UV absorbing compound and photoresist composition containing the same

Abstract

The present invention provides a UV absorbing compound and a photoresist composition containing the same. The UV absorbing compound of the photoresist of the present invention can significantly reduce or even eliminate unwanted reflections of exposure radiation, especially deep ultraviolet light, such as 248nm. Such UV absorbing compounds are applied to photoresist compositions, which can not only improve the standing wave effect, but also significantly improve CDU and reduce the risk of development residues. The UV absorbing compound can reduce reflections from the substrate during exposure, so that the photoresist has a larger photolithography process window and better DOF performance, thereby providing higher resolution images.

Description

Technical Field

[0001] The invention relates to the technical field of semiconductor materials, in particular to a photoresist composition, and is particularly suitable for deep ultraviolet photoresists. Background Art

[0002] To form even smaller logic and memory transistors, advanced lithography techniques are constantly being developed, such as 193nm immersion lithography to achieve high quality and smaller feature sizes in microlithography processes. In addition to other process and exposure tool related requirements, further reducing the pattern size requires the development of high-resolution, chemically amplified photoresist compositions. It has been proven that an important feature of photoresists is resolution, and semiconductor devices with critical dimensions of 0.3μm-0.13μm are usually processed by KrF excimer lasers with a wavelength of 248nm. In order to accurately transfer the designed circuit pattern to the substrate below, the smaller the line size, the more vertical or substantially vertical sidewalls are required in the process. However, many current photoresists cannot provide such high-resolution line patterns.

[0003] For example, reflections off the substrate of incident light used to expose the photoresist often limit the resolution of the image patterned in the photoresist layer. Radiation reflected from the substrate / photoresist interface can produce radiation intensity variations in the photoresist during exposure, resulting in non-uniform photoresist line widths during development, such as the typical standing wave effect. Bottom reflections can also scatter from the substrate / photoresist interface to areas of the photoresist that are not intended to be exposed, again resulting in line width variations. The scattered and reflected light often varies from area to area, resulting in further line width non-uniformities.

[0004] Changes in substrate morphology can also cause reflection problems that limit resolution. Any image on the substrate will cause the incident light to scatter or reflect in various uncontrolled directions, which in turn affects the uniformity of photoresist exposure and development. As semiconductor processes improve, circuit complexity continues to increase, and substrate morphology becomes more complex. How to reduce the impact of reflected light becomes increasingly critical for advanced lithography technology. For example, the metal interconnect structures used on many microelectronic substrates have added many process challenges to previous photoresists due to their morphology and high reflectivity areas.

[0005] With the recent trend toward high-density semiconductor devices, the industry is taking action to shorten the wavelength of deep ultraviolet (DUV) light (wavelength of 300nm or shorter) from the exposure source, including excimer lasers (about 248nm) and ArF excimer lasers (193nm). Imaging the photoresist coating using light with a shortened wavelength results in greater penetration of the photoresist layer and increased exposure energy reflected back to the photoresist layer. Therefore, the use of shorter wavelengths exacerbates the reflection problem on the substrate surface. The current solution is to add naphthalene and anthracene compounds to the photoresist to enhance the characteristic absorption intensity of the film at 248nm, but the commonly used compounds of this type have the disadvantage of being easy to sublimate, and there is a risk of contaminating the machine and causing process fluctuations. In addition, the solubility of such compounds in photoresist solvents is generally poor, which is not conducive to the uniform distribution of the formulation components.

[0006] Therefore, it is hoped to design a new photoresist composition that can provide high-resolution fine line images. It is also hoped to have such a new photoresist composition that can be used for deep ultraviolet light imaging and has the ability to reduce reflected light from the substrate to adapt to the increasingly complex substrate materials and structures. Summary of the invention

[0007] In order to solve the problems existing in the prior art, the present invention provides a new photoresist composition, which has the advantages of improving CDU and reducing the risk of development residues.

[0008] The first aspect of the present invention provides a UV absorbing compound having strong absorption at an applicable wavelength:

[0009] A UV absorbing compound, characterized in that it has a structure represented by the following general formula:

[0010]

[0011] wherein Ar is selected from the reaction residue of monohydric phenol, dihydric phenol, trihydric phenol or tetrahydric phenol, and the carbon number of Ar is 10-40; R D1 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an acyl group having 1 to 16 carbon atoms, an integer of 1 to 5, and m is an integer of 1 to 4;

[0012] Furthermore,

[0013] The Ar is preferably a reaction residue of a monohydric phenol or a dihydric phenol;

[0014] And / or, the number of carbon atoms of Ar is preferably 10-30; more preferably 10-16;

[0015] and / or, the R D1Preferably, it is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an acyl group having 5 to 16 carbon atoms; further, R D1 Preferably, it is an alkyl group having 1 to 4 carbon atoms or an acyl group having 5 to 16 carbon atoms;

[0016] and / or, n is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1;

[0017] and / or, m is preferably an integer of 1 to 2;

[0018] Furthermore,

[0019] The Ar is selected from at least one of bisphenol compounds, anthracenol, anthracenediol, naphthol, naphthalenediol, anthracene, pyrenephenol, pyrenediol, and biphenol; the bisphenol compounds include bisphenol A, bisphenol B, bisphenol AP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, bisphenol Z, bisphenol AF, etc.;

[0020] and / or, the R D1 At least one selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzoyl, naphthoyl, anthracoyl;

[0021] Further, the UV absorbing compound is selected from at least one of the following structures:

[0022]

[0023] The second aspect of the present invention provides a method for preparing the above-mentioned UV absorbing compound;

[0024] In the presence of an acid, a phenol compound is reacted with a vinyl ether compound to obtain the UV absorbing compound; further,

[0025] The vinyl ether compound is selected from at least one of the following structures:

[0026]

[0027] And / or, the acid is selected from at least one of p-toluenesulfonic acid, trifluoroacetic acid, phosphoric acid, and p-trifluoromethylbenzenesulfonic acid;

[0028] And / or, the phenolic compound is a phenolic compound containing an Ar structure;

[0029] Furthermore, the preparation method of the UV absorbing compound is specifically as follows: add phenolic compounds, p-toluenesulfonic acid, and PGMEA to a reaction container, control the solid content of the reaction liquid to 10%, control the reaction temperature to 70°C, and perform reduced pressure concentration, and finally measure the water content of the reaction liquid to be less than 300ppm and the solid content to be 30%. Replace the reaction with a nitrogen atmosphere, slowly add a PGMEA solution of a vinyl ether compound at a uniform speed, and control the reaction temperature to 60°C. After the addition is completed, the reaction continues; after the reaction is completed, the product is obtained by solvent replacement, filtration, washing, and other steps.

[0030] The third aspect of the present invention provides a photoresist composition comprising the above-mentioned UV absorbing compound:

[0031] A photoresist composition comprising the above-mentioned UV absorbing compound, a polymer resin, a photoacid generator, a quencher, a surfactant and a solvent;

[0032] Furthermore,

[0033] In the photoresist composition, the total solid content of the photoresist may be 0.5-50% by weight, preferably 1-45% by weight, further preferably 2-40% by weight, and more preferably 5-35% by weight, based on the total weight of the solid and the solvent; the solid includes the copolymer, the photoacid generator, the quencher, the surfactant, the additive, etc., but does not include the solvent;

[0034] And / or, in the photoresist composition, the content of the photoacid generator is 0.01-20 wt %, preferably 0.1-15 wt %, based on the total weight of the solid;

[0035] and / or, based on the total weight of the solid, the content of the polymer resin may be 50-99 wt %, preferably 55-95 wt %, further preferably 60-90 wt %, more preferably 65-90 wt %;

[0036] and / or, based on the total weight of the solid, the content of the surfactant may be 0.01-5% by weight, preferably 0.1-4% by weight, more preferably 0.2-3% by weight;

[0037] and / or, based on the total weight of the solid, the amount of the quencher is 0.03-5 wt %;

[0038] and / or, based on the total weight of the solid, the amount of the UV absorber is 0.03-5 wt %;

[0039] And / or, the photoresist composition may further include other additives, and the amount of the other additives included may be less than or equal to 30 weight %, preferably less than or equal to 20 weight %, and more preferably less than or equal to 10 weight %, based on the total weight of the solids.

[0040] Furthermore,

[0041] The polymer resin includes repeating unit A, repeating unit B, and repeating unit C.

[0042] Furthermore,

[0043] The repeating unit A is a repeating unit that can dissociate under the action of an acid, the repeating unit B is a repeating unit having a hydroxyl group or a carboxyl group in the side chain, and the repeating unit C is an acid-stable alkali-insoluble repeating unit;

[0044] And / or, in the photoresist composition, based on 100 mol % of the total repeating units in the polymer, the polymer comprises 5-35 mol % of the repeating unit A, preferably 10-30 mol % of the repeating unit A;

[0045] And / or, in the photoresist composition, based on 100 mol % of the total repeating units in the polymer, the polymer comprises 40-80 mol % of the repeating unit B, preferably 50-70 mol % of the repeating unit B;

[0046] And / or, in the photoresist composition, the polymer comprises 5-35 mol % of the repeating unit C, preferably 10-25 mol % of the repeating unit C, based on 100 mol % of the total repeating units in the polymer.

[0047] Furthermore,

[0048] In the repeating unit A, the carboxyl group, phenolic hydroxyl group, sulfonic acid group and other alkali-soluble groups are protected by acid-dissociable dissolution-inhibiting groups; the repeating unit A is preferably a repeating unit in which the carboxyl group, phenolic hydroxyl group, sulfonic acid group and the like in the repeating unit derived from (meth) acrylic acid or hydroxystyrene are protected by acid-dissociable dissolution-inhibiting groups;

[0049] The acid dissociative dissolution inhibiting group is selected from the structure represented by formula (a1) or (a2):

[0050]

[0051] In formula a1, * represents a bonding site of formula a1, R1 and R2 each independently represent a hydrocarbon group having 1 to 4 carbon atoms, R3 represents a hydrocarbon group having 1 to 12 carbon atoms, and R3 may be bonded to R1 or R2 to form a ring;

[0052] Preferably, R3 is selected from a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms;

[0053] More preferably, R1 and R2 are each independently selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl; R3 is selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclopentyl, cyclohexyl, norbornyl, tricyclo[5.2.1.02,6]decyl, adamantyl, tetracyclo[4.4.0.12,5.17,10]dodecyl, phenyl, and naphthyl;

[0054] Furthermore, the ring formed by R3 and R2 or R1 or R3 is preferably an alicyclic ring having 5 to 12 carbon atoms, more preferably a cyclopentane ring, a cyclohexane ring, a norbornane ring, a tricyclo[5.2.1.02,6]decane ring, an adamantane ring, or a tetra[4.4.0.12,5.17,10]dodecane ring;

[0055] In formula a2, * represents a bonding site of formula a2, R4 and R5 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R6 represents a hydrocarbon group having 1 to 12 carbon atoms, and R4 may be bonded to R5 or R6 to form a ring;

[0056] Preferably, R6 is selected from a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms;

[0057] More preferably, R4 and R5 are each independently selected from one of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl; R6 is selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, norbornyl, tricyclo[5.2.1.02,6]decyl, adamantyl, and tetracyclo[4.4.0.12,5.17,10]dodecyl;

[0058] Furthermore, the ring formed by bonding R4 and R6 is selected from a cyclopentane ring, a cyclohexane ring, a norbornane ring, a tricyclo[5.2.1.02,6]decane ring, an adamantane ring, and a tetracyclo[4.4.0.12,5.17,10]dodecane ring; the ring formed by bonding R4 and R5 is selected from a hydrogenated furan ring and a hydrogenated pyran ring.

[0059] The structure of the repeating unit B is preferably a structure represented by formula b1 to b3:

[0060]

[0061] In formula b1, R7 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, R8 is a substituted or unsubstituted aromatic hydrocarbon group. R9 represents a single bond, or a divalent hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, or a carbonyl group; a represents an integer of 1 or 2;

[0062] Furthermore,

[0063] R7 is preferably one of a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a trifluoromethyl group, more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group;

[0064] and / or, R9 is preferably a single bond, methylene, 1,1-ethylene, 2,2-propylene, 1,1,1,3,3,3-hexafluoro-2,2-propylene, 1,1,1-trifluoro-2-trifluoromethyl-2,3-propylene, etc., an alkylene group having 1 to 4 carbon atoms which may be substituted with a fluorine atom, more preferably a single bond, 1,1,1,3,3,3-hexafluoro-2,2-propylene, 1,1,1-trifluoro-2-trifluoromethyl-2,3-propylene, etc., and particularly preferably a single bond;

[0065] And / or, R8 is preferably phenyl, benzyl, naphthyl or anthracenyl.

[0066] In formula b2, R 10 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a fluorine atom; R 11 represents a divalent to tetravalent hydrocarbon group having 2 to 14 carbon atoms which may contain a fluorine atom, an oxygen atom or a sulfur atom; R 12 represents a single bond or a divalent hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a fluorine atom; and b represents an integer of 1 to 3.

[0067] Furthermore,

[0068] R 10 Preferably, it is a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a trifluoromethyl group; More preferably, it is a hydrogen atom, a methyl group or a trifluoromethyl group;

[0069] and / or, R 11 Preferably, it is a straight-chain or branched saturated hydrocarbon group having 2 to 4 carbon atoms, or a saturated alicyclic hydrocarbon group having 5 to 14 carbon atoms which may contain an oxygen atom or a sulfur atom; more preferably, it is one of an ethylene group, an isopropylene group, a cyclohexane ring, a norbornane ring, a 7-oxa-norbornane ring, a 7-thia-norbornane ring, an adamantane ring, and a tetracyclo[4.4.0.12,5.17,10]dodecane ring; more preferably, it is a cyclohexane ring, a norbornane ring, or an adamantane ring;

[0070] and / or, R 12Preferred are single bonds and alkylene groups having 1 to 4 carbon atoms which may be substituted with fluorine atoms. More preferred are single bonds, methylene groups, 1,1-ethylene groups, 2,2-propylene groups, 1,1,1,3,3,3-hexafluoro-2,2-propylene groups, and 1,1,1-trifluoro-2-trifluoromethyl-2,3-propylene groups; and more preferred are single bonds, 1,1,1,3,3,3-hexafluoro-2,2-propylene groups, and 1,1,1-trifluoro-2-trifluoromethyl-2,3-propylene groups.

[0071] R is particularly preferred 11 is adamantyl and R 12 A combination of single keys.

[0072] In formula b3, R 13 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a fluorine atom, R 14 represents a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms which may contain an oxygen atom or a sulfur atom, and c represents an integer of 0 or 1.

[0073] Furthermore, R 13 One selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a trifluoromethyl group, preferably a hydrogen atom, a methyl group, and a trifluoromethyl group;

[0074] and / or, R 14 It represents one of a norbornane ring, a 7-oxa-norbornane ring, a 7-thia-norbornane ring, and a tetracyclo[4.4.0.12,5.17,10]dodecane ring, and preferably a norbornane ring or a tetracyclo[4.4.0.12,5.17,10]dodecane ring.

[0075] The repeating unit C is preferably a repeating unit in which a carboxyl group or a phenolic hydroxyl group in a repeating unit derived from (meth)acrylic acid, hydroxystyrene or the like is protected with an acid-stable dissolution inhibitory group.

[0076] The acid-stable dissolution inhibition group is selected from a structure formed by replacing the hydrogen atoms of the carboxyl group and the phenolic hydroxyl group and the carbon atoms bonded to the oxygen atom are 1 to 2 carbon atoms of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a methyl group and a 1-adamantyl group. It is further preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a cyclopentyl group, a cyclohexyl group, a 2-norbornyl group, a 2-isobornyl group, an 8-tricyclo[5.2.1.02,6]decyl group, a 1-adamantyl group, a 2-adamantyl group, a 4-tetracyclo[4.4.0.12,5.17,10]dodecyl group, a phenyl group, a benzyl group, a naphthyl group, and an anthracenyl group.

[0077] Furthermore,

[0078] The repeating unit A is selected from at least one of the following structures:

[0079]

[0080]

[0081] And / or, the repeating unit B is selected from at least one of the following structures:

[0082]

[0083] And / or, the repeating unit C is selected from at least one of the following structures:

[0084]

[0085]

[0086] Further, the weight average molecular weight (Mw) of the polymer is 2000-100000 g / mol, preferably 7000-30000 g / mol, more preferably 12000-20000 g / mol;

[0087] and / or, the polydispersity index (PDI) is from 1.3 to 3, preferably from 1.3 to 2, more preferably from 1.4 to 2.

[0088] Furthermore,

[0089] The photoacid generator includes iodonium salts, sulfonium salts, oxime sulfonates, diazomethanes, nitrobenzyl sulfonates, iminosulfonates, disulfones, etc.; preferably triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-f-nitrobenzyl-p-toluenesulfonate, 2,4-g-nitrobenzyl-p-toluenesulfonate, At least one of toluenesulfonate, 1,2,3-tris(methylsulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, N-hydroxysuccinimide methanesulfonate, and N-hydroxysuccinimide trifluoromethanesulfonate;

[0090] and / or, the quencher comprises hydroxide, carboxylate / ester, amine, imine and amide, preferably tetrabutylammonium hydroxide (TBAH), tetrabutylammonium lactate, N-tert-butylcarbonyl-1,1-bis(hydroxymethyl)-2-hydroxyethylamine (TBOC-TRIS), diazabicycloundecene (DBU) or diazabicyclononene (DBN), One of

[0091] And / or, the solvent includes ethers, alcohols, esters, ketones, preferably anisole, ethyl lactate, methyl 2-hydroxybutyrate (HBM), 1-methoxy-2-propanol (also known as propylene glycol methyl ether, PGME), 1-ethoxy-2-propanol, n-butyl acetate, 1-methoxy-2-propyl acetate (also known as propylene glycol methyl ether acetate, PGMEA), methoxyethoxy propionate, ethoxyethoxy propionate and γ-butyrolactone, cyclohexanone, 2-heptanone, etc. One or a combination of several thereof;

[0092] and / or, the surfactant comprises a fluorinated surfactant and a non-fluorinated surfactant, preferably a nonionic surfactant, more preferably at least one of FC-4430, FC-4432, PF-636, PF-6320, PF-656 and PF-6520;

[0093] A fourth aspect of the present invention provides a photoresist film formed by curing the above-mentioned photoresist composition.

[0094] A fifth aspect of the present invention provides use of the above-mentioned photoresist composition in preparing a deep ultraviolet photoresist film.

[0095] Beneficial effects:

[0096] The UV absorbing compound of the photoresist of the present invention can significantly reduce or even eliminate the unwanted reflection of exposure radiation, especially deep ultraviolet light, such as 248nm. Such UV absorbing compounds are applied to photoresist compositions, which can not only improve the standing wave effect, but also significantly improve CDU and reduce the risk of development residues. The UV absorbing compound can reduce the reflection from the substrate during the exposure process, so that the photoresist has a larger lithography process window and better DOF performance, thereby providing higher resolution images.

[0097] The UV absorbing compound of the present invention is a reaction product of a polyphenol and a vinyl ether compound. This type of compound can not only act as a UV absorber, but also act as a dissolution inhibitor under a suitable structure, which is very helpful in eliminating the influence of reflected light from the substrate, and also increases the contrast of the photoresist and expands the process window. DETAILED DESCRIPTION

[0098] Hereinafter, the specific embodiments of the UV absorbing compound compounds, the photoresist compositions containing the same and the applications according to the present invention are described in detail, but the present invention is not limited to the embodiments including the following examples and can be modified in various ways within the scope of the gist of the invention so as to achieve the purpose of the invention.

[0099] In the following examples, unless otherwise specified, the raw materials, reagents or processing techniques used are all commercially available raw materials or conventional processing techniques commonly used in the art.

[0100] The embodiment of the present invention provides a UV absorbing compound represented by the following general formula D1:

[0101]

[0102] In formula D1, Ar is the reaction residue of polyphenol, that is, the part of the polyphenol structure that does not contain phenolic hydroxyl groups. According to the number of phenolic hydroxyl groups, the polyphenol can be a monophenol, a diphenol, a triphenol or a tetraphenol; in the present invention, Ar is the reaction residue of a monophenol, a diphenol, a triphenol or a tetraphenol, preferably a reaction residue of a monophenol or a diphenol; the carbon number of the polyphenol is 10-40, preferably 10-30, and more preferably 10-16. Specifically, Ar can include various bisphenol compounds, anthracene, anthracene diphenol, naphthol, naphthane diphenol, anthracene, pyrene phenol, pyrene diphenol, biphenol; among them, bisphenol compounds can include bisphenol A, bisphenol B, bisphenol AP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, bisphenol Z, bisphenol AF and other compounds.

[0103] In formula D1, R D1 It is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 16 carbon atoms, or an acyl group having 1 to 16 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an acyl group having 5 to 16 carbon atoms, and in the present invention, an alkyl group having 1 to 4 carbon atoms or an acyl group having 5 to 16 carbon atoms is more preferred. D1 When the structure contains an acyl group, it is generally a benzoyl group or a condensed ring acyl group such as naphthalene or anthracene, which enhances UV absorption; n is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and more preferably 1; m is an integer of 1 to 4, preferably m is an integer of 1 to 2. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, etc.; examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; examples of the acyl group include benzoyl, naphthoyl, anthracene, etc. It should be noted that the compound structure that absorbs light of a specific wavelength can be embodied in the polyphenol structure of Ar, and can also be embodied in R D1 In the structure, both can be reflected at the same time.

[0104] The embodiment of the present invention also provides a method for synthesizing the above-mentioned UV absorbing compound: reacting a phenolic compound with a vinyl ether compound in the presence of an acid, wherein the acid may be p-toluenesulfonic acid, trifluoroacetic acid, phosphoric acid, p-trifluoromethylbenzenesulfonic acid, etc.; the phenolic compound is a phenolic compound containing an Ar structure, such as bisphenol compounds, anthracene, anthracenediol, naphthol, naphthalenediol, anthracenediol, pyrenol, pyrenediol, biphenyldiol, etc.

[0105] Specific examples of the vinyl ether compounds described above are given below, but they do not limit the present invention.

[0106]

[0107] Specifically, the above-mentioned synthesis method is: add phenolic compounds and p-toluenesulfonic acid to a round-bottom flask equipped with a thermometer, add PGMEA, control the solid content of the reaction liquid to 10%, control the reaction temperature to 70°C, and perform reduced pressure concentration, and finally measure the water content of the reaction liquid to be less than 300ppm and the solid content to be 30%. Replace the reaction with a nitrogen atmosphere, slowly add the PGMEA solution of the vinyl ether compound at a uniform speed, and control the reaction temperature to 60°C. After the dropwise addition is completed, the reaction continues; after the reaction is completed, the product is obtained by solvent replacement, filtration, washing and other steps.

[0108] The present invention also provides a photoresist composition, comprising a common resin for general photoresists, a photoacid generator, a quencher, and the above-mentioned UV absorbing compound. The material can reduce reflection from the substrate during exposure, so that it has a larger photolithography process window and better DOF performance, thereby providing a higher resolution image.

[0109] UV absorbing materials should be used in combination with common photoresist resins such as specific acid-sensitive or alkali-soluble resins, or they can be directly connected to the molecular chain of acid-sensitive or alkali-soluble resins, and other basic components such as photoacid generators, quenchers, etc. can be added to form commercially usable photoresist products.

[0110] Acid-sensitive or alkali-soluble resins include acid-deprotectable monomers, alkali-soluble monomers, dissolution rate-modified monomers, and anti-corrosive monomers. Such monomers can be randomly matched to form copolymeric resins, or more than one copolymeric resin can be blended and used to form photoresist polymer resins suitable for 248nm photolithography. Preferably, the above-mentioned monomers include p-hydroxystyrene and its derivative compounds, (methyl) acrylic monomers, (methyl) acrylic monomers grafted with tert-butyl, cyclohexane, adamantane, and norbornene, (methyl) acrylate monomers with acid-sensitive functional groups, and (methyl) styrene monomers with hydrophobic inert groups, etc. Any recognized known monomers that can be used as photoresist should be within the scope described herein. The following are exemplary monomers, including but not limited to:

[0111] Repeating unit A

[0112] Repeating unit A is acid-sensitive and can be dissociated under the action of acid. In repeating unit A, alkali-soluble groups such as carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups are protected by acid-dissociable dissolution-inhibiting groups. Repeating unit A is preferably a repeating unit in which carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups in repeating units derived from (meth)acrylic acid or hydroxystyrene are protected by acid-dissociable dissolution-inhibiting groups; as acid-dissociable dissolution-inhibiting groups, structures represented by formula (a1) or (a2) can be cited.

[0113]

[0114] In formula a1, * represents a bonding site as formula a1, R1 and R2 each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and specifically, alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc. R3 represents a hydrocarbon group having 1 to 12 carbon atoms, and specifically, linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclopentyl, cyclohexyl, norbornyl, tricyclo[5.2.1.02,6]decyl, adamantyl, tetracyclo[4.4.0.12,5.17,10]dodecyl, and aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl can be mentioned.

[0115] It should be noted that R3 may be bonded to R1 or R2 to form a ring, specifically, an alicyclic ring having 5 to 12 carbon atoms such as a cyclopentane ring, cyclohexane ring, norbornane ring, tricyclo[5.2.1.02,6]decane ring, adamantane ring, tetra[4.4.0.12,5.17,10]dodecane ring, etc.

[0116] In particular, if R3, or R3 is bonded to R2 or R1 and contains a saturated alicyclic ring, specifically a cyclopentane ring, a cyclohexane ring, a norbornane ring, a tricyclo[5.2.1.02,6]decane ring, an adamantane ring, a tetracyclo[4.4.0.12,5.17,10]dodecane ring, etc., the difference in solubility in alkaline developer before and after deprotection is relatively large, which is preferred for photolithography patterns with smaller CDs.

[0117] In formula a2, * represents a bonding site of formula a2, and R4 and R5 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and specifically, hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and other alkyl groups having 1 to 4 carbon atoms can be mentioned. R6 represents a hydrocarbon group having 1 to 12 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, norbornyl, tricyclo[5.2.1.02,6]decyl, adamantyl, tetracyclo[4.4.0.12,5.17,10]dodecyl and other linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms can be mentioned. It should be noted that R4 may be bonded to R5 or R6 to form a ring. Specific examples of the ring formed by bonding R4 and R5 include a cyclopentane ring, a cyclohexane ring, a norbornane ring, a tricyclo[5.2.1.02,6]decane ring, an adamantane ring, a tetracyclo[4.4.0.12,5.17,10]dodecane ring, and the like. Specific examples of the ring formed by bonding R4 and R5 include a hydrogenated furan ring, a hydrogenated pyran ring, and the like.

[0118] Specific chemical structure examples of repeating unit A are listed below, and non-limiting examples of monomers having formula A include:

[0119]

[0120] Repeating unit B

[0121] Repeating unit B is a repeating unit having a hydroxyl group or a carboxyl group in the side chain, which can improve the adhesion between the photoresist film and the substrate, control the dissolution rate in an organic or alkaline developer solvent, and also form a cross-linked structure. As the structure of repeating unit B, the structure represented by formula b1 to b3 is particularly preferred:

[0122]

[0123] In formula b1, R7 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, and specifically, includes a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a trifluoromethyl group and an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. R8 is a substituted or unsubstituted aromatic hydrocarbon group. R9 represents a single bond, or a divalent hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a fluorine atom, or a carbonyl group. Specifically, examples thereof include a single bond, a methylene group, a 1,1-ethylene group, a 2,2-propylene group, a 1,1,1,3,3,3-hexafluoro-2,2-propylene group, a 1,1,1-trifluoro-2-trifluoromethyl-2,3-propylene group, and other alkylene groups having 1 to 4 carbon atoms which may be substituted with a fluorine atom. Preferably, it includes a single bond, a 1,1,1,3,3,3-hexafluoro-2,2-propylene group, a 1,1,1-trifluoro-2-trifluoromethyl-2,3-propylene group, and particularly preferably a single bond. a represents an integer of 1 or 2.

[0124]

[0125] In formula b2, R 10 R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a fluorine atom. Specifically, examples thereof include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a trifluoromethyl group and an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom. Preferably, the alkyl group is a hydrogen atom, a methyl group or a trifluoromethyl group. 11 R represents a divalent to tetravalent hydrocarbon group having 2 to 14 carbon atoms which may contain fluorine atoms, oxygen atoms or sulfur atoms, and specifically includes a linear or branched saturated hydrocarbon group having 2 to 4 carbon atoms such as ethylene and isopropylene; and a saturated alicyclic hydrocarbon group having 5 to 14 carbon atoms which may contain an oxygen atom or a sulfur atom, such as a cyclohexane ring, a norbornane ring, a 7-oxa-norbornane ring, a 7-thia-norbornane ring, an adamantane ring, a tetracyclo[4.4.0.12,5.17,10]dodecane ring, and preferably a cyclohexane ring, a norbornane ring, and an adamantane ring. 12 represents a single bond or a divalent hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. Specifically, examples include a single bond, a methylene group, a 1,1-ethylene group, a 2,2-propylene group, a 1,1,1,3,3,3-hexafluoro-2,2-propylene group, a 1,1,1-trifluoro-2-trifluoromethyl-2,3-propylene group and other alkylene groups having 1 to 4 carbon atoms which may be substituted with a fluorine atom. Preferably, a single bond, a 1,1,1,3,3,3-hexafluoro-2,2-propylene group, a 1,1,1-trifluoro-2-trifluoromethyl-2,3-propylene group are preferred. R is particularly preferred. 11 is adamantyl, and R 12 b represents an integer of 1 to 3.

[0126]

[0127] In formula b3, R 13 R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, and specifically includes a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a trifluoromethyl group and an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, preferably a hydrogen atom, a methyl group or a trifluoromethyl group. 14 represents a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms which may contain an oxygen atom or a sulfur atom, and specifically includes an alicyclic hydrocarbon group having a norbornane ring, a 7-oxa-norbornane ring, a 7-thia-norbornane ring, a tetracyclo[4.4.0.12,5.17,10]dodecane ring or the like which may contain an oxygen atom or a sulfur atom, and preferably a norbornane ring or a tetracyclo[4.4.0.12,5.17,10]dodecane ring. c represents an integer of 0 or 1.

[0128] Specific examples of the repeating unit B are given below, but the present invention is not limited thereto. One or more repeating units B may be selected and used.

[0129]

[0130] Repeating unit C

[0131] The repeating unit C has an acid-stable dissolution-retarding group, which is generally a structure that protects alkali-soluble groups such as carboxyl groups and phenolic hydroxyl groups by acid-stable dissolution-repressing groups, or a structure that does not have alkali solubility itself. It is generally preferred that the repeating unit is a repeating unit in which the carboxyl groups and phenolic hydroxyl groups in the repeating unit derived from (meth) acrylic acid or hydroxystyrene are protected by acid-stable dissolution-repressing groups. The repeating unit can control the dissolution rate of the polymer in an organic or alkaline developer solvent, the refractive index of the film, the light transmittance and other optical properties within a certain range to achieve more application value.

[0132] Examples of the acid-stable dissolution inhibiting group include a structure in which the hydrogen atom of a carboxyl group or a phenolic hydroxyl group is substituted and the carbon atom bonded to the oxygen atom is a primary or secondary carbon atom and an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 12 carbon atoms, or a methyl group and a 1-adamantyl group are bonded. Specifically, examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a cyclopentyl group, a cyclohexyl group, a 2-norbornyl group, a 2-isobornyl group, an 8-tricyclo[5.2.1.02,6]decyl group, a 1-adamantyl group, a 2-adamantyl group, a 4-tetracyclo[4.4.0.12,5.17,10]dodecyl group, a phenyl group, a benzyl group, a naphthyl group, an anthracenyl group, and the like.

[0133] Specific examples of the repeating unit C are given below, but the present invention is not limited thereto. One or more repeating units C having different structures can be selected and used.

[0134]

[0135] The acid-sensitive or alkali-soluble resin of the present invention is obtained by combining the above A, B, C and repeating units derived therefrom. Generally speaking, the polymer may include 5-35% by mole, preferably 10-30% of repeating unit A; the polymer may include 40-80% by mole, preferably 50-70% of repeating unit B; the polymer may include 5-35% by mole, preferably 10-25% of repeating unit C.

[0136] For example, the polymer may include 10-30% of repeating unit A, 50-70% of repeating unit B, and 10-25% of repeating unit C, each based on 100 mol % of the total repeating units in the polymer.

[0137] In some embodiments of the present invention, the polymer may be a mixture of two or more polymers;

[0138] The polymer may have a weight average molecular weight (Mw) of 2000 to 100000 g / mol, for example preferably 7000 to about 30000 g / mol, more preferably 12000 to about 20000 g / mol, and a polydispersity index (PDI) of 1.3 to 3, preferably 1.3 to 2, more preferably 1.4 to 2.

[0139] In the present invention, the UV absorbing compound is used in combination with the above-mentioned polymer in the form of a mixture or by polymerization to form a photoresist.

[0140] In the present invention, the photoresist composition may further include one or more photoacid generators (PAGs). Photoacid generators generally include substances that can be used as chemically amplified photoresists and are appropriately selected and used. Photoacid generators include onium salts such as iodonium salts and sulfonium salts, oxime sulfonates, diazomethanes such as dialkyl or diaryl sulfonyl diazomethanes, nitrobenzyl sulfonates, iminosulfonates, disulfones, etc.

[0141] Suitable photoacid generators are known in the art of chemically amplified photoresists and include, for example: onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonates such as 1,2,3-tris(methylsulfonyloxy)benzene, 1,2,3-tris(trifluoromethyl)benzene; diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane and bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate; these may be used alone or in combination of two or more.

[0142] The photoresist composition may further include an amine or amide compound, which is referred to as a quencher in the present invention. Quenchers may more broadly include quenchers such as those based on hydroxides, carboxylates / esters, amines, imines and amides. In one embodiment, available quenchers are amines, amides or a combination of at least one of the above substances. Preferably, this quencher includes C1-C30 organic amines, imines or amides, or may be a C1-C30 quaternary ammonium salt of a strong base (such as a hydroxide or an alkoxide) or a weak base (such as a carboxylate). Exemplary quenchers include amines, such as Trogers bases, hindered amines, such as diazabicycloundecene (DBU) or diazabicyclononene (DBN), N-protected amines, such as N-tert-butylcarbonyl-1,1-bis(hydroxymethyl)-2-hydroxyethylamine (TBOC-TRIS), or ionic quenchers, including alkyl quaternary ammonium salts, such as tetrabutylammonium hydroxide (TBAH) or tetrabutylammonium lactate.

[0143] In the present invention, other components of the photoresist may include solvents and surfactants. The solvents generally suitable for dissolving, distributing and coating the components include ethers, alcohols, esters, ketone solvents, specifically selected from, for example, anisole, ethyl lactate, 2-hydroxybutyric acid methyl ester (HBM), 1-methoxy-2-propanol (also known as propylene glycol methyl ether, PGME), 1-ethoxy-2-propanol, n-butyl acetate, 1-methoxy-2-propyl acetate (also known as propylene glycol methyl ether acetate, PGMEA), methoxyethoxy propionate, ethoxyethoxy propionate and one or more combinations of gamma-butyrolactone, cyclohexanone, 2-heptanone, etc.; surfactants include fluorinated surfactants and non-fluorinated surfactants, preferably nonionic surfactants. Exemplary fluorinated nonionic surfactants include perfluorinated C4 surfactants, such as FC-4430 and FC-4432 surfactants, available from 3M Company; and fluoroglycols, such as POLYFOX PF-636, PF-6320, PF-656 and PF-6520 fluorinated surfactants available from Omnova.

[0144] In the present invention, the content of the photoacid generator in the photoresist is 0.01-20% by weight, preferably 0.1-15% by weight, based on the total weight of the solid. When a polymer combined with a photoacid generator is used, the polymer combined with a photoacid generator is present in the same amount as the corresponding monomer. Based on the total weight of the solid, the content of the copolymer can be 50-99% by weight, preferably 55-95% by weight, further preferably 60-90% by weight, and more preferably 65-90% by weight. It should be understood that the "polymer" used in the photoresist component of the present invention only represents the copolymer disclosed herein, or a combination of the polymer and another polymer that can be used for the photoresist. Based on the total weight of the solid, the content of the surfactant included can be 0.01-5% by weight, preferably 0.1-4% by weight, and more preferably 0.2-3% by weight. Based on the total weight of the solid, the amount of the quencher that can be included is relatively small, such as 0.03-5% by weight. Based on the total weight of the solid, the amount of the UV absorber is 0.03-5 wt %; based on the total weight of the solid, the amount of other additives included can be less than or equal to 30 wt %, preferably less than or equal to 20 wt %, or more preferably less than or equal to 10 wt %. Based on the total weight of the solid and the solvent, the total solid content of the photoresist composition can be 0.5-50 wt %, preferably 1-45 wt %, more preferably 2-40 wt %, more preferably 5-35 wt %. It should be understood that the solid includes the copolymer, the photoacid generator, the quencher, the surfactant and any optional additives, but does not include the solvent.

[0145] Example

[0146] Hereinafter, embodiments of the present invention will be described in detail.

[0147] Synthesis Example 1 Synthesis of Compound A1

[0148] 2-hydroxyanthracene and 0.003 molar equivalents of p-toluenesulfonic acid (relative to 2-hydroxyanthracene) were added to a round-bottom flask equipped with a thermometer, and propylene glycol methyl ether acetate (PGMEA) was added. The solid content of the reaction solution was controlled at 10%, the reaction temperature was controlled at 70°C, and the reaction was concentrated under reduced pressure. The water content of the reaction solution was finally measured to be less than 300 ppm and the solid content was 30%. The reaction was replaced with a nitrogen atmosphere, and 1 molar equivalent of 2-methoxyethyl vinyl ether in a 10% PGMEA solution was added at a uniform rate within 2 hours, and the reaction temperature was controlled at 60°C. The reaction continued for 6 hours after the addition was completed. After the reaction was completed, the product A1 was obtained by solvent replacement, filtration, washing and other steps, ESI-MS m / z: 297.1412 [M+H] +.

[0149]

[0150] Synthesis Example 2 Synthesis of Compound A2

[0151] Add 1,8-anthraquinone and 0.003 molar equivalents of p-toluenesulfonic acid (relative to 1,8-anthraquinone) to a round-bottom flask equipped with a thermometer, add PGMEA, control the solid content of the reaction solution to 10%, control the reaction temperature to 70°C, and concentrate under reduced pressure. Finally, the water content of the reaction solution is measured to be less than 300ppm and the solid content is 30%. Replace the reaction with a nitrogen atmosphere, add 2 molar equivalents of 10% PGMEA solution of 2-methoxyethyl vinyl ether at a uniform rate within 2 hours, and control the reaction temperature to 60°C. The reaction continues for 6 hours after the addition is completed. After the reaction is completed, the product A2 is obtained by solvent replacement, filtration, washing and other steps, ESI-MSm / z: 415.2042[M+H]+.

[0152]

[0153] Synthesis Example 3 Synthesis of Compound A3

[0154] Add anthralin and 0.003 molar equivalents of p-toluenesulfonic acid (relative to anthralin) to a round-bottom flask equipped with a thermometer, add PGMEA, control the solid content of the reaction solution to 10%, control the reaction temperature to 70°C, and concentrate under reduced pressure. Finally, the water content of the reaction solution is measured to be less than 300ppm and the solid content is 30%. Replace the reaction with a nitrogen atmosphere, add 2 molar equivalents of 10% PGMEA solution of 2-methoxyethyl vinyl ether at a uniform rate within 2 hours, and control the reaction temperature to 60°C. The reaction continues for 6 hours after the addition is completed. After the reaction is completed, the product A3 is obtained by solvent replacement, filtration, washing and other steps, ESI-MS m / z: 431.1992 [M+H] +.

[0155]

[0156] Synthesis Example 4 Synthesis of Compound A4

[0157] Add 1,5-naphthalene diol and 0.003 molar equivalents of p-toluenesulfonic acid (relative to 1,5-naphthalene diol) to a round-bottom flask equipped with a thermometer, add PGMEA, control the solid content of the reaction solution to 10%, control the reaction temperature to 70°C, and concentrate under reduced pressure. Finally, the water content of the reaction solution is measured to be less than 300ppm and the solid content is 30%. Replace the reaction with a nitrogen atmosphere, and add 2 molar equivalents of 10% PGMEA solution of 2-methoxyethyl vinyl ether at a uniform rate within 2 hours, and control the reaction temperature to 60°C. After the addition is completed, the reaction continues for 6 hours. After the reaction is completed, the product A4 is obtained by solvent replacement, filtration, washing and other steps, ESI-MSm / z: 365.1886[M+H]+

[0158]

[0159] Synthesis Example 5 Synthesis of Precursor Vinyl Ether A-5a of Compound A5 Anthracenecarboxylic acid and 1 molar equivalent of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) were added to a three-necked flask equipped with a thermometer, and dichloromethane was used as the reaction solvent. The solid content of the reaction solution was controlled at 30%. After reacting at 45°C for 1 hour, 1.05 molar equivalents of 2-methoxyethyl vinyl ether were added, and the reaction was continued for 18 hours before the reaction was terminated. The reaction solution was initially purified by repeated water extraction, and then recrystallization and purification could be determined according to the situation.

[0160]

[0161] Synthesis of Compound A5

[0162] Add bisphenol A and 0.003 molar equivalents of p-toluenesulfonic acid (relative to bisphenol A) to a round-bottom flask equipped with a thermometer, add PGMEA, control the solid content of the reaction solution to 10%, control the reaction temperature to 70°C, and concentrate under reduced pressure. The final measured moisture content of the reaction solution is below 300ppm and the solid content is 30%. Replace the reaction with a nitrogen atmosphere, and add 2 molar equivalents of a 10% PGMEA solution of A-05a at a uniform rate within 2 hours, and control the reaction temperature to 60°C. The reaction continues for 6 hours after the addition is completed. After the reaction is completed, the product A5 is obtained by solvent replacement, filtration, washing and other steps, ESI-MS m / z: 813.3349 [M+H] +,

[0163]

[0164] Synthesis Example 6 Synthesis of Vinyl Ether A-6a, a Synthesis Precursor of Compound A6 1-naphthoic acid and 1 molar equivalent of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) were added to a three-necked flask equipped with a thermometer, and dichloromethane was used as the reaction solvent. The solid content of the reaction solution was controlled at 30%. After reacting at 45°C for 1 hour, 1.05 molar equivalents of 2-methoxyethyl vinyl ether were added, and the reaction was continued for 18 hours before the reaction was terminated. The reaction solution was initially purified by repeated water extraction, and then recrystallization and purification could be determined according to the situation.

[0165]

[0166] Synthesis of Compound A6: Add bisphenol A and 0.003 molar equivalents of p-toluenesulfonic acid (relative to bisphenol A) to a round-bottom flask equipped with a thermometer, add PGMEA, control the solid content of the reaction solution to 10%, control the reaction temperature to 70°C, and concentrate under reduced pressure. The final measured moisture content of the reaction solution is below 300 ppm and the solid content is 30%. Replace the reaction with a nitrogen atmosphere, and add 2 molar equivalents of a 10% PGMEA solution of A-06a at a uniform rate within 2 hours, and control the reaction temperature to 60°C. The reaction continues for 6 hours after the addition is completed. After the reaction is completed, the product A6 is obtained by solvent replacement, filtration, washing and other steps, ESI-MS m / z: 713.3036 [M+H] +,

[0167]

[0168] Example 1

[0169] 10 g of polymer, 0.4 g of photoacid generator, 0.1 g of quencher, 0.1 g of UV absorber A1, and 0.05 g of surfactant were dissolved in 80 g of PGMEA and ethyl lactate. The mixture was dissolved and dispersed on a shaker for 12 h, and filtered through a filter with a precision of 0.45 μm to obtain a finished product.

[0170] Among them, polymer: Where x:Y:Z=60:20:20, molecular weight is 16800, distribution PDI 1.65; photoacid generator: Quencher: Surfactant: POLYFOX PF-636 surfactant (Onofa Chemical);

[0171] Examples 2-6 and Comparative Examples 1-2

[0172] According to the raw material ratio in Table 1, the photoresist compositions of Examples 2-6 and Comparative Examples 1-2 were obtained using the same preparation method. Among them, UV absorber A7:

[0173] Table 1

[0174]

[0175] test:

[0176] After cleaning and pretreatment of a 200 mm silicon wafer, hexamethyldisilazane (HMDS) was evaporated onto the surface of the silicon wafer using a viscosity-enhancing oven. The photoresist compositions of Examples 1-6 and Comparative Examples 1-2 were spin-coated on the silicon wafers treated with viscosity-enhancing treatment, and pre-baked using a hot plate at a temperature of 100°C for 60 seconds to form a resist film with a thickness of 280 nm. The photoresist was exposed to a KrF excimer laser (248 nm) through a mask pattern whose target was a line and space pattern (L / S pattern) with a line width of 180 nm and a pitch of 360 nm. The silicon wafer was post-exposure baked (PEB) at 120°C for 60 seconds, followed by development with 0.26N tetramethylammonium hydroxide (TMAH) aqueous developer.

[0177] Hitachi 9380CD SEM was used to observe the pattern formed after development, and the exposure latitude (EL), depth of focus (DOF), and line width uniformity (CDU) of 180nm dense space were tested. Then the exposed film was sliced, and the development residue and standing wave of 180nm dense space were observed using HitachiS-4800 scanning electron microscope. The test data are shown in Table 2.

[0178] Table 2

[0179] Standing wave situation EL DOF CDU Development residue Example 1 none 15.2％ 300nm B B Example 2 none 16.3％ 300nm A A Example 3 slight 11.7％ 200nm B A Example 4 slight 15.9％ 300nm A A Example 5 none 15.7％ 350nm A A Example 6 none 15.3％ 300nm A A Comparative Example 1 slight 15.0％ 250nm C B Comparative Example 2 serious 12.5％ 250nm B A

[0180] In Table 2, in the line width uniformity (CDU) test item, A represents excellent, B represents good, and C represents poor. In the development residue test item, A represents no development residue, B represents occasional residue, and C represents multiple residues. As shown in Table 2, the photoresist compositions of Examples 1 to 6 of the present invention use a UV absorber with a specific structure modification, which can significantly improve CDU and development residue while improving the standing wave effect.

Claims

1. A UV absorbing compound, characterized in that A structure having the following general formula: Wherein Ar is the reaction residue of monohydric phenol, dihydric phenol, trihydric phenol or tetrahydric phenol, and the carbon number of Ar is 10-40; R D1 It is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an acyl group having 1 to 16 carbon atoms, n is an integer of 1 to 5, and m is an integer of 1 to 4.

2. The compound according to claim 1, characterized in that: Ar is a reaction residue of a monohydric phenol or a dihydric phenol, the carbon number of Ar is 10 to 30, and R D1 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an acyl group having 5 to 16 carbon atoms, n is 1 or 2, and m is 1 or 2; D1 An alkyl group having 1 to 4 carbon atoms or an acyl group having 5 to 16 carbon atoms is preferred.

3. The compound according to claim 1 or 2, characterized in that: Ar is one of the reaction residues of bisphenol compounds, anthracenol, anthracenediol, naphthol, naphthalenediol, anthracene, pyrenol, pyrenediol, and biphenyldiol; and / or R D1 At least one selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzoyl, naphthoyl and anthracoyl.

4. The compound according to any one of claims 1 to 3, characterized in that: The UV absorbing compound is selected from at least one of the following structures:

5. The method for synthesizing the UV absorbing compound according to any one of claims 1 to 4, characterized in that: It is obtained by reacting a phenol compound with a vinyl ether compound in the presence of an acid.

6. The method for synthesizing the compound according to claim 5, characterized in that: The acid is selected from at least one of p-toluenesulfonic acid, trifluoroacetic acid, phosphoric acid, and p-trifluoromethylbenzenesulfonic acid; and / or the phenolic compound is a phenolic compound containing an Ar structure; and / or the vinyl ether compound is selected from at least one of the following structures:

7. A photoresist composition, characterized in that: Includes the following components: polymer resin, 50-99 weight percent, based on the total weight of solids; Photoacid generator, 0.01-20 wt %, based on the total weight of the solid; Quencher, 0.03-5 wt %, based on the total weight of the solid; The UV absorbing compound of any one of claims 1 to 4, 0.03 to 5% by weight, based on the total weight of the solids; Surfactant, 0.01-5% by weight, based on the total weight of solids; Solvents; The total solid content of the photoresist is 0.5-50 wt % based on the total weight of solid and solvent.

8. The photoresist composition according to claim 7, characterized in that: The polymer resin comprises: Repeating unit A, 5-35 mol%, based on 100 mol% of the total repeating units in the polymer; Repeating unit B, 40-80 mol%, based on 100 mol% of the total repeating units in the polymer; and repeating unit C, 5 to 35 mol%, based on 100 mol% of the total repeating units in the polymer; And / or, the repeating unit A is selected from at least one of the following structures: The repeating unit B is selected from at least one of the following structures: The repeating unit C is selected from at least one of the following structures:

9. A photoresist film, characterized in that: The photoresist composition according to any one of claims 7 and 8 is cured.

10. Use of the photoresist composition according to claim 7 or 8 in preparing a deep ultraviolet photoresist film.

Images