Metalloporphyrin derivatives, process for their preparation and use in photolithography

Abstract

The present application relates to a kind of metal porphyrin derivatives and its preparation method and application in photoetching.The metal porphyrin derivative has higher melting point, can meet the requirement of photoetching technology, and structure is stable, and there is no change in high-temperature baking film structure.It can be used for negative photoresist.The obtained negative photoresist composition has higher thermal stability, is not easy to change during storage, and has low viscosity, and does not need to use additional solvent dilution during use.After exposure, the exposure pattern obtained has excellent resolution and contrast, and better sensitivity.

Description

Technical Field

[0001] This invention relates to the field of photolithography, specifically to a class of metalloporphyrin derivatives, their preparation methods, and their applications in photolithography. Background Technology

[0002] The semiconductor integrated circuit industry, as a crucial strategic foundational industry, is a significant indicator of a nation's technological progress and industrial competitiveness. Integrated circuits are one of the core products of modern electronics, widely used in computers, communications, military, medical, and automotive fields. Photoresist is a vital material used in the photolithography process during semiconductor chip manufacturing. Advances in photolithography technology have enabled the continuous reduction of device feature sizes, leading to continuous improvements in chip integration and performance.

[0003] Guided by Moore's Law, optical lithography technology has undergone transformations in exposure methods, including contact / proximity, equal-magnification projection, shrinkage step projection, and step-scan projection. The wavelengths of light sources used in lithography have evolved from ultraviolet to g-line (436nm), i-line (365nm), KrF (248nm), ArF (193nm, including dry and immersion types) and extreme ultraviolet (EUV, 13.5nm). Chip manufacturing has also progressed alongside these changes in exposure wavelengths, crossing 90, 45, 32, 22nm, and up to 5nm technology nodes, and is moving towards more advanced 3nm and below process nodes (Intel 20A). As integrated circuit manufacturing processes continue to advance, photoresists are also constantly being updated and replaced.

[0004] Currently, the most mature photolithography technologies are based on optical principles, and their resolution is limited by the diffraction limit. Even with EUV lithography, which uses a light source wavelength of 13.5 nm, the smallest patterned feature size that can be fabricated in a single exposure at this wavelength is around 13 nm (0.33 NA (numerical aperture of the projection lithography objective)). Increasing the EUV numerical aperture (0.55 NA) is expected to further improve the pattern resolution in the future. However, the high cost of EUV lithography equipment means that electron beam lithography (EBL), which can also generate high-energy electrons, is often used to verify the performance of photoresists for high-resolution patterning. However, chemically amplified photoresists based on traditional polymer systems are limited in their application in EUV lithography due to their large size and low EUV absorption.

[0005] Therefore, it is necessary to develop compounds suitable for EUV lithography. Summary of the Invention

[0006] The purpose of this invention is to provide a metalloporphyrin derivative and its preparation method.

[0007] Another object of the present invention is to provide the application of porphyrin derivatives containing different metals in photolithography and a negative photoresist composition.

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

[0009]

[0010] Wherein, M is one of the metals Mn, Fe, Co, Ni, Zn, Cu, Zr, Hf, Pd, In, Sn, La, Ce, Nd, Eu, Gd, Er, and Tm;

[0011] X is a halogen;

[0012] --X indicates the presence or absence of coordinated halide ions. When M is selected from Zn, Cu, Mn, Fe, Co, Ni, or Pd, coordinated halide ions are not present.

[0013] When M is selected from In, La, Ce, Nd, Eu, Gd, Er, Tm, there is a coordinating halide ion;

[0014] When M is selected from Zr, Hf, and Sn, there are two coordinated halide ions;

[0015] R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from H, OH, and C. 1-20 Alkyl, C 1-20 The alkoxy group or the Z group; said Z group is selected from unsubstituted groups, or optionally surrounded by one, two or more R groups. a The following groups are substituted: 3-20 membered heterocyclic group -O-, 3-20 membered heterocyclic group -C 1-20 Alkoxy- or C 2-20 alkenyl-C 1-20 Alkyloxy-;

[0016] The condition is that at least one of the five substituents (R1, R2, R3, R4, R5) of the four benzene rings surrounding formula (I) is selected from group Z;

[0017] Each R a Whether the two are the same or different, they are independently selected from oxygen (=O) and C. 1-20 Alkyl, C 1-20 Alkoxy, C 3-20 Cycloalkyl.

[0018] According to an embodiment of the present invention, R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from H and C. 1-12 Alkyl, C 1-12 alkoxy group, or group Z, wherein group Z is unsubstituted or optionally surrounded by one, two or more R groups. aThe following groups are substituted: 3-12 membered heterocyclic group -O-, 3-12 membered heterocyclic group -C 1-6 Alkoxy-, C 2-6 alkenyl-C 1-6 Alkyloxy-;

[0019] The condition is that at least one of the five substituents in at least one of the four benzene rings surrounding formula (I) is selected from group Z;

[0020] Each R a Whether the two are the same or different, they are independently selected from oxygen (=O) and C. 1-12 Alkyl, C 1-12 Alkoxy, C 3-12 Cycloalkyl.

[0021] In some embodiments of the present invention, in the compound shown in formula (I), at least one of the five substituents in each of the four peripheral benzene rings is selected from group Z, and the other groups are selected from H and C. 1-6 Alkyl or C 1-6 Alkoxy;

[0022] For example, the compound shown in formula (I) has a symmetrical structure, in which one of the substituents (R2 or R4) at the intermediate position of the four peripheral benzene rings is a Z group, and the other groups are selected from H, C 1-6 Alkyl or C 1-6 Alkoxy;

[0023] Alternatively, in the four peripheral benzene rings, the para-substituent R3 is always a Z group, and the other groups are selected from H and C. 1-6 Alkyl or C 1-6 Alkoxy;

[0024] Alternatively, one of the intermediate substituents (R2 or R4) on the four peripheral benzene rings and the para-substituent R3 are both groups Z, and the other groups are selected from H and C. 1-6 Alkyl or C 1-6 Alkyl group.

[0025] In some embodiments of the present invention, the 3-12 member heterocyclic group -C 1-6 The 3-12-membered heterocyclic groups in alkoxy- and 3-12-membered heterocyclic groups-O- may be the same or different, and are independently O-, S- or N-containing 3-12-membered heterocyclic groups, such as 3-8-membered oxetane or 3-6-membered oxetane, such as oxetanepropyl, oxetanebutyl, oxetanepentyl, and oxetanehexyl.

[0026] In some embodiments of the present invention, the group Z is surrounded by an R a The following groups are substituted: 3-12 membered heterocyclic group -O-, 3-12 membered heterocyclic group -C 1-6 Alkoxy-; R aSelected from =O; for example, the 3-12 membered heterocyclic group -O-, 3-12 membered heterocyclic group -C 1-6 The 3-12 membered heterocyclic group of the alkoxy group is exocyclicly substituted by the =O group.

[0027] According to an embodiment of the present invention, the group Z is, for example: * indicates a connection point.

[0028] According to embodiments of the present invention, the compound represented by formula (I) preferably has the structure represented by formula (A) or formula (B):

[0029]

[0030] Where M is selected from Mn, Fe, Co, Ni, Zn, Cu, Zr, Hf, Pd, In, Sn, La, Ce, Nd, Eu, Gd, Er, Tm;

[0031] X is chlorine or bromine;

[0032] --X indicates the presence or absence of a coordinated halide ion. When M is selected from Zn, Cu, Mn, Fe, Co, Ni, or Pd, the coordinated halide ion X is absent.

[0033] When M is selected from In, La, Ce, Nd, Eu, Gd, Er, Tm, there exists a coordinating halide ion X;

[0034] When M is selected from Zr, Hf, or Sn, there are two coordinated halide ions X.

[0035] The present invention also provides a method for preparing the compound shown in formula (I), comprising the following steps:

[0036]

[0037] Compound (I-2) reacts with compound Z'L1 to give the compound shown in formula (I);

[0038] Among them, --X, M, and R1-R5 have the definitions described above;

[0039] Z' is the structure of the above group Z after removing the O;

[0040] L1 is a leaving group, such as F, Cl, Br or I;

[0041] In compound (I-2), R'1-R'5 may be the same or different, and are independently selected from H, OH, and C. 1-20 Alkyl or C 1-20 Alkoxy, provided that at least one of the five substituents R'1-R'5 in each of the four benzene rings surrounding it is OH.

[0042] According to an embodiment of the present invention, the reaction is carried out in an organic solvent selected from formamide, chloroform, DMF, acetonitrile, tetrahydrofuran, N-methylpyrrolidone, etc., wherein N-methylpyrrolidone is preferred as the reaction solvent;

[0043] 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.

[0044] According to an embodiment of the present invention, the reaction temperature is 30-100°C, preferably 80-90°C; the reaction time is 12-36 h, preferably 18-24 h.

[0045] According to an embodiment of the present invention, compound (I-2) is prepared by the following method:

[0046] Compound (I-1) reacts with the metal salt MX to give compound (I-2);

[0047]

[0048] Among them, --X, M, R'1-R'5 have the definitions described above;

[0049] The anion X in the metal salt MX is F. - Cl - ,Br - Or I - ;

[0050] The metal salt MX is a halide of manganese, iron, cobalt, nickel, zinc, copper, zirconium, halide of hafnium, palladium, indium, tin, lanthanum, cerium, neodymium, europium, gadolinium, erbium, or thulium.

[0051] 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.

[0052] The present invention also provides a photoresist composition comprising: a substrate; said substrate being selected from at least one compound represented by formula (I).

[0053] According to an embodiment of the present invention, the photoresist composition is a negative photoresist composition.

[0054] According to an embodiment of the present invention, the photoresist composition further includes a photoacid generator; the photoacid generator is selected, for example, from ionic or nonionic acid generators, such as at least one of triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonate perfluorobutylsulfonate, di(4-tert-butylphenyl)iodonium p-toluenesulfonate, N-hydroxynaphthalimide trifluoromethanesulfonate, and benzyl(4-hydroxyphenyl)methylthiodonium hexafluoroantimonate.

[0055] According to an embodiment of the present invention, the photoresist 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.

[0056] According to an embodiment of the present invention, the concentration of the substrate in the photoresist composition is 5 to 50 mg / mL, for example, 10 to 30 mg / mL.

[0057] 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%.

[0058] 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.

[0059] According to an embodiment of the present invention, the photoresist composition further includes other additives, such as sensitizers, surfactants, dyes, stabilizers, etc.

[0060] 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).

[0061] Beneficial effects

[0062] The present invention provides a small molecule metal complex of formula (I), which has a metalloporphyrin as the central structure, has a high melting point, meets the requirements of photolithography technology, and has a stable structure, with no change in film structure during high-temperature baking.

[0063] The metal complex described in this invention can be used in negative photoresists. The resulting negative photoresist composition exhibits high thermal stability, is not easily denatured during storage, and has low viscosity, requiring no additional solvent dilution during use. The exposed pattern obtained after exposure has excellent resolution and contrast, and good sensitivity.

[0064] The photoresist composition of the present invention can realize electron beam lithography (EBL) and extreme ultraviolet lithography for high-energy electrons, and the resulting lithographic pattern has excellent resolution and contrast, and good sensitivity. Attached Figure Description

[0065] Figure 1 Thermogravimetric analysis image of compound TP-A-1 prepared in Example 1.

[0066] Figure 2 Electron beam lithography image of the photoresist composition prepared for Example 39.

[0067] Figure 3 Electron beam lithography image of the photoresist composition prepared for Example 40.

[0068] Figure 4 Electron beam lithography image of the photoresist composition prepared in Example 41.

[0069] Terminology Definitions and Explanations

[0070] 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.

[0071] The term "halogen" includes F, Cl, Br, or I.

[0072] 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.

[0073] 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-chain 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-chain 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 ... 2-3 Alkenyl). 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.

[0074] 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. Detailed Implementation

[0075] 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.

[0076] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0077] Example 1: Preparation of compound TP-A-1

[0078] Synthetic route of compound TP-A-1:

[0079]

[0080] Synthesis of compound A2-1:

[0081] Add 20 mL of DMF, 20 mL of chloroform, and 0.6 g of compound A1 to a 100 mL three-necked flask. After reflux begins, add 360 mg of ZnCl2. Monitor the reaction progress using UV-Vis absorption spectroscopy. After the reaction is complete, extract with distilled water, collect the chloroform layer, evaporate to dryness, and perform column chromatography using silica gel as the stationary phase and a mixture of dichloromethane and methanol (v / v = 9:1) as the eluent. Collect the concentrated red chromatographic band, evaporate to dryness, and vacuum dry for 24 h to obtain 510 mg of compound A2-1.

[0082] Synthesis of compound TP-A-1:

[0083] 475 mg of K₂CO₃ and 468 mg of bromopropylene oxide were placed in a two-necked flask (each flask was connected to a constant-pressure dropping funnel and a rubber stopper). 10 mL of DMF was added. 510 mg of compound A₂-1 was dissolved in 10 mL of DMF, and the solution was added to the dropping funnel. The reaction system was stirred at 80-90 °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 subjected to column chromatography to obtain 430 mg of compound TP-A-1.

[0084] The TGA curve of the obtained compound TP-A-1 is as follows: Figure 1 As shown. By Figure 1 It can be seen that compound TP-A-1 remains stable below 300℃, exhibiting high thermal stability.

[0085] 1 H NMR (400MHz, DMSO-d6) δ8.81(s,8H),7.75(s,8H),7.69(t,J=8.0Hz,4H),7.42(d,J=8.0Hz,4H),4.56(d,J=8.0H z,4H),4.06-4.01(m,4H),3.47-3.40(m,4H),2.87(t,J=8.0Hz,4H),2.75-2.72(m,4H).HRMS(MALDI) theoretical value: [M+H] + 964.25; Experimental value: 964.24.

[0086] Examples 2-18: Porphyrin-like compounds similar to those in Example 1 were prepared according to the above method.

[0087] Example 2: Preparation of compound TP-A-2

[0088]

[0089] The compound (TP-A-2) was synthesized by referring to Example 1, except that ZnCl2 was replaced with MnCl2.

[0090] Example 3: Preparation of compound TP-A-3

[0091]

[0092] The compound (TP-A-3) was synthesized by replacing ZnCl2 with FeCl2, as described in Example 1.

[0093] Example 4: Preparation of compound TP-A-4

[0094]

[0095] The compound (TP-A-4) was synthesized by replacing ZnCl2 with CoCl2, as described in Example 1.

[0096] Example 5: Preparation of compound TP-A-5

[0097]

[0098] The compound (TP-A-5) was prepared by replacing ZnCl2 with NiCl2, as described in Example 1.

[0099] Example 6: Preparation of compound TP-A-6

[0100]

[0101] The compound (TP-A-6) was synthesized by referring to Example 1, except that ZnCl2 was replaced with ZrCl4.

[0102] Example 7: Preparation of compound TP-A-7

[0103]

[0104] The compound (TP-A-7) was synthesized by replacing ZnCl2 with HfCl4, as described in Example 1.

[0105] Example 8: Preparation of compound TP-A-8

[0106]

[0107] The compound (TP-A-8) was synthesized by referring to Example 1, except that ZnCl2 was replaced with PdCl2.

[0108] Example 9: Preparation of compound TP-A-9

[0109]

[0110] The compound (TP-A-9) was synthesized by referring to Example 1, except that ZnCl2 was replaced with InCl3.

[0111] Example 10: Preparation of compound TP-A-10

[0112]

[0113] The compound (TP-A-10) was synthesized by referring to Example 1, except that ZnCl2 was replaced with SnCl4.

[0114] Example 11: Preparation of compound TP-A-11

[0115]

[0116] The compound (TP-A-11) was synthesized by referring to Example 1, except that ZnCl2 was replaced with LaCl3.

[0117] Example 12: Preparation of compound TP-A-12

[0118]

[0119] The compound (TP-A-12) was synthesized by referring to Example 1, except that ZnCl2 was replaced with CeCl3.

[0120] Example 13: Preparation of compound TP-A-13

[0121]

[0122] The compound (TP-A-13) was synthesized by referring to Example 1, except that ZnCl2 was replaced with NdCl3.

[0123] Example 14: Preparation of compound TP-A-14

[0124]

[0125] The compound (TP-A-14) was synthesized by referring to Example 1, except that ZnCl2 was replaced with EuCl3.

[0126] Example 15: Preparation of compound TP-A-15

[0127]

[0128] The compound (TP-A-15) was synthesized by referring to Example 1, except that ZnCl2 was replaced with GdCl3.

[0129] Example 16: Preparation of compound TP-A-16

[0130]

[0131] The compound (TP-A-16) was synthesized by referring to Example 1, except that ZnCl2 was replaced with ErCl3.

[0132] Example 17: Preparation of compound TP-A-17

[0133]

[0134] The compound (TP-A-17) was synthesized by referring to Example 1, except that ZnCl2 was replaced with TmCl3.

[0135] Example 18: Preparation of compound TP-A-18

[0136]

[0137] The compound (TP-A-18) was synthesized by referring to Example 1, except that ZnCl2 was replaced with CuCl2.

[0138] Example 19: Preparation of compound TP-B-1

[0139] Synthetic route of compound TP-B-1:

[0140]

[0141] Synthesis of compound B1:

[0142] Pyrrole was distilled at atmospheric pressure. 10 mL of the distilled pyrrole was diluted with 20 mL of propionic acid and set aside. 9 g of 3,4-dimethoxybenzaldehyde and 500 mL of propionic acid were measured into a 1000 mL three-necked flask, stirred rapidly, and heated to reflux. After the reagents were completely dissolved, the pyrrole-propionic acid solution was added dropwise through a constant pressure funnel, completing the addition in approximately 30 minutes. The mixture was then refluxed for another 1 hour. After the reaction was complete, approximately 200 mL of propionic acid was distilled off, and 100 mL of anhydrous methanol was added. The mixture was then cooled overnight in an ice-water bath. The next day, it was filtered to obtain a purple powdery solid, which was dried and separated to obtain 1.8 g of compound B1.

[0143] Synthesis of compound B2:

[0144] 1 g of compound B1 was dissolved in 100 mL of anhydrous CH2Cl2, and N2 was bubbled through it. The solution was placed in an ice-water bath, and 10.2 mL of 1 M BBr3 dichloromethane solution was slowly added dropwise to the mixture using a constant-pressure funnel. The mixture was stirred, and the solution was slowly brought to room temperature and stirred overnight. After the reaction was complete, the reaction mixture 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 the mixture was slowly added dropwise under an ice-water bath. The mixture was stirred for 2 hours. After the reaction was complete, the reaction mixture 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 sonicated and filtered to obtain 0.87 g of compound B2.

[0145] Synthesis of compound B3-1:

[0146] Add 20 mL DMF, 20 mL chloroform, and 500 mg of compound B2 to a 100 mL three-necked flask. After reflux begins, add 450 mg of ZnCl2. Monitor the reaction progress using UV-Vis absorption spectroscopy. After the reaction is complete, extract with distilled water, collect the chloroform layer, evaporate to dryness, and perform column chromatography using silica gel as the stationary phase and a mixture of dichloromethane and methanol (v / v = 8:1) as the eluent. Collect the concentrated red chromatographic band, evaporate to dryness, and vacuum dry for 24 h to obtain 480 mg of compound B3-1.

[0147] Synthesis of compound TP-B-1:

[0148] 712 mg of K₂CO₃ and 707 mg of bromopropylene oxide were placed in a two-necked flask (each flask was connected to a constant-pressure dropping funnel and a rubber stopper). 10 mL of DMF was added. 480 mg of compound B3-1 was dissolved in 10 mL of DMF, 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 subjected to column chromatography to obtain 300 mg of compound TP-B-1.

[0149] 1 ¹H NMR (300MHz, DMSO-d⁶) δ 8.92 (s, 8H), 7.42 (d, J = 3.0Hz, 8H), 7.07 (d, J = 3.0Hz, 4H), 4.55 (m, 8H), 4.05–3.95 (m, 8H), 3.43–3.40 (m, 8H), 2.88–2.84 (m, 8H), 2.73–2.70 (m, 8H). HRMS (MALDI): Theoretical value [M+H] + : 1252.33; Experimental value: 1252.32.

[0150] Examples 20-36: Porphyrin-like compounds from Example 19 were prepared according to the above method.

[0151] Example 20: Preparation of compound TP-B-2

[0152]

[0153] The compound (TP-B-2) was synthesized by referring to Example 19, except that ZnCl2 was replaced with MnCl2.

[0154] Example 21: Preparation of compound TP-B-3

[0155]

[0156] The compound (TP-B-3) was synthesized by referring to Example 19, except that ZnCl2 was replaced with FeCl2.

[0157] Example 22: Preparation of compound TP-B-4

[0158]

[0159] The compound (TP-B-4) was synthesized by referring to Example 19, except that ZnCl2 was replaced with CoCl2.

[0160] Example 23: Preparation of compound TP-B-5

[0161]

[0162] The compound (TP-B-5) was synthesized by referring to Example 19, except that ZnCl2 was replaced with NiCl2.

[0163] Example 24: Preparation of compound TP-B-6

[0164]

[0165] The compound (TP-B-6) was synthesized by referring to Example 19, except that ZnCl2 was replaced with ZrCl4.

[0166] Example 25: Preparation of compound TP-B-7

[0167]

[0168] The compound (TP-B-7) was synthesized by replacing ZnCl2 with HfCl4, as described in Example 19.

[0169] Example 26: Preparation of compound TP-B-8

[0170]

[0171] The compound (TP-B-8) was synthesized by replacing ZnCl2 with PdCl2, as described in Example 19.

[0172] Example 27: Preparation of compound TP-B-9

[0173]

[0174] The compound (TP-B-9) was synthesized by referring to Example 19, except that ZnCl2 was replaced with InCl3.

[0175] Example 28: Preparation of compound TP-B-10

[0176]

[0177] The compound (TP-B-10) was synthesized by referring to Example 19, except that ZnCl2 was replaced with SnCl4.

[0178] Example 29: Preparation of compound TP-B-11

[0179]

[0180] The compound (TP-B-11) was synthesized by referring to Example 19, except that ZnCl2 was replaced with LaCl3.

[0181] Example 30: Preparation of compound TP-B-12

[0182]

[0183] The compound (TP-B-12) was synthesized by referring to Example 19, except that ZnCl2 was replaced with CeCl3.

[0184] Example 31: Preparation of compound TP-B-13

[0185]

[0186] The compound (TP-B-13) was synthesized by referring to Example 19, except that ZnCl2 was replaced with NdCl3.

[0187] Example 32: Preparation of compound TP-B-14

[0188]

[0189] The compound (TP-B-14) was synthesized by referring to Example 19, except that ZnCl2 was replaced with EuCl3.

[0190] Example 33: Preparation of compound TP-B-15

[0191]

[0192] The compound (TP-B-15) was synthesized by referring to Example 19, except that ZnCl2 was replaced with GdCl3.

[0193] Example 34: Preparation of compound TP-B-16

[0194]

[0195] The compound (TP-B-16) was synthesized by referring to Example 19, except that ZnCl2 was replaced with ErCl3.

[0196] Example 35: Preparation of compound TP-B-17

[0197]

[0198] The compound (TP-B-17) was synthesized by referring to Example 19, except that ZnCl2 was replaced with TmCl3.

[0199] Example 36: Preparation of compound TP-B-18

[0200]

[0201] The compound (TP-B-18) was synthesized by replacing ZnCl2 with CuCl2, as described in Example 19.

[0202] Example 37: Preparation of a photoresist composition containing compound TP-A-1

[0203] Weigh 100 mg of compound (TP-A-1) and 7.5 mg of the photoacid-generating agent benzyl(4-hydroxyphenyl)methylthionyl hexafluoroantimonate. Measure 5 mL of the photoresist solvent propylene glycol methyl ether acetate (PGMEA) to prepare a photoresist solution containing compound TP-A-1 (concentration 20 mg / mL). After ultrasonic treatment for 30 min, filter three times through a 0.20 μm polytetrafluoroethylene membrane to prepare a negative photoresist composition.

[0204] Example 38: Photoresist composition containing compound TP-B-1

[0205] Following the basic example of Example 35, compound (TP-A-1) was replaced with compound (TP-B-1). A negative photoresist composition containing compound TP-B-1 at a concentration of 30 mg / mL was prepared.

[0206] Example 39: Photolithographic properties of a negative photoresist composition containing compound (TP-A-1)

[0207] Untreated blank silicon wafers were selected, and the surface dust was removed by blowing with a nitrogen gun. The negative photoresist composition prepared in Example 35 was spin-coated onto the silicon wafer, with spin-coating parameters set to 3000 rpm / 90 s and pre-baking parameters set to 80°C / 180 s. The film thickness was measured using an optical ellipsometry and found to be 43 nm. Exposure was performed using an electron beam with an accelerating voltage of 100 kV, and the post-baking parameters were set to 90°C / 120 s. Development was then performed with a developer solution of methyl isobutyl ketone:isopropanol = 10:1 (volume ratio) for 60 s, followed by isopropanol rinsing for 60 s. After development, SEM images were acquired using a Hitachi 8230 scanning electron microscope. The specific photolithography results are shown below. Figure 2 As shown. By Figure 2 It is known that the photoresist composition can achieve 30nm photolithographic stripes and has high contrast.

[0208] The negative photoresist composition containing compound (TP-A-1) achieved high-resolution patterning in electron beam lithography, demonstrating its potential for achieving high-resolution EUV patterning.

[0209] Example 40: Photolithographic properties of a negative photoresist composition containing compound (TP-B-1)

[0210] Untreated blank silicon wafers were selected, and surface dust was removed using a nitrogen gun. The negative photoresist composition prepared in Example 36 was spin-coated onto the silicon wafer, with spin-coating parameters set to 4500 rpm / 90 s and pre-baking parameters set to 80°C / 180 s. The film thickness was measured to be 41.5 nm using an optical ellipsometry. Exposure was performed using an electron beam with an accelerating voltage of 100 kV, and post-baking parameters were set to 90°C / 120 s. Development was performed with methyl isobutyl ketone developer for 60 s, followed by rinsing with isopropanol for 60 s. After development, SEM images were acquired using a Hitachi 8230 scanning electron microscope. The specific photolithography results are shown below. Figure 3 As shown. By Figure 3 It is known that the photoresist composition can achieve 25nm photolithographic stripes and has high contrast.

[0211] The negative photoresist composition containing compound (TP-B-1) achieved high-resolution patterning in electron beam lithography, demonstrating its potential for achieving high-resolution EUV patterning.

[0212] Example 41: Photolithographic properties of a negative photoresist composition containing compound (TP-A-18)

[0213] Referring to Example 39, TP-A-1 is replaced with TP-A-18. The specific photolithography results are as follows: Figure 4 As shown. By Figure 4 It is known that the photoresist composition containing compound TP-A-18 can achieve 30nm photolithographic stripes and has high contrast, and its photolithographic performance is almost identical to that of the photoresist composition containing compound TP-A-1.

[0214] 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, M is one of the following metals: Mn, Fe, Co, Ni, Zn, Cu, Zr, Hf, Pd, In, Sn, La, Ce, Nd, Eu, Gd, Er, and Tm. X is a halogen; --X indicates the presence or absence of coordinated halide ions. When M is selected from Zn, Cu, Mn, Fe, Co, Ni, or Pd, coordinated halide ions are not present. When M is selected from In, La, Ce, Nd, Eu, Gd, Er, Tm, there is a coordinating halide ion; When M is selected from Zr, Hf, and Sn, there are two coordinated halide ions; R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from H, OH, and C. 1-20 Alkyl, C 1-20 The alkoxy group or the Z group; said Z group is selected from unsubstituted groups, or optionally surrounded by one, two or more R groups. a The following groups are substituted: 3-20 membered heterocyclic group -O-, 3-20 membered heterocyclic group -C 1-20 Alkoxy- or C 2-20 alkenyl-C 1-20 Alkyloxy-; The condition is that at least one of the five substituents (R1, R2, R3, R4, R5) of the four benzene rings surrounding formula (I) is selected from group Z; Each R a Whether the two are the same or different, they are independently selected from oxygen (=O) and C. 1-20 Alkyl, C 1-20 Alkoxy, C 3-20 Cycloalkyl.

2. The compound according to claim 1, wherein, R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from H and C. 1-12 Alkyl, C 1-12 alkoxy group, or group Z, wherein group Z is unsubstituted or optionally surrounded by one, two or more R groups. a The following groups are substituted: 3-12 membered heterocyclic group -O-, 3-12 membered heterocyclic group -C 1-6 Alkoxy-, C 2-6 alkenyl-C 1-6 Alkyloxy-; The condition is that at least one of the five substituents in at least one of the four benzene rings surrounding formula (I) is selected from group Z; Each R a Whether the two are the same or different, they are independently selected from oxygen (=O) and C. 1-12 Alkyl, C 1-12 Alkoxy, C 3-12 Cycloalkyl.

3. The compound according to claim 1 or 2, wherein, The compound shown in formula (I) has a symmetrical structure, with one of the substituents at the middle position of the four peripheral benzene rings being a Z group, and the other groups being selected from H, C. 1-6 Alkyl or C 1-6 Alkoxy; Alternatively, in the four peripheral benzene rings, the para-substituent R3 is always a Z group, and the other groups are selected from H and C. 1-6 Alkyl or C 1-6 Alkoxy; Alternatively, one of the intermediate substituents (R2 or R4) on the four peripheral benzene rings and the para-substituent R3 are both groups Z, and the other groups are selected from H and C. 1-6 Alkyl or C 1-6 Alkyl group.

4. The compound according to any one of claims 1-3, wherein, The 3-12 membered heterocyclic group -C 1-6 The 3-12-membered heterocyclic groups in alkoxy- and 3-12-membered heterocyclic groups-O- may be the same or different, and are independently O-, S- or N-containing 3-12-membered heterocyclic groups, such as 3-8-membered oxetane or 3-6-membered oxetane, such as oxetanepropyl, oxetanebutyl, oxetanepentyl, and oxetanehexyl.

5. The compound according to any one of claims 1-4, wherein, The compound shown in formula (I) has the structure shown in formula (A) or formula (B): Where M is selected from Mn, Fe, Co, Ni, Zn, Cu, Zr, Hf, Pd, In, Sn, La, Ce, Nd, Eu, Gd, Er, Tm; X is chlorine or bromine; --X indicates the presence or absence of a coordinated halide ion. When M is selected from Zn, Cu, Mn, Fe, Co, Ni, or Pd, the coordinated halide ion X is absent. When M is selected from In, La, Ce, Nd, Eu, Gd, Er, Tm, there exists a coordinating halide ion X; When M is selected from Zr, Hf, or Sn, there are two coordinated halide ions X.

6. A method for preparing the compound of formula (I) according to any one of claims 1-5, wherein, Includes the following steps: Compound (I-2) reacts with compound Z'L1 to give the compound shown in formula (I); Wherein, --X, M, R1-R5 have the definitions described in any one of claims 1-5; Z' is the structure of the above group Z after removing the O; L1 is a leaving group; In compound (I-2), R'1-R'5 may be the same or different, and are independently selected from H, OH, and C. 1-20 Alkyl or C 1-20 Alkoxy, provided that at least one of the five substituents R'1-R'5 in each of the four benzene rings surrounding it is OH.

7. The use of the compound of formula (I) according to any one of claims 1-5 in photolithography, such as in photoresist, preferably in the preparation of negative photoresist.

8. A photoresist composition comprising: Matrix; The matrix is ​​selected from at least one of the compounds represented by formula (I) according to any one of claims 1-5.

9. The photoresist composition according to claim 8, wherein, The photoresist composition is a negative photoresist composition; Preferably, the photoresist composition further includes a photoacid generator; the photoacid generator is selected from ionic or nonionic acid generators, 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; Preferably, the photoresist composition further includes other additives, such as sensitizers, surfactants, dyes, and stabilizers.

10. The use of the photoresist composition of claim 8 or 9 in ultraviolet (365nm) lithography, deep ultraviolet (248nm, 193nm) lithography, extreme ultraviolet (13.5nm, EUV) lithography and electron beam lithography (EBL).

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