the same or different, and is independently selected from H, -OC. 1-20 Alkyl or OR1, provided that at least one R is OR1, H; R1 is selected from unsubstituted or optionally surrounded by one, two or more Rs. 11 The following groups are substituted: C 2-20 Alkenyl, 3-20 member epoxy groups; each R 11 They may be identical or different, and are independently selected from oxidized (=O), unsubstituted, or optionally substituted by one, two, or more R groups. 12 The following groups are substituted: C 1-20 Alkyl, C 1-20 Alkoxy, C 2-20 alkenyl, 3-20 membered heterocyclic groups, C 6-20 Aryl; each R 12 Same or different, selected independently from C 1-20 Alkyl, C 2-20 alkenyl, C 1-20 Alkoxy, C 6-20 Aryl.

[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 dSame 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 embodiments of the invention, each R is the same or different, and is independently selected from H or OR1, provided that not all R are H; R1 is selected from unsubstituted or optionally replaced by one, two or more R. 11 The following groups are substituted: C 1-6 Alkyl, 3-8 membered heterocyclic groups; each R 11 They may be identical or different, and are independently selected from oxidized (=O), unsubstituted, or optionally substituted by one, two, or more R groups. 12 The following groups are substituted: C 1-6 Alkyl, C 2-6 Alkenyl groups and oxygen-containing 3-8 membered heterocyclic groups.

[0018] According to embodiments of the invention, each R is the same or different, and is independently selected from H or OR1, provided that not all R are H; R1 is selected from unsubstituted or optionally replaced by one, two or more R. 11 The following groups are substituted: oxygen-containing 3-8 membered heterocyclic groups, C 2-6 alkenyl-C 1-6 Alkyl groups, oxygen-containing 3-8 membered heterocyclic groups -C 1-6 Alkyl; each R 11 Whether the two are the same or different, they are independently selected from oxygen (=O) and C. 1-6 alkyl;

[0019] According to an embodiment of the invention, each R is the same or different, and is independently selected from H or OR1, provided that not all R are H; R1 is selected from The The location is the connection point.

[0020] According to an embodiment of the present invention, the derivative represented by formula (I) preferably has the structure represented by formula (A) or formula (B):

[0021]

[0022] R and A have the definitions described above.

[0023] According to a preferred embodiment of the present invention, the compound represented by formula (Ⅰ) is selected from the following structures:

[0024]

[0025]

[0026] The present invention also provides a method for preparing the compound shown in formula (I), comprising the following steps:

[0027]

[0028] Compound (II) was reacted with R1-L to give the compound shown in formula (I);

[0029] Among them, A and R a R b R c R d R1 has the definition described above;

[0030] R' a 、R' b 、R' c 、R' d for 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; L is selected from leaving groups, such as halogens or p-toluenesulfonates.

[0031] According to an embodiment of the present invention, the compound of formula (I) is obtained by introducing an R1 group to fully or partially protect the compound (II).

[0032] According to an embodiment of the present invention, R1-L is selected from bromopropylene oxide, allyl bromide, α-bromo-γ-butyrolactone, or 3-methyl-3-(toluenesulfonyloxymethyl)oxetane.

[0033] According to an embodiment of the present invention, L is selected from bromine.

[0034] According to an embodiment of the present invention, in the above method, the reaction is carried out in an organic solvent, the organic solvent being selected from formamide, chloroform, DMF, acetonitrile, tetrahydrofuran, N-methylpyrrolidone, etc., wherein N-methylpyrrolidone is preferred as the reaction solvent;

[0035] According to an embodiment of the present invention, in the above method, the reaction is carried out in the presence of an alkaline compound, which is selected from Na2CO3, K2CO3, NaHCO3, Cs2CO3, etc.

[0036] According to an embodiment of the present invention, in the above method, the reaction temperature is 30-80°C, preferably 60-70°C; the reaction time is 12-36 hours, preferably 18-24 hours.

[0037] The present invention also provides the use of the compound of formula (I) in photolithography, such as in photoresist, preferably in the preparation of negative photoresist.

[0038] The present invention also provides a negative photoresist composition, comprising: a substrate; said substrate being selected from at least one compound represented by formula (I).

[0039] According to an embodiment of the present invention, the composition further includes a photoacid-generating agent; the photoacid-generating agent is selected, for example, from ionic or nonionic acid-generating agents, such as at least one of triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutylsulfonate, di(4-tert-butylphenyl)iodonium p-toluenesulfonate, N-hydroxynaphthalimide trifluoromethanesulfonate, and benzyl(4-hydroxyphenyl)methylthiodonium hexafluoroantimonate.

[0040] According to embodiments of the present invention, the composition further includes an organic solvent. The organic solvent is selected, for example, from alkanes, esters, ethers, and haloalkanes. Preferred organic solvents are 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.

[0041] 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 negative photoresist composition, preferably 4-20%.

[0042] 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%.

[0043] 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.

[0044] According to an embodiment of the present invention, the photoresist composition further includes other additives, such as sensitizers, surfactants, dyes, stabilizers, etc.

[0045] The present invention also provides the application of the photoresist composition in ultraviolet (365nm) lithography, deep ultraviolet (248nm, 193nm) lithography, extreme ultraviolet (13.5nm, EUV) lithography and electron beam lithography (EBL).

[0046] Beneficial effects

[0047] The matrix component of the negative 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;

[0048] The negative molecular glass photoresist provided by this invention is an amorphous small molecule compound with good film-forming properties, high thermal stability, and is not easily denatured during storage. It also has low viscosity, eliminating the need for additional solvent dilution during use. After exposure, the exposed pattern exhibits excellent resolution and good sensitivity. Attached Figure Description

[0049] Figure 1 The image shows the thermogravimetric analysis result of compound C prepared in Example 1.

[0050] Figure 2 The image shows an X-ray diffraction test image of compound C prepared in Example 1.

[0051] Figure 3 Electron beam lithography image of the photoresist composition prepared in Example 3.

[0052] Figure 4 Electron beam lithography image of the photoresist composition prepared in Example 3.

[0053] Figure 5 Electron beam lithography image of the photoresist composition prepared in Example 4.

[0054] Terminology Definitions and Explanations

[0055] 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.

[0056] The term "halogen" includes F, Cl, Br, or I.

[0057] 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.

[0058] Term "C" 2-20 "Alkenyl" should be understood as representing a straight-chain or branched monovalent hydrocarbon group containing one or more double bonds and having 2 to 20 carbon atoms, preferably "C". 2-12 "Alkenyl". "C" 2-12 "Alkenyl" should be understood to preferably represent a straight or branched monovalent hydrocarbon group containing one or more double bonds and having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, more preferably "C 2-8 "Alkenyl". "C" 2-8 "Alkenyl" should be understood to preferably represent a straight or branched monovalent hydrocarbon group containing one or more double bonds and having 2, 3, 4, 5, 6, 7 or 8 carbon atoms, for example, having 2, 3, 4, 5 or 6 carbon atoms (i.e., C... 2-6 alkenyl), having 2 or 3 carbon atoms (i.e., C24, C34, C4 ... 2-3Alkenyl). It should be understood that when the alkenyl group contains more than one double bond, the double bonds may be separable or conjugated. The alkenyl group is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)- Pentyl-1-enyl, (Z)-pentyl-1-enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-enyl, (Z)-hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl 2-Methylprop-1-enyl, (E)-1-methylprop-1-enyl, (Z)-1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1-methylbut-2-enyl, (Z)-1-methyl But-2-enyl, (E)-3-methylbut-1-enyl, (Z)-3-methylbut-1-enyl, (E)-2-methylbut-1-enyl, (Z)-2-methylbut-1-enyl, (E)-1-methylbut-1-enyl, (Z)-1-methylbut-1-enyl, 1,1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl.

[0059] The term "3-20 membered heterocyclic group" refers to a saturated or unsaturated non-aromatic ring or ring system, for example, a 4-, 5-, 6-, or 7-membered monocyclic ring, a 7-, 8-, 9-, 10-, 11-, or 12-membered bicyclic ring (such as a fused ring, bridged ring, or spirocyclic ring), or a 10-, 11-, 12-, 13-, 14-, or 15-membered tricyclic ring system, and contains at least one, for example, 1, 2, 3, 4, 5, or more heteroatoms selected from O, S, and N, wherein N and S may optionally be oxidized to various oxidation states to form nitrides, -S(O)-, or -S(O)2- states. Preferably, the heterocyclic group may be selected from "3-10 membered heterocyclic groups". The term "3-10 membered heterocyclic group" means a saturated or unsaturated non-aromatic ring or ring system containing at least one heteroatom selected from O, S, and N. The heterocyclic group can be connected to the rest of the molecule via any one of the carbon atoms or a nitrogen atom (if present). The heterocyclic group can include fused or bridged rings and spirocyclic rings. Specifically, the heterocyclic group can include, but is not limited to: 4-membered rings, such as azirrobutyl or oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoalkyl, pyrazolealkyl, or pyrrololinyl; or 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazineyl, or trithiaalkyl; or 7-membered rings, such as diazacycloheptyl. Optionally, the heterocyclic group can be benzofused.

[0060] 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

[0061] 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.

[0062] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0063] Example 1: Preparation of compound C

[0064] Synthetic route of compound C:

[0065]

[0066] Synthesis of compound C1:

[0067] 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.

[0068] Synthesis of compound C2:

[0069] 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.

[0070] Synthesis of compound C3:

[0071] 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.

[0072] Synthesis of compound C4:

[0073] 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.

[0074] Synthesis of compound C:

[0075] 673 mg of KOH and 1 mL of bromopropylene oxide were placed in a two-necked flask (each flask was connected to a constant-pressure dropping funnel and a rubber stopper). 5 mL of NMP was added. 1.24 g of compound C4 was dissolved in 10 mL of NMP, and the solution was added to the dropping funnel. The reaction system was stirred at 60-70 °C, and the solution in the dropping funnel was added dropwise. After the addition was complete, the reaction mixture was allowed to react for 24 h. After the reaction was complete, the reaction mixture was diluted with dichloromethane, washed with a large amount of saturated brine, dried over anhydrous Na2SO4 for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and separated by column chromatography to obtain 720 mg of compound C.

[0076] Thermogravimetric analysis of compound C is shown in Figure 1The decomposition temperature is around 350℃; XRD analysis is shown below. Figure 2 This indicates that compound C is an amorphous compound and will not crystallize out.

[0077] 1 ¹H NMR (300MHz, CDCl₃) δ 8.35 (s, 4H), 8.21 (s, 2H), 7.81 (s, 12H), 7.66 (d, J = 8.6Hz, 16H), 7.01 (d, J = 8.5Hz, 16H), 4.27 (dd, J = 10.9, 2.9Hz, 8H), 4.00 (dd, J = 10.9, 5.7Hz, 8H), 3.38 (s, 8H), 2.92 (t, J = 4.4Hz, 8H), 2.78 (s, 8H). HRMS (MALDI): Theoretical value [M+H] + ,1691.63, experimental value,1691.62.

[0078] Example 2: Preparation of compound F

[0079] Synthetic route of compound F:

[0080]

[0081] Synthesis of compound F3:

[0082] 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.

[0083] Synthesis of compound F4:

[0084] 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.

[0085] Synthesis of compound F:

[0086] 450 mg of KOH and 1 mL of bromopropylene oxide were placed in a two-necked flask (each flask was connected to a constant-pressure dropping funnel and a rubber stopper). 5 mL of NMP was added. 722.84 mg of compound F4 was dissolved in 10 mL of NMP, and the solution was added to the dropping funnel. The reaction system was stirred at 60-70 °C, and the solution in the dropping funnel was added dropwise. After the addition was complete, the reaction mixture was allowed to react for 24 h. After the reaction was complete, the reaction mixture was diluted with dichloromethane, washed with a large amount of saturated brine, dried over anhydrous Na2SO4 for 1 hour, filtered to obtain the filtrate, evaporated to dryness, and separated by column chromatography to obtain 220 mg of compound F. 1 H NMR (300MHz, CDCl3) δ8.33(d,J=9.4Hz,2H),8.24(d,J=7.9Hz,2H),8.13–8.04(m,4H),7.82(d,J=21.6Hz,6H),7.70(d,J=8.5Hz,8H),7.05(d ,J=8.5Hz,6H),6.98(s,2H),4.29(d,J=8.1Hz,4H),4.03(dd,J=11.0,5.6Hz,4H),3.40(s,4H),2.94(t,J=4.4Hz,4H),2.82(d,J=14.1Hz,4H).

[0087] Example 3: Photoresist composition containing compound C

[0088] Photoresist composition:

[0089] (1) Matrix: (Compound C) 50mg;

[0090] (2) Photoinduced acid production agent: Benzyl (4-hydroxyphenyl)methylthionium hexafluoroantimonate 3.75 mg;

[0091] (3) Organic solvent: 2 mL of propylene glycol methyl ether acetate (PGMEA).

[0092] Example 4: Photoresist composition containing compound F

[0093] (1) Matrix: (Compound F) 50mg;

[0094] (2) Photoinduced acid production agent: Benzyl (4-hydroxyphenyl)methylthionium hexafluoroantimonate 3.75 mg;

[0095] (3) Organic solvent: 2 mL of propylene glycol methyl ether acetate (PGMEA).

[0096] Example 5: Photoresist composition containing compound D

[0097] (1) Matrix: (Compound D) 50mg;

[0098] (2) Photoinduced acid production agent: Benzyl (4-hydroxyphenyl)methylthioonium hexafluoroantimonate 2.5 mg;

[0099] (3) Organic solvent: 2 mL of propylene glycol methyl ether acetate (PGMEA).

[0100] Compound D was prepared using a method similar to that in Example 1 or 2. HRMS(MALDI)[M+H] + : 922.34.

[0101] Example 6: Photoresist composition containing compound G

[0102] (1) Matrix: (Compound G) 50mg;

[0103] (2) Photoinduced acid production agent: Benzyl (4-hydroxyphenyl)methylthioonium hexafluoroantimonate 2.5 mg;

[0104] (3) Organic solvent: 2 mL of propylene glycol methyl ether acetate (PGMEA).

[0105] Compound G was prepared using a method similar to that in Example 1 or 2. HRMS(MALDI)[M+H] + : 872.32.

[0106] Test Example 1

[0107] Using the photoresist composition containing compound C from Example 3, 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 at 46 μC / cm². 2At the specified dosage, lithographic patterns with linewidths of 30 nm and 25 nm were obtained, see [reference needed]. Figure 3 and Figure 4 When used as a negative adhesive, it offers high resolution and high sensitivity.

[0108] Test Example 2

[0109] Using the photoresist composition containing compound F from Example 4, 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 30 nm linewidth lithographic pattern, as shown below. Figure 5 When used as a negative adhesive, it offers high resolution and high sensitivity.

[0110] 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 ; Each R is either the same or different, and is independently selected from H or OR1, provided that not all R are H; R1 is selected from , The " The location marked with a "" is the connection point.

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 a group, when there is only one R that is OR1, it is connected at position 4; when there are two R that are OR1, they are connected at positions 3 and 4, or positions 4 and 5; when there are three R that are OR1, they are connected at positions 3, 4 and 5.

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

4. The compound according to claim 1, characterized in that, The compound is selected from the following structures: 。 5. A method for preparing the compound according to any one of claims 1-4, comprising the following steps: Compound (II) was reacted with R1-L to give the compound shown in formula (I); in, A, R a R b R c R d R1 has the definition as described in any one of claims 1-4; 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 is independently selected from OH or H, provided that not all of them are H; L is selected from halogens.

6. The use of the compound according to any one of claims 1-4 in the preparation of negative photoresists.

7. A negative photoresist composition, comprising: Matrix; The matrix is ​​selected from at least one of the compounds described in any one of claims 1-4.

8. The negative photoresist composition according to claim 7, characterized in that, The composition further comprises a photoacid-generating agent selected from at least one of triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutylsulfonate, di(4-tert-butylphenyl)iodonium p-toluenesulfonate, N-hydroxynaphthalimide trifluoromethanesulfonate, and benzyl(4-hydroxyphenyl)methylthiodonium hexafluoroantimonate. Alternatively, the composition may further contain 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.

9. The negative photoresist composition according to claim 8, characterized in that, In the negative photoresist composition, the mass of the substrate accounts for 2%-30% of the total mass of the negative photoresist composition; Alternatively, in the negative photoresist composition, the photoacid-generating agent accounts for 2%-30% of the mass of the substrate; Alternatively, in the negative photoresist composition, the organic solvent accounts for 70%-96% of the total mass of the negative photoresist.

10. The negative photoresist composition according to claim 8, characterized in that, In the negative photoresist composition, the mass of the substrate accounts for 4-20% of the total mass of the negative photoresist composition; Alternatively, in the negative photoresist composition, the photoacid generator accounts for 5%-20% of the mass of the substrate.

11. The use of the negative photoresist composition of claim 8 or 9 in ultraviolet 365nm lithography, deep ultraviolet 248nm lithography, deep ultraviolet 193nm lithography, extreme ultraviolet 13.5nm lithography and electron beam lithography.

Images