Adamantane structure-based polybenzyl chloride type monomolecular resin photoresist as well as preparation method and application thereof

Abstract

The invention provides a polybenzyl chloride type monomolecular resin photoresist based on an adamantane structure as well as a preparation method and application of the polybenzyl chloride type monomolecular resin photoresist. According to the invention, the advantages of non-chemically amplified photoresist and monomolecular resin are combined, and a series of monomolecular resin based on adamantane core and periphery grafted benzyl chloride groups are synthesized. The series of compounds are simple in synthesis process, have very high thermal stability and good film-forming property, and can meet the requirements of a photoresist process. Electron beam and extreme ultraviolet lithography show that the series of photoresist materials are expected to meet the requirement of high-resolution lithography.

Description

Technical Field

[0001] The present invention belongs to the technical field of lithography materials, and particularly relates to a class of adamantane-based multi-benzyl chloride single-molecule resin photoresists, their preparation methods and applications. Background Art

[0002] Photoresist, also known as photoresist, is a type of etching-resistant thin film material whose solubility changes after being irradiated by energy such as light beam, electron beam, ion beam or x-ray. It is an indispensable core material in the microelectronics industry for fabricating large-scale and ultra-large-scale integrated circuits. By coating the photoresist on the surface of semiconductors, conductors or insulators, the remaining part after exposure and development protects the underlying layer, and then an etchant is used for etching to transfer the required fine pattern from the mask to the substrate to be processed. Therefore, photoresist is a key material in device microfabrication technology. With the large-scale production of extreme ultraviolet lithography in the semiconductor industry, the resolution required by nanoscale lithography technology is getting higher and higher, and the requirement for edge roughness is also getting smaller and smaller, posing higher requirements for the comprehensive performance that photoresist materials can achieve. Developing new photoresists that can meet strict specifications such as resolution, sensitivity, line edge roughness and defect rate remains a core challenge. The main materials of traditional photoresists are polymer resins with a molecular weight of 5000 - 15000 daltons. These polymer resins usually affect the resolution and edge roughness of lithography patterns due to reasons such as too large molecular volume, polydispersity of molecular weight and entanglement of molecular chains, and cannot meet the requirements for finer resolution. To solve these problems, a method of controlling through chemical synthesis to reduce the molecular weight of the main resin material of the photoresist to a single molecular state, forming a single-molecule resin (also known as molecular glass), is an important method to achieve high-resolution lithography. The single-molecule resin not only retains the film-forming characteristics and easy processing performance of the resin itself, but also has a definite molecular structure, is easy to synthesize and modify. Photoresist materials based on single-molecule resins are expected to meet the requirements of high-resolution lithography.

[0003] From the mechanism of solubility change, photoresists are divided into chemically amplified resists (CAR) and non-chemically amplified resists (n-CAR). Chemically amplified resists (CAR) mainly consist of a main material, an acid generator and an acid diffusion inhibitor. During the process of spin-coating the photoresist into a film, due to the different structures of the acid generator molecules and the main material, the acid generator molecules will aggregate and phase separate, which leads to problems such as micro-bridging and footing in the photoresist pattern, and a large LER, limiting the improvement of resolution. In contrast, non-chemically amplified resists (n-CAR) rely on the photoreaction of photosensitive groups in the main material to generate solubility changes, avoiding problems such as uneven component distribution and acid diffusion, and are more likely to achieve higher resolution and lower LER.

[0004] Therefore, in high-resolution lithography, single-component non-chemically amplified photoresists have more advantages. Non-chemically amplified photoresists can be classified into chain scission mechanism types, crosslinking mechanism types, decomposition types, etc. according to their reaction mechanisms. However, there are few reports on single-molecule resin photoresists based on the crosslinking mechanism. Summary of the Invention

[0005] To solve the above problems, the present invention provides an adamantane-based benzyl chloride type single-molecule resin, which can be used as the main material of a non-chemically amplified photoresist.

[0006] The technical solution of the present invention is as follows:

[0007] Compounds represented by the following formula (I), formula (II), or formula (III):

[0008]

[0009] Wherein, in formula (I), R 1a ~R 20a ; in formula (II), R 1b ~R 30b ; in formula (III), R 1c ~R 40c are the same or different and are each independently selected from the group Z, -CH2Cl, -O-C 1-15 alkyl-C 6-20 aryl-CH2Cl; the group Z is H, an unsubstituted or optionally substituted by one, two or more R S substituted following groups: C 1-15 alkyl, C 1-15 alkoxy, C 3-20 cycloalkyl, C 6-20 aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclic group, -C 1-15 alkyl-C 6-20 aryl, -C 1-15 alkyl-5-20 membered heteroaryl, -C 1-15 alkyl-CO-C 6-20 aryl, -C 1-15 alkyl-CO-5-20 membered heteroaryl, -C 1-15 alkyl-CO-C 1-15 alkyl, -C 1-15 alkyl-CO-C 3-20 cycloalkyl;

[0010] Provided that:

[0011] R 1a ~R 20a at least one of the groups is -CH2Cl;

[0012] R 1b ~R30b At least one of the groups is -CH2Cl;

[0013] R 1c ~R 40c At least one of the groups is -CH2Cl;

[0014] R is selected from -CH2Cl, -O-C 1-15 alkyl-C 6-20 aryl-CH2Cl or group Z as described above;

[0015] R S is selected from =O, NO2, C 1-15 alkyl, C 1-15 alkoxy, C 3-20 cycloalkyl, C 6-20 aryl, 5-20 membered heteroaryl.

[0016] In some embodiments of the present invention, the compound of formula (I) has 4-6 -CH2Cl groups, for example, 4, 5, or 6 -CH2Cl.

[0017] In some embodiments of the present invention, the compound of formula (II) has 6-9 -CH2Cl groups, for example, 6, 7, 8, or 9 -CH2Cl.

[0018] In some embodiments of the present invention, the compound of formula (III) has 8-12 -CH2Cl groups, for example, 8, 9, 10, 11, or 12 -CH2Cl.

[0019] In some embodiments of the present invention, R 1a -R 20a has 4 -CH2Cl, and each phenyl has 1 -CH2Cl.

[0020] In some embodiments of the present invention, R 1b -R 30b has 6 -CH2Cl, and each phenyl has 1 -CH2Cl.

[0021] In some embodiments of the present invention, R 1c -R 40c has 8 -CH2Cl, and each phenyl has 1 -CH2Cl.

[0022] In some embodiments of the present invention, the -CH2Cl is located at the ortho, meta, or para position of the benzene ring it substitutes.

[0023] In some embodiments of the present invention, R is H or -C 1-6 alkoxy (such as methoxy).

[0024] In some embodiments of the present invention, the compound represented by formula (I) has a symmetric structure, that is, the structures on the 4 peripheral benzene rings are completely the same.

[0025] In some embodiments of the present invention, the compound represented by formula (II) has a symmetric structure, that is, the structures on the 6 peripheral benzene rings are completely the same.

[0026] In some embodiments of the present invention, the compound represented by formula (III) has a symmetric structure, that is, the structures on the 8 peripheral benzene rings are completely the same.

[0027] As an example, the compound represented by formula (I) has the following structure:

[0028]

[0029] As an example, the compound represented by formula (II) has the following structure:

[0030] As an example, the compound represented by formula (III) has the following structure:

[0031]

[0032] The present invention also provides a method for preparing the compound represented by formula (I), formula (II) or formula (III), comprising:

[0033] Mixing the compound (V') with thionyl chloride and reacting under the catalysis of N,N-dimethylformamide to obtain the compound represented by formula (I);

[0034]

[0035] Alternatively, mixing the compound (V”) with thionyl chloride and reacting under the catalysis of N,N-dimethylformamide to obtain the compound represented by formula (II);

[0036]

[0037] Alternatively, mixing the compound (V”') with thionyl chloride and reacting under the catalysis of N,N-dimethylformamide to obtain the compound represented by formula (III);

[0038]

[0039] Wherein, R 1a ’ ~R 20a ’ 、R 1b ’ ~R 30b’ , R 1c ’ ~R 40c ’ are the same or different and each independently selected from -CH2OH, -O-C 1-15 alkyl-C 6-20 aryl-CH2OH or group Z, where the groups Z, R, R 1a ~R 20a , R 1b ~R 30b , R 1c ~R 40c have the above definitions;

[0040] Provided that:

[0041] R 1a ’ ~R 20a ’ at least one of the groups is -CH2OH;

[0042] R 1b ’ ~R 30b ’ at least one of the groups is -CH2OH;

[0043] R 1c ’ ~R 40c ’ at least one of the groups is -CH2OH.

[0044] According to an embodiment of the present invention, the reaction is carried out at room temperature.

[0045] The present invention also provides the use of the compound represented by the above formula (I), formula (II) or formula (III) for preparing a photoresist.

[0046] The present invention also provides a photoresist composition comprising one or more of the compounds represented by formula (I), formula (II) or formula (III).

[0047] According to an embodiment of the present invention, the compound represented by formula (I), formula (II) or formula (III) is used as the main material of the photoresist composition.

[0048] According to an embodiment of the present invention, the photoresist composition further comprises a photoresist solvent.

[0049] According to an embodiment of the present invention, the photoresist solvent is selected from one, two or more of the following substances: propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), N,N-dimethylformamide (DMF), cyclohexanone, ethyl n-pentanone, ethyl isopentanone, ethanol, acetonitrile, isopropanol, acetone, methyl n-pentanone, methyl isopentanone.

[0050] According to an embodiment of the present invention, the photoresist composition is a positive or negative photoresist composition, which comprises the compound shown in the formula (I) and / or (II) and / or (III) and a photoresist solvent.

[0051] In one embodiment, the photoresist is a single-component photoresist, which is composed of the compound shown in the formula (I) and / or (II) and / or (III) and a photoresist solvent, that is, in the photoresist composition, except for the photoresist solvent, only the compound shown in the formula (I) and / or (II) and / or (III) is included.

[0052] The present invention also provides a photoresist coating, which comprises one or more of the compounds shown in the formula (I), formula (II) or formula (III).

[0053] The present invention also provides a method for preparing the above photoresist coating, comprising: applying the above photoresist composition on a substrate to obtain it.

[0054] Preferably, the applying method is spin coating.

[0055] Preferably, the substrate is, for example, a silicon wafer substrate.

[0056] Preferably, the applying method is spin coating.

[0057] Preferably, the substrate is, for example, a silicon wafer substrate.

[0058] Preferably, the photoresist coating is a thin film.

[0059] The present invention also provides the application of the photoresist coating in lithography.

[0060] The compound of the present invention has high thermal stability and photosensitivity due to its unique multi-benzyl chloride structure and can be used for lithography processing.

[0061] According to the present invention, the photoresist coating can be used in modern lithography technologies such as 365 nm lithography, 254 nm lithography, 248 nm lithography, 193 nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography or electron beam lithography, etc., and is preferably used in extreme ultraviolet and electron beam lithography technologies.

[0062] The beneficial effects of the present invention are as follows:

[0063] (1) The present invention provides a series of novel single-molecule resins of benzyl chloride type based on adamantane structure, namely the compounds represented by formula (I), or (II), or (III), which can be used as the main material of photoresist. Their raw materials are cheap and easily available, and the synthesis process is simple;

[0064] (2) The novel single-molecule resin of benzyl chloride type based on adamantane structure provided by the present invention has good solubility in various polar solvents, and good films can be prepared by spin coating method. The thermal decomposition temperature of the main material is greater than 110 °C, which meets the requirements of photolithography processing technology. The compounds represented by formula (I), or (II), or (III) can be used as single-component non-chemically amplified photoresists, avoiding problems such as uneven distribution of acid generators and acid diffusion inhibitors and uneven acid diffusion in chemically amplified photoresists. The obtained patterns have high resolution and low line edge roughness.

[0065] (3) The compounds of the present invention use adamantane as the core unit, with multiple benzyl chloride groups externally connected. The core structures of adamantane and benzene ring, plus the introduction of chlorine atoms, can maximize the etching resistance of the main material.

[0066] (4) The multi-benzyl chloride type single-molecule resin based on adamantane structure of the present invention has a definite molecular structure by itself, with a single molecular size. After exposure, it shows obvious solubility differences in various organic developers, and high-resolution photolithography can be well achieved.

[0067] In summary, the present invention combines the advantages of non-chemically amplified photoresists and single-molecule resins, and synthesizes a series of single-molecule resins with benzyl chloride groups grafted on the periphery of an adamantane core. The synthesis process of this series of compounds is simple, and they have high thermal stability, good film-forming properties, and can meet the requirements of photoresist processes.

[0068] Terms and Definitions

[0069] Unless otherwise defined, all scientific and technical terms used herein have the same meanings as those commonly understood by those skilled in the art to which the subject matter of the claims pertains.

[0070] "More than" means three or more.

[0071] The term "C 1-15 alkyl" should be understood to represent a straight-chain or branched-chain saturated monovalent hydrocarbon group having 1 to 15 carbon atoms. For example, "C 1-6"Alkyl" means straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-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, 1,2-dimethylbutyl, etc., or their isomers.

[0072] The term "C 1-15 alkoxy" should be understood as -O-C 1-15 alkyl, where C 1-15 alkyl has the above definition.

[0073] The term "C 3-20 cycloalkyl" should be understood to represent a saturated monovalent monocyclic, bicyclic, or polycyclic hydrocarbon ring (also known as a fused-ring hydrocarbon ring) having 3 - 20 carbon atoms. Bicyclic or polycyclic cycloalkyls include spirocycloalkyls, bridged cycloalkyls, and fused cycloalkyls; the fused cycloalkyls refer to a fused-ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing a bond). The bridged cycloalkyls refer to a fused-ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. The spirocycloalkyls refer to a fused-ring structure formed by two or more cyclic structures sharing one ring atom. For example, the C 3-20 cycloalkyl can be a C 3-8 monocyclic cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or a C 7-12 fused cycloalkyl, such as decahydronaphthalene ring; it can also be a C 7-12 bridged cycloalkyl, such as norbornane, adamantane, bicyclo[2,2,2]octane.

[0074] The term "3-20 membered heterocyclic group" means a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring which contains 1-5 heteroatoms independently selected from N, O and S, preferably "3-10 membered heterocyclic group". The term "3-10 membered heterocyclic group" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring which contains 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the remainder of the molecule through any one of the carbon atoms or a nitrogen atom (if present). In particular, the heterocyclic group may include but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings such as tetrahydrofuranyl, dioxolanyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or 6-membered rings such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or 7-membered rings such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, for example but not limited to 5,5-membered rings such as hexahydrocyclopenta[c]pyrrol-2(1H)-yl ring, or 5,6-membered bicyclic rings such as hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl ring. The ring containing a nitrogen atom may be partially unsaturated, i.e. it may contain one, two or more double bonds, for example but not limited to 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl or 4H-[1,4]thiazinyl, or it may be benzo-fused, for example but not limited to dihydroisoquinolinyl, 1,3-benzoxazolyl, 1,3-benzodioxolyl. According to the present invention, the heterocyclic group is non-aromatic.

[0075] The term "C 6-20 aryl" should be understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 aryl". The term "C 6-14 aryl" should preferably be understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms ("C 6-14 aryl"), in particular a ring having 6 carbon atoms ("C6 aryl") such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C9 aryl") such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl") such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl") such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl") such as anthracenyl. When the C 6-20When the aryl is substituted, it can be mono-substituted or multi-substituted. Moreover, there is no restriction on the substitution site, for example, it can be ortho-substituted, para-substituted or meta-substituted.

[0076] The term "5-20 membered heteroaryl" should be understood to include a monovalent monocyclic, bicyclic or tricyclic aromatic ring system having 5 to 20 ring atoms and containing 1-5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" should be understood to include a monovalent monocyclic, bicyclic or tricyclic aromatic ring system having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, especially 5 or 6 or 9 or 10 carbon atoms, and containing 1-5, preferably 1-3 heteroatoms independently selected from N, O and S and, additionally, may be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, etc. and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzoisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and their benzo derivatives, such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or azocinyl, indolizinyl, purinyl, etc. and their benzo derivatives; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc.

[0077] The above definition of the term "C 1-15 alkyl" also applies to other groups containing C 1-15 alkyl, such as -C 1-15 alkyl-C 6-20 aryl, -C 1-15 alkyl-5-20 membered heteroaryl, -C 1-15 alkyl-CO-C 6-20 aryl, -C 1-15 alkyl-CO-5-20 membered heteroaryl, -C 1-15 alkyl-CO-C 1-15 alkyl, -C 1-15 alkyl-CO-C 3-20 cycloalkyl, etc.

[0078] Similarly, C 6-20 aryl, 5-20 membered heteroaryl, C 3-20 cycloalkyl have the same definition throughout the text. BRIEF DESCRIPTION OF THE DRAWINGS

[0079] Figure 1 This is the thermogravimetric curve of compound I-1 in Example 1 of the present invention.

[0080] Figure 2 This is the thermogravimetric curve of Compound I-2 in Example 2 of the present invention.

[0081] Figure 3 This is the atomic force microscope (AFM) image of the film of Compound I-1 in Example 1 of the present invention.

[0082] Figure 4 This is the scanning electron microscope (SEM) image of the electron beam lithography stripes (exposure period is 80 nm) of the negative photoresist film formed by the host material of Compound I-1 in Example 1 of the present invention.

[0083] Figure 5 This is the scanning electron microscope (SEM) image of the electron beam lithography stripes (exposure period is 60 nm) of the negative photoresist film formed by the host material of Compound I-1 in Example 1 of the present invention.

[0084] Figure 6 This is the scanning electron microscope (SEM) image of the electron beam lithography stripes (exposure period is 50 nm) of the negative photoresist film formed by the host material of Compound I-1 in Example 1 of the present invention.

[0085] Figure 7 This is the scanning electron microscope (SEM) image of the deep ultraviolet (254 nm) lithography stripes (exposure period is 6 μm) of the negative photoresist film formed by the host material of Compound II-1 of the present invention.

[0086] Figure 8 This is the scanning electron microscope (SEM) image of the extreme ultraviolet lithography stripes (exposure period is 50 nm) of the negative photoresist film formed by the host material of Compound I-1 of the present invention. Detailed Embodiments

[0087] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only illustrative of and explanatory of the present invention, and should not be construed as limiting the protection scope 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.

[0088] Unless otherwise specified, the raw materials and reagents used in the following embodiments are all commercially available products, or can be prepared by known methods.

[0089] Example 1

[0090] Prepare Compound V-1, and the synthesis route is as follows:

[0091]

[0092] Experimental procedure: In a 100 mL two-necked flask, 1,3-dibromoadamantane (1 g, 3.4 mmol, 1 eq), 1,3-dibromobenzene (2.41 g, 10.3 mmol, 3 eq) and 15 mL of dry 1,2-dichloroethane were added successively. The reaction system was stirred uniformly and placed in an ice-water bath. Under a nitrogen atmosphere, anhydrous aluminum trichloride (150 mg, 1.1 mmol, 0.33 eq) was ground finely and added to the reaction system in three portions, with an interval of 5 min each time. The reaction system was first reacted in an ice-water bath for 1 h, and then stirred vigorously for 20 min. The reaction solution was filtered to obtain a white solid, which was washed three times with water and petroleum ether to obtain the crude product. The crude product was precipitated three times in n-hexane to obtain 1.6 g of a white solid. 1 1H NMR (400 MHz, chloroform-d) δ 7.51 (2H, s), 7.42 (4H, s), 2.34 (2H, s), 1.90 (10H, m), 1.77 (2H, s); MS (EI): m / z = 603.83, calculated for C 22 H 19 Br4 + m / z = 603.83 ([M] + ).

[0093] Compound IV-1 was prepared, and the synthetic route was as follows:

[0094]

[0095] Experimental procedure:

[0096] Compound V-1 (2.5 g, 4.13 mmol, 1.0 eq), 3-(hydroxymethyl)phenylboronic acid (3.77 g, 24.83 mmol, 6.0 eq) and 20 mL of 1,4-dioxane were added to a 250 ml Schlenk reaction flask. When the temperature was raised to 60 °C, it could not be completely dissolved. Anhydrous potassium carbonate (4.09 g, 24.83 mmol, 6.0 eq) was dissolved in 5 ml of deionized water and then added to the reaction flask. The vacuum was evacuated and filled with nitrogen three times repeatedly. Under nitrogen protection, the catalyst tetrakis(triphenylphosphine)palladium (143 mg, 0.207 mmol, 0.06 eq) was added, and the temperature was slowly raised to the reflux temperature (set temperature 100 °C). After 1 hour, the reaction solution was light yellow and transparent. After 12 hours, heating and stirring were stopped, and after cooling to room temperature, most of the solvent was removed by distillation under reduced pressure. The crude product was extracted with ethyl acetate / water, and the organic phase was washed twice with water and once with saturated brine, and the organic phases were combined. Dried over anhydrous magnesium sulfate, filtered by suction, and the filtrate was distilled under reduced pressure to obtain a yellow foamy solid, which was dissolved in a small amount of ethyl acetate. After separation and purification by column chromatography (eluent ethyl acetate: petroleum ether = 2:1), 2.22 g of a white foamy solid was obtained. 11H NMR (600 MHz, chloroform-d) δ 7.64 (10H, m), 7.58 (4H, dt, J 7.7, 1.5), 7.45 (4H, t, J 7.6), 7.36 (4H, m), 4.78 (8H, s), 2.42 (2H, m), 2.27 (2H, s), 2.12 (8H, m), 1.88 (2H, d, J 3.3). MS (ESI): m / z = 735.36, calcd for C 50 H 48 O4Na + m / z = 735.35 ([M+Na] + ).

[0097] Compound I-1 was prepared as follows:

[0098]

[0099] Experimental procedure:

[0100] Compound IV-1 (1 g, 1.40 mmol, 1.0 eq), N,N-dimethylformamide (0.102 g, 1.40 mmol, 1.0 eq) and 10 mL of dichloromethane were added to a 100 mL single-necked round-bottom flask. Thionyl chloride (1.33 g, 11.22 mmol, 8.0 eq) was dissolved in 2 mL of dichloromethane and added dropwise to the reaction flask under an ice bath (within 5 minutes). The reaction mixture was white and turbid, and the reaction was slowly warmed to room temperature. After 1 hour, the reaction mixture became colorless and transparent. After 10 hours, stirring was stopped and the solvent was removed under reduced pressure. The crude product was extracted with dichloromethane / saturated brine, and the organic phases were combined and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, filtered by suction, and the solvent was removed from the filtrate under reduced pressure to obtain the crude product. The crude product was separated and purified by column chromatography (DCM:PE = 1:2) to give 0.95 g of a white foamy solid. 1 1H NMR (600 MHz, chloroform-d) δ 7.61 (14H, m), 7.43 (8H, m), 4.67 (8H, s), 2.44 (2H, m), 2.24 (2H, s), 2.14 (8H, m), 1.88 (2H, s). MS (MALDI): m / z = 786.70, calcd for C 50 H 44 Cl4 m / z = 786.70 [M] + .

[0101] Example 2

[0102] Compound IV-2 was prepared as follows:

[0103]

[0104] The specific steps are the same as those in the preparation process of IV-1 in Example 1, except that 3-(hydroxymethyl)phenylboronic acid is replaced by 4-(hydroxymethyl)phenylboronic acid, and the reaction yield is 76%. 1 H NMR(600MHz, chloroform-d) δ7.64(10H, m), 7.61(4H, d, J 1.6), 7.46(8H, m), 4.76(8H, s), 2.42(2H, s), 2.25(2H, s), 2.14(8H, m), 1.87(2H, s). MS(ESI): m / z=735.36, calculated value C 50 H 48 O4Na + m / z=735.35([M+Na] + )。

[0105] To prepare Compound I-2, the synthetic route is as follows:

[0106]

[0107] The specific steps are the same as those in the preparation process of I-1 in Example 1, and the reaction yield is 85%. 1 H NMR(600MHz, chloroform-d) δ7.62(14H, m), 7.48(8H, m), 4.65(8H, s), 2.43(2H, p, J 3.1), 2.23(2H, s), 2.12(8H, m), 1.87(2H, d, J 3.2). MS(MALDI): m / z=786.70, calculated value C 50 H 44 Cl4 m / z=786.70[M] + 。

[0108] Example 3

[0109] To prepare Compound V-2, the synthetic route is as follows:

[0110]

[0111] Experimental procedure: In a 250 mL three-necked reaction flask, one end is connected to a nitrogen gas source, and the other end is connected to a tail gas absorption device. Add 1,3-dibromoadamantane (8.89 g, 30 mmol, 1.0 eq), 2,6-dibromophenol (19 g, 75 mmol, 2.5 eq) and 30 mL of dry 1,2-dichloroethane. Place the reaction in an ice bath and purge with nitrogen. Under a nitrogen atmosphere, add the catalyst aluminum trichloride (1.32 g, 9.9 mmol, 0.33 eq). React the reaction solution in an ice bath for 5 h. After the reaction is completed, the system is a brick-red turbid solution. Quench the reaction with 2 M hydrochloric acid solution, and filter to obtain the crude product. Extract the crude product with dichloromethane / water, combine the organic phases, dry over anhydrous magnesium sulfate, distill off the solvent under reduced pressure, add petroleum ether and sonicate to dissolve the excess phenol, and dry to obtain a white solid with a yield of 80%. 1 HNMR (400 MHz, chloroform-d) δ 7.42 (4H, s), 5.75 (2H, s), 2.32 (2H, s), 2.17 (2H, s), 2.04 (8H, q, J 11.6, 10.9), 1.83 (2H, s); MS (ESI): m / z = 636.02, calculated for C 22 H 20 Br4O2 + m / z = 636.02 ([M] + )。

[0112] To prepare compound V-3, the synthetic route is as follows:

[0113]

[0114] Experimental procedure: Add compound V-2 (8 g, 12.6 mmol, 1.0 eq) and 80 mL of the solvent acetone to a 250 mL Schlenk flask. Stir and heat to 60 °C until completely dissolved, then add potassium carbonate (6.95 g, 50.3 mmol, 4.0 eq). Add methyl iodide (8.47 g, 50.3 mmol, 4.0 eq) dropwise into the reaction flask using a syringe. After dropping, react at 60 °C for 22 h. Stop heating, distill off the solvent under reduced pressure, and extract with dichloromethane / water. Combine the organic phases, dry over anhydrous magnesium sulfate, and distill off most of the solvent under reduced pressure. Add approximately 20 mL of methanol to the crude product, sonicate to precipitate a white solid, and distill under reduced pressure to obtain a white solid with a yield of 93%. 1 HNMR (400 MHz, chloroform-d) δ 7.41 (4H, s), 3.87 (6H, s), 2.34 (2H, s), 2.17 (2H, s), 2.04 (8H, q, J 11.6, 10.9), 1.83 (2H, s). MS (ESI): m / z = 663.85, calculated for C 24 H 24 Br4O2+ m / z = 663.85 ([M] + )。

[0115] Compound IV-3 was prepared as follows:

[0116]

[0117] The specific steps were the same as those for the preparation of IV-1 in Example 1, except that compound V-1 was replaced by compound V-3, and the reaction yield was 73%. 1 H NMR (600 MHz, chloroform-d) δ 7.66 (10H, m), 7.59 (4H, dt, J 7.7, 1.5), 7.47 (4H, t, J 7.6), 7.36 (4H, m), 4.88 (8H, s), 3.87 (6H, s), 2.42 (2H, m), 2.27 (2H, s), 2.12 (8H, m), 1.87 (2H, d, J 3.3). MS (ESI): m / z = 795.97, calculated for C 52 H 52 O6Na + m / z = 795.97 ([M+Na] + )。

[0118] Compound I-3 was prepared as follows:

[0119]

[0120] The specific steps were the same as those for the preparation of I-1 in Example 1, except that compound IV-1 was replaced by compound IV-3, and the reaction yield was 85%. 1 H NMR (600 MHz, chloroform-d) δ 7.66 (10H, m), 7.59 (4H, dt, J 7.7, 1.5), 7.47 (4H, t, J 7.6), 7.36 (4H, m), 4.88 (8H, s), 3.86 (6H, s), 2.42 (2H, m), 2.27 (2H, s), 2.12 (8H, m), 1.87 (2H, d, J 3.3). MS (MALDI): m / z = 846.75, calculated for C 52 H 48 O2Cl4 + m / z = 846.75 [M] + 。

[0121] Example 4

[0122] Compound IV-4 was prepared as follows:

[0123]

[0124] The specific steps are the same as the preparation process of IV-1 in Example 1, except that compound V-1 is replaced by compound V-3, and 3-(hydroxymethyl)phenylboronic acid is replaced by 4-(hydroxymethyl)phenylboronic acid, and the reaction yield is 79%. 1 H NMR(600MHz, chloroform-d) δ7.64(10H, m), 7.61(4H, d, J 1.6), 7.46(8H, m), 4.76(8H, s), 3.90(6H, s), 2.42(2H, s), 2.25(2H, s), 2.14(8H, m), 1.87(2H, s). MS(ESI): m / z = 795.97, calculated value C 52 H 52 O6Na + m / z = 795.97([M+Na] + )

[0125] Prepare compound I-4, and the synthesis route is as follows:

[0126]

[0127] The specific steps are the same as the preparation process of I-1 in Example 1, except that compound IV-1 is replaced by compound IV-4, and the reaction yield is 88%. 1 H NMR(600MHz, chloroform-d) δ7.65(10H, m), 7.60(4H, d, J 1.6), 7.43(8H, m), 4.90(8H, s), 3.91(6H, s), 2.42(2H, s), 2.22(2H, s), 2.14(8H, m), 1.87(2H, s). MS(MALDI): m / z = 846.75, calculated value C 52 H 48 O2Cl4 + m / z = 846.75[M] + 。

[0128] Example 5

[0129] Prepare compound V-4, and the synthesis route is as follows:

[0130]

[0131] Experimental procedure: The specific steps are the same as the preparation process of V-1 in Example 1, except that 1,3-dibromoadamantane is replaced by 1,3,5-tribromoadamantane, and the yield is 79%. 11H NMR (600 MHz, chloroform-d) δ 9.71 (s, 3H), 7.62 (s, 6H), 2.40 (s, 1H), 2.03 (d, J = 11.8 Hz, 3H), 1.83 (m, 9H). MS (EI): m / z = 837.68, calcd for C 28 H 22 Br6 + m / z = 837.68 ([M] + )。

[0132] To prepare compound IV-5, the synthetic route is as follows:

[0133]

[0134] The specific steps are the same as those for the preparation of IV-1 in Example 1, except that compound V-1 is replaced by compound V-4, and the reaction yield is 65%. 1 1H NMR (600 MHz, chloroform-d) δ 7.69 (9H, dt, J 12.4, 1.4), 7.55 (6H, dt, J 7.5, 1.5), 7.47 (12H, m), 7.36 (6H, m), 4.79 (12H, s), 2.40 (s, 1H), 2.03 (d, J = 11.8 Hz, 3H), 1.83 (m, 9H). MS (ESI): m / z = 1023.46, calcd for C 70 H 64 O6 Na + m / z = 1023.46 ([M+Na] + )。

[0135] To prepare compound II-1, the synthetic route is as follows:

[0136]

[0137] The specific steps are the same as those for the preparation of I-1 in Example 1, except that compound IV-1 is replaced by compound IV-5, and the reaction yield is 85%. 1 1H NMR (600 MHz, chloroform-d) δ 7.69 (9H, dt, J 12.4, 1.4), 7.55 (6H, dt, J 7.5, 1.5), 7.47 (12H, m), 7.36 (6H, m), 4.90 (12H, s), 2.40 (s, 1H), 2.03 (d, J = 11.8 Hz, 3H), 1.83 (m, 9H). MS (MALDI): m / z = 1110.26, calcd for C 70 H 58 Cl6 + m / z = 1110.26 ([M] +)。

[0138] Example 6

[0139] To prepare compound IV-6, the synthetic route is as follows:

[0140]

[0141] The specific steps are the same as those in the preparation process of I-1 in Example 1, except that compound V-1 is replaced by compound V-4, and 3-(hydroxymethyl)phenylboronic acid is replaced by 4-(hydroxymethyl)phenylboronic acid, and the reaction yield is 79%. 1 H NMR(600MHz, chloroform-d)δ8.00(3H, s),δ7.83(6H, s), 7.42(24H, m), 4.81(12H, s), 2.40(s, 1H), 2.03(d, J = 11.3Hz, 3H), 1.73(m, 9H). MS(ESI): m / z = 1023.46, calculated value C 70 H 64 O6Na + m / z = 1023.46([M+Na] + )。

[0142] To prepare compound II-2, the synthetic route is as follows:

[0143]

[0144] The specific steps are the same as those in the preparation process of I-1 in Example 1, except that compound IV-1 is replaced by compound IV-6, and the reaction yield is 80%. 1 H NMR(600MHz, chloroform-d)δ8.05(3H, s),δ7.83(6H, s), 7.42(24H, m), 4.93(12H, s), 2.35(s, 1H), 2.03(d, J = 11.3Hz, 3H), 1.78(m, 9H). MS(MALDI): m / z = 1110.26, calculated value C 70 H 58 Cl6 + m / z = 1110.26([M] + )。

[0145] Example 7

[0146] To prepare compound V-5, the synthetic route is as follows:

[0147]

[0148] Experimental procedure: The specific procedure is the same as the preparation process of V-1 in Example 1, except that compound 1,3-dibromoadamantane is replaced by compound 1,3,5,7-tetrabromoadamantane, and the yield is 76%. 1 H NMR (600 MHz, deuterochloroform) δ 8.31 (4H, s), 7.62 (8H, s), 2.03 (12H, s). MS (EI): m / z = 1071.53, calculated for C 34 H 24 Br8 + m / z = 1071.53 ([M] + ).

[0149] To prepare compound IV-7, the synthetic route is as follows:

[0150]

[0151] The specific procedure is the same as the preparation process of IV-1 in Example 1, except that compound V-1 is replaced by compound V-5, and the reaction yield is 69%. 1 H NMR (600 MHz, deuterochloroform) δ 8.01 (4H, s), 7.90 (8H, s), 7.62 (8H, s), 7.50 (24H, m), 4.62 (16H, s), 2.03 (12H, s). MS (ESI): m / z = 1311.58, calculated for C 90 H 80 O8Na + m / z = 1311.58 ([M+Na] + ).

[0152] To prepare compound III-1, the synthetic route is as follows:

[0153]

[0154] The specific procedure is the same as the preparation process of I-1 in Example 1, except that compound IV-1 is replaced by compound IV-7, and the reaction yield is 83%. 1 H NMR (600 MHz, deuterochloroform) δ 8.00 (4H, s), 7.90 (8H, s), 7.60 (8H, s), 7.40 (24H, m), 4.82 (16H, s), 2.01 (12H, s). MS (MALDI): m / z = 1436.31, calculated for C 90 H 72 Cl8 + m / z = 1436.31 ([M] + ).

[0155] Example 8

[0156] To prepare Compound IV-8, the synthetic route is as follows:

[0157]

[0158] The specific steps are the same as those for the preparation of IV-1 in Example 1, except that Compound V-1 is replaced by Compound V-5, and 3-(hydroxymethyl)phenylboronic acid is replaced by 4-(hydroxymethyl)phenylboronic acid, and the reaction yield is 70%. 1 H NMR (600 MHz, chloroform-d) δ 8.01 (4H, s), 7.68 (8H, s), 7.50 (32H, m), 4.66 (16H, s), 2.02 (12H, s). MS (ESI): m / z = 1311.58, calculated for C 90 H 80 O8Na + m / z = 1311.58 ([M+Na] + )。

[0159] To prepare Compound III-2, the synthetic route is as follows:

[0160]

[0161] The specific steps are the same as those for the preparation of I-1 in Example 1, except that Compound IV-1 is replaced by Compound IV-8, and the reaction yield is 83%. 1 H NMR (600 MHz, chloroform-d) δ 7.91 (4H, s), 7.70 (8H, s), 7.52 (32H, m), 4.70 (16H, s), 2.04 (12H, s). MS (MALDI): m / z = 1436.31, calculated for C 90 H 72 Cl8 + m / z = 1436.31 ([M] + )。

[0162] Example 9

[0163] Determine the thermal stability of Compounds I-1 and I-2 prepared in Example 1 and Example 2. The thermogravimetric analysis curve of Compound I-1 in Example 1 is shown in Figure 1 , and the thermogravimetric analysis curve of Compound I-2 in Example 2 is shown in Figure 2 . The results show that the thermal decomposition temperatures of both compounds are above 110 °C, indicating good thermal stability.

[0164] Example 10

[0165] Compound I-1 in Example 1 was dissolved in propylene glycol methyl ether acetate to prepare a solution with a concentration of 30 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. A film was formed by spin coating on a silicon substrate, and the film uniformity was analyzed using an atomic force microscope (AFM). The test results are shown in the appendix Figure 3 , and it can be seen from Figure 3 that the obtained film is very uniform.

[0166] Example 11

[0167] A negative photoresist formulation and lithography: Compound I-1 in Example 1 was dissolved in propylene glycol methyl ether acetate to prepare a solution with a mass concentration of 20 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. A film was formed by spin coating on a silicon substrate and pre-baked at 80 °C for 2 minutes. The film thickness was measured using an ellipsometer. The prepared film was exposed using an electron beam light source from the National Center for Nanoscience and Technology. The exposure periods were 80 nm, 60 nm, and 50 nm, and very uniform lithography stripes could be obtained. The test results are shown in Figure 4 , Figure 5 and Figure 6 . Among them, Figure 4 is the lithography pattern with a photoresist exposure period of P80, and the stripe width is 36 nm. Figure 5 is the lithography pattern with a photoresist exposure period of P60, and the stripe width is 28 nm. Figure 6 is the lithography pattern with a photoresist exposure period of P50, and the stripe width is 25 nm. The results show that the obtained patterns have good resolution, contrast, and very low line edge roughness.

[0168] Example 12

[0169] A negative photoresist formulation and lithography: Compound II-1 was dissolved in acetonitrile to prepare a solution with a mass concentration of 25 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. A film was formed by spin coating on an untreated silicon substrate and pre-baked at 80 °C for 2 minutes. The film thickness was measured using an ellipsometer. The prepared film was exposed using a 254 nm mercury lamp light source, and very uniform lithography stripes could be obtained. The test results are shown in Figure 7 . Among them, Figure 7 is the lithography pattern with a photoresist exposure period of 6 μm, and the width of the lithography stripes is about 3 μm. The results show that the obtained patterns have good resolution, contrast, and very low line edge roughness.

[0170] Example 13

[0171] Negative Photoresist Formulation and Lithography: Dissolve Compound I-1 in acetonitrile to prepare a solution with a mass concentration of 10 mg / ml. Filter it through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. Spin-coat and form a film on an untreated silicon substrate, pre-bake it at 80 °C for 2 minutes, and measure the film thickness using an ellipsometer. Perform EUV exposure experiments on the prepared thin film at the Swiss Light Source (SLS) Paul Scherrer Institute (PSI), and very uniform lithography stripes can be obtained. The test results are shown in Figure 8 . Among them Figure 8 is the lithography pattern with a photoresist exposure period of 50 nm, and the width of the lithography stripes is about 25 nm. The results show that the obtained pattern has good resolution, contrast, and very low line-edge roughness at the same time.

[0172] Above, the embodiments of the present invention have been described. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. Compounds represented by formula (I), formula (II) or formula (III): Among them, R in formula (I) 1a ~R 20a ; R in formula (II) 1b ~R 30b ; R in formula (III) 1c ~R 40c are the same or different and each independently selected from the group consisting of group Z, -CH2Cl, -O-C 1-15 alkyl-C 6-20 aryl-CH2Cl; said group Z is H, an unsubstituted or optionally substituted by one, two or more R S substituted following groups: C 1-15 alkyl, C 1-15 alkoxy, C 3-20 cycloalkyl, C 6-20 aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclic group, -C 1-15 alkyl-C 6-20 aryl, -C 1-15 alkyl-5-20 membered heteroaryl, -C 1-15 alkyl-CO-C 6-20 aryl, -C 1-15 alkyl-CO-5-20 membered heteroaryl, -C 1-15 alkyl-CO-C 1-15 alkyl or -C 1-15 alkyl-CO-C 3-20 cycloalkyl; Provided that: R 1a ~R 20a at least one of the groups is -CH2Cl; R 1b ~R 30b at least one of the groups is -CH2Cl; R 1c ~R 40c at least one of the groups is -CH2Cl; R is selected from -CH2Cl, -O-C 1-15 alkyl-C 6-20 aryl-CH2Cl or group Z as described above; R S Selected from =O, NO2, C 1-15 alkyl, C 1-15 alkoxy, C 3-20 cycloalkyl, C 6-20 aryl or 5-20 membered heteroaryl.

2. The compound according to claim 1, wherein The compound of formula (I) has 4, 5 or 6 -CH2Cl; Alternatively, the compound of formula (II) has 6, 7, 8 or 9 -CH2Cl; Alternatively, the compound of formula (III) has 8, 9, 10, 11 or 12 -CH2Cl; Preferably, R 1a -R 20a has 4 -CH2Cl, and each phenyl group has 1 -CH2Cl; Alternatively, R 1b -R 30b has six -CH2Cl in it and one -CH2Cl on each phenyl group; Alternatively, R 1c -R 40c has eight -CH2Cl in it and one -CH2Cl on each phenyl group.

3. The compound according to claim 1, wherein The -CH2Cl is located at the ortho, meta or para position of the benzene ring it substitutes; 4. The compound according to claim 1, wherein The compound represented by formula (I) has a symmetric structure, that is, the structures on the 4 peripheral benzene rings are exactly the same; Alternatively, the compound represented by formula (II) has a symmetric structure, that is, the structures on the 6 peripheral benzene rings are exactly the same; Alternatively, the compound represented by formula (III) has a symmetric structure, that is, the structures on the 8 peripheral benzene rings are exactly the same; 5. The compound according to claim 1, characterized in that, The compound represented by formula (I) has the following structure: Alternatively, the compound represented by formula (II) has the following structure: Alternatively, the compound represented by formula (III) has the following structure:

6. A process for preparing the compound represented by formula (I), formula (II) or formula (III) according to any one of claims 1-5, characterized in that, Including: Mixing compound (V') with thionyl chloride and reacting under the catalysis of N,N-dimethylformamide to obtain the compound represented by formula (I); Alternatively, mixing compound (V”) with thionyl chloride and reacting under the catalysis of N,N-dimethylformamide to obtain the compound represented by formula (II); Alternatively, mixing compound (V''') with thionyl chloride and reacting under the catalysis of N,N-dimethylformamide to obtain the compound represented by formula (III); Wherein, R 1a ’ ~R 20a ’ 、R 1b ’ ~R 30b ’ 、R 1c ’ ~R 40c ’ are the same or different and each independently selected from -CH2OH, -O-C 1-15 alkyl-C 6-20 aryl-CH2OH or group Z; said group Z, R, R 1a ~R 20a 、R 1b ~R 30b 、R 1c ~R 40c have the definition as described in any one of claims 1-6; Provided that: R 1a ’ ~R 20a ’ at least one of the groups is -CH2OH; R 1b ’ ~R 30b ’ at least one of the groups is -CH2OH; R 1c ’ ~R 40c ’ At least one of the groups is -CH2OH.

7. Use of the compound represented by formula (I), formula (II) or formula (III) according to any one of claims 1 - 6 for preparing a photoresist.

8. A photoresist composition comprising one or more of the compounds represented by formula (I), formula (II) or formula (III); Preferably, the photoresist composition further comprises a photoresist solvent, and the photoresist solvent is selected from one, two or more of the following substances: propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), N,N-dimethylformamide (DMF), cyclohexanone, ethyl n-pentanone, ethyl isopentanone, ethanol, acetonitrile, isopropanol, acetone, methyl n-pentanone, methyl isopentanone; Preferably, the photoresist is composed of the compound represented by formula (I) and / or (II) and / or (III) and a photoresist solvent.

9. A photoresist coating, which comprises one or more of the compounds represented by formula (I), formula (II) or formula (III) according to any one of claims 1 - 6.

10. Application of the compound according to any one of claims 1 - 5, the photoresist composition according to claim 8 or the photoresist coating according to claim 9 in lithography; Preferably, the lithography is 365nm lithography, 254nm lithography, 248nm lithography, 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography or electron beam lithography.

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