CN108147983A - A kind of sulfosalt bonding benzene polyphenol type molecular glass photoresist and its preparation method and application - Google Patents

A kind of sulfosalt bonding benzene polyphenol type molecular glass photoresist and its preparation method and application Download PDF

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CN108147983A
CN108147983A CN201611105094.4A CN201611105094A CN108147983A CN 108147983 A CN108147983 A CN 108147983A CN 201611105094 A CN201611105094 A CN 201611105094A CN 108147983 A CN108147983 A CN 108147983A
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alkyl
compound
logical formula
photoresist
glue composition
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CN108147983B (en
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杨国强
袁华
许箭
彭晓曼
王亮乾
王双青
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The present invention relates to a kind of sulfosalt bonding benzene polyphenol type molecular glass photoresists and its preparation method and application.The sulfosalt bonding benzene polyphenol type molecular glass photoresist is three-dimensional asymmetric amorphous micromolecular compound, with higher fusing point and glass transition temperature (fusing point is above 100 DEG C), it disclosure satisfy that lithography requirement, membrane structure is unchanged in high-temperature baking.Such compound can be re-dubbed positivity or negative photoresist individually or with other photoresists, photo-acid generator, crosslinking agent etc., and photoresist coating in homogeneous thickness can be made by spin-coating method on substrate.The photoetching glue formula can be used in the modern lithographic technologies such as 365nm photoetching, 248nm photoetching, 193nm photoetching, extreme ultraviolet photolithographic and electron beam lithography, be particularly suitable in extreme ultraviolet carving technology.

Description

A kind of sulfosalt bonding benzene polyphenol type molecular glass photoresist and preparation method thereof and Using
Technical field
The present invention relates to technical field of lithography, and in particular to a kind of sulfosalt bonding benzene polyphenol molecular glass photoresist and its Preparation method and application.
Background technology
IC industry has been deep into the every field of the modern life, especially so-called 3C fields, i.e., consumer Electronic product (consumer), computer (computer) and communicate (communication).Its extensive use and fast development All it be unable to do without the lasting follow-up that photoetching technique updates with Other substrate materials.
Photoresist is a kind of mixing material to light or radiation-sensitive, usually by photoresist material of main part, photosensitizer, molten The compositions such as agent, acid-proof diffusant and some other additive, photoresist material of main part mainly has film-forming resin, molecular glass Close several classes such as object, inorganic oxide.After illumination, in exposure region photopolymerization, photodegradation or photo-crosslinking occur for photoresist, make It obtains the physical properties such as dissolubility, the adhesion of material and significant changes occurs, and develop in appropriate solvent.According to photoresist Removal retains, and photoresist can be divided into two major class of positive photoresist and negative photoresist again.With the update of photoetching technique, photoetching Glue material experienced the polyvinyl cinnamate from early stage, thermoprene-azido compound, near ultraviolet phenolic resin-diazonium Naphthoquinones class, deep ultraviolet vacuum ultraviolet photoresist, to photoetching techniques photoetching such as the extreme ultraviolet, electron beam, nano impressions of a new generation Glue material.
Extreme ultraviolet lithography is the photoetching technique that a new generation is most expected, and mainly uses light of the wavelength for 13.5nm Source has lower diffraction limit, can reach 32nm and 22nm nodes, even lower technology node.Corresponding extreme ultraviolet Photoresist material also will be provided with more strict requirements, need low absorptance, the high grade of transparency, high etch resistance, and high-resolution (is less than 22nm), it is highly sensitive, high environmental stability, low yield tolerance and low line edge roughness etc..Presently used extreme ultraviolet photolithographic Glue material mainly has the systems such as high-molecular compound, organic molecule glass, inorganic compound, organic metal hydridization.Wherein, it is organic Molecular glass has determining structure, and molecule can be modified, compared with traditional polymeric photoresist material, have high sensitivity, The advantages that roughness is good, monodisperse, moulding property are good.
Chemically-amplified resist is a kind of common photoresist system, and chemistry amplification refers under the action of light, passes through light The decomposition of acid agent (Photoacid generator, PAG) is caused to generate strong acid, cascade reaction is induced under heat effect and generates More acid, are the soluble group of developer solution by the decomposed of acid labile in photoresist material of main part, and according to solubility Difference portion body material is dissolved, so as to obtain erect image or negative image pattern.Photo-acid generator is generally divided into ionic and non- Two class of ionic.Ionic PAG is often made of diaryl iodonium salt or triaryl sulfonium salts etc., and non-ionic PAG is most common It is the compounds such as nitrobenzyl ester, diazonium naphthoquinone sulphonate or N- sulfimides.Chemically-amplified resist has very high comparison Degree and resolution ratio, etch resistance can also very well, but its distinctive rear baking process may result in acid diffusion excessively or postpone to imitate It should wait, figure is caused to cave in or intersect, so that reducing resolution ratio, increase roughness.
Invention content
To overcome deficiency of the prior art, molecular glass material of main part is bonded by the present invention with sulfosalt, with overcoming The shortcomings of being separated caused by learning coarse graphic edge caused by acid diffusion in amplification process, resolution ratio reduction and multicomponent.
The purpose of the present invention is to provide a kind of sulfosalt bonding benzene polyphenol type molecular glass photoresists and preparation method thereof.
Another object of the present invention is to provide above-mentioned sulfosalt to be bonded benzene polyphenol type molecular glass photoresist in extreme ultraviolet Application in photoetching process.
The object of the invention is achieved by following technical solution：
A kind of below formula (I) or logical formula (II) compound represented：
In formula (I) or formula (II), X-Selected from Cl-、BF4 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、CF3CF2CF2CF2SO3 -、R is independent of each other to be selected from H ,-C1-8Alkyl, aryl (such as)；R1That This is independent to be selected from H ,-C1-8Alkyl ,-COOC1-8Alkyl (such as)、-C1-8Alkyl-O-C1-8Alkyl (such as)、-C1-8Alkyl-OCO- aryl (such as)、-C1-8Alkyl-OC1-8Alkyl- OCOC1-8Alkyl ,-C1-8Alkyl-OC1-8Alkyl-OCO- aryl (such as)、
The alkyl is the linear or branched alkyl group that carbon atom number is 1-8 (preferably 1-6), for example, methyl, ethyl, propyl, Butyl, isobutyl group, tertiary butyl etc..
According to the present invention, the aryl refers to the monocyclic or polycyclic aromatic base with 6-20 (preferably 6-14) carbon atoms Group, representative aryl include：Phenyl, naphthalene, anthryl etc..
The present invention also provides a kind of preparations of sulfosalt bonding benzene polyphenol type molecular glass prepared shown in above-mentioned logical formula (I) Method, including：
Wherein X-、R、R1As described above, and R1It is not all H；
(1) compound (III) is reacted with R-SO-R or R-S-R generation sulfoniums, and wherein R is independent of each other to be selected from H ,-C1-8 Alkyl, aryl；It is optional later to carry out anion exchange reaction with salt, obtain compound (I-A)；Wherein, X independences are selected from Cl-、BF4 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、CF3CF2CF2CF2SO3 -、
(2) compound (I-A) and R obtained in above-mentioned steps (1)2OR2、R3Z or CH2=CR5-OR4Reaction, wherein R2 For-COOC1-8Alkyl,In one kind, R3、R4Independent optionally-C1-8Alkyl ,-COOC1-8Alkyl ,-C1-8Alkyl- O-C1-8Alkyl ,-C1-8Alkyl-OCO- aryl ,-C1-8Alkyl-OC1-8Alkyl-OCOC1-8Alkyl ,-C1-8Alkyl-OC1-8Alkyl- OCO- aryl,R5Independent optionally H ,-C1-8Alkyl, Z are halogen；Obtain compound (I- B), wherein, R1It is as defined above, and R1Be not all H, i.e., the logical formula (I) compound that hydroxyl full guard or part are protected.
The present invention also provides a kind of systems of sulfosalt bonding benzene polyphenol type molecular glass prepared shown in above-mentioned logical formula (II) Preparation Method, including：
Wherein X-、R、R1As described above, and R1It is not all H；
(1 ') compound (IV) occurs sulfonium with R-SO-R or R-S-R and reacts, and wherein R is independent of each other to be selected from H, C1-8 Alkyl, aryl, it is optional later to carry out anion exchange reaction, generation compound (II-A) with salt；Wherein, X independences are selected from Cl-、BF4 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、CF3CF2CF2CF2SO3 -、
General formula (II-A) compound and R obtained in (2 ') above-mentioned steps (1 ')2OR2、R3Z or CH2=CR5-OR4Reaction, Wherein R2For-COOC1-8Alkyl,In one kind, R3、R4Independent optionally-C1-8Alkyl ,-COOC1-8Alkyl ,-C1-8 Alkyl-O-C1-8Alkyl ,-C1-8Alkyl-OCO- aryl ,-C1-8Alkyl-OC1-8Alkyl-OCOC1-8Alkyl ,-C1-8Alkyl-OC1-8Alkane Base-OCO- aryl, R5Independent optionally H ,-C1-8Alkyl, Z are halogen；Obtain compound (II-B), wherein, R1It is as defined above, and R1Be not all H, i.e., the logical formula (II) chemical combination that hydroxyl full guard or part are protected Object.
In step (1) described above or step (1 '), sulfoniumization reaction preferably in a solvent, in the presence of hydrogen chloride into Row, the solvent are preferably methanol or ethyl alcohol, and reaction temperature is preferably -10 to 20 DEG C (such as 0 DEG C), and the time is preferably 2~3h, Wherein compound (I-A) (or compound (II-A)) and the rate of charge preferred molar ratio 1 of sulfoxide RSOR or thioether RSR：1.
In step (1) described above or step (1 '), after reaction, optional carries out anion to the sulfoniumization with salt again Exchange reaction, for example, reacted with KY (Y independences selected from BF4 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、 CF3CF2CF2CF2SO3 -、).Above-mentioned anion exchange reaction preferably carries out (such as water) in a solvent, reaction Temperature is preferably room temperature, and the time is preferably 1h.
In step (2) described above or step (2 '), the reaction preferably carries out in the presence of a catalyst, the catalyst Preferably potassium carbonate or 4-dimethylaminopyridine (DMAP) or sodium hydride.The reaction temperature is preferably room temperature.Reaction time is excellent It is selected as 2-12h.The reaction carries out under solvent, and reaction dissolvent is preferably tetrahydrofuran or acetone.Product is preferably through acetic acid second Ester/n-hexane recrystallization purifying.
According to the present invention, in step (2) or step (2 '), the compound (I-B) (or compound (II-B)) with R2OR2、R3Z or CH2=CR5OR4Molar ratio be 1:When 1~1.2, the sulfosalt bonding benzene of hydroxyl full guard can be obtained Polyphenol type molecular glass.The compound (I-B) (or compound (II-B)) and R2OR2、R3Z or CH2=CR5OR4Feed intake and rub You are than being 1:When 0.2~0.8, the sulfosalt bonding benzene polyphenol type molecular glass of hydroxylic moiety protection can be obtained.
Sulfosalt group is introduced benzene polyphenol type molecular glass (containing bisphenol A skeleton structure or containing four benzene by the present invention The benzene polyphenol type molecular glass of base thiophene skeleton structure) structure in, form logical formula (I) of the present invention or logical formula (II) Object is closed, the compound is at the same time as the material of main part and photo-acid generator of photoresist, phase caused by so as to overcome multicomponent The shortcomings of graphic edge caused by excessive acid diffusion is coarse in separation and chemical amplification process, resolution ratio reduces.
The present invention also provides logical formula (I) or the purposes of logical formula (II) compound, which is characterized in that for 365nm light In the photoetching processes such as quarter, 248nm photoetching, 193nm photoetching, extreme ultraviolet (EUV) photoetching and electron beam lithography (EBL).Preferably, should For in extreme ultraviolet carving technology.
The logical formula (I) of the present invention or the sulfosalt bonding benzene polyphenol molecular glass shown in (II), wherein hydroxyl is (i.e. in structure Phenolic hydroxyl group) unprotected molecular glass can use as negative photoresist, the molecular glass of hydroxyl full guard can be used as positivity Photoresist uses, and the molecular glass of hydroxylic moiety protection can be used as positivity or negative photoresist to use.
In the structure shown in logical formula (I) or (II), the unprotected molecular glass of hydroxyl described above refers to group R1Entirely Portion is the compound of H.The molecular glass of hydroxyl full guard described above refers to group R1The compound of all non-H groups, i.e., Hydroxyl is not contained in structure.The molecular glass of the hydroxylic moiety protection refers to group R1Middle part is selected from H, partly selected from non-H The compound of group.
The present invention further provides a kind of positive-tone photo glue composition, the general formula including hydroxyl full guard or part protection (I) or (II) compound.
Above-mentioned hydroxyl full guard or the logical formula (I) or (II) compound of part protection, refer to R in logical formula (I) or (II)1In At least one is non-H groups.
According to the present invention, the positive-tone photo glue composition also contains photoresist solvent.
According to the present invention, the positive-tone photo glue composition, by hydroxyl full guard or the logical formula (I) or (II) of part protection Compound and photoresist solvent composition.I.e. the positive-tone photo glue composition is a kind of positivity unimolecule photoresist.Preferably, it is described Positivity unimolecule photoresist contains the logical formula (I) of 0.1%~10% (mass ratio) or (II) compound.
According to the present invention, the positive-tone photo glue composition also optionally contains photoresist, photo-acid generator or acid Dispersion inhibitor etc..Preferably, the positive-tone photo glue composition, logical formula (I) or (II) containing 1%~10% (mass ratio) Compound, the photoresist of 0%~5% (mass ratio), the photo-acid generator of 0%~1% (mass ratio), 0.001%~0.1% The sour dispersion inhibitor of (mass ratio).
The present invention also provides a kind of negative photo glue composition, including hydroxyl is unprotected or part protect logical formula (I) or (II) compound.
Above-mentioned hydroxyl is unprotected or the logical formula (I) or (II) compound of part protection, refers to R in logical formula (I) or (II)1Extremely It is few that there are one be H.
According to the present invention, the negative photo glue composition also contains photoresist solvent.
According to the present invention, the negative photo glue composition, by hydroxyl it is unprotected or part protection logical formula (I) or (II) Compound and photoresist solvent composition.I.e. the negative photo glue composition is a kind of negativity unimolecule photoresist.Preferably, it is described Negativity unimolecule photoresist contains the logical formula (I) of 0.1%~10% (mass ratio) or (II) compound.
According to the present invention, the negative photo glue composition is also optionally containing photoresist, photo-acid generator, crosslinking Agent.
According to the present invention, the negative photo glue composition preferably comprise 0.1%~10% (mass ratio) logical formula (I) or (II) compound, the photoresist of 0%~5% (mass ratio), the photo-acid generator of 0%~1% (mass ratio), 0.01%~1% The crosslinking agent of (mass ratio).
According to the present invention, the photoresist can be photoresist well known in the prior art, such as the China of Yang Guoqiang etc. The photoresist that patent 201210156675.6,201210070713.6 is reported.
According to the present invention, the photo-acid generator include ionic or non-ionic, as triphenylsulfonium triflate sulfonate, Triphenylsulfonium perfluoro butyl sulfosalt, two (4- tert-butyl-phenyls) iodine tosilate, N- hydroxynaphthylimide fluoroforms Sulfonate etc..
According to the present invention, the photoresist solvent includes propylene glycol methyl ether acetate (PGMEA), ethyl lactate, ethylene glycol Monomethyl ether, cyclohexanone etc..
According to the present invention, the acid dispersion inhibitor includes n-octyl amine, tri-n-octyl amine, two n-octyl amine of N- methyl, t-octanylamine Deng.The crosslinking agent includes tetramethoxymethylglycoluril, bisphenol type epoxy propyl ether etc..
According to the present invention, above-mentioned positive-tone photo glue composition or negative photo glue composition can also include other additions Agent, such as sensitizer, surfactant, dyestuff, stabilizer, cosolvent.
The present invention provides the application of a kind of above-mentioned positive-tone photo glue composition or negative photo glue composition again, and feature exists In for photoetching works such as 365nm photoetching, 248nm photoetching, 193nm photoetching, extreme ultraviolet (EUV) photoetching and electron beam lithographies (EBL) In skill.Preferably, applied in extreme ultraviolet carving technology.
The present invention also provides a kind of photoresist coatings, which is characterized in that by the positive-tone photo glue composition or negativity light Photoresist composition carries out spin coating in substrate and obtains.
Preferably, the smearing mode is that spin coating is carried out in substrate by sol evenning machine.
Preferably, the substrate can be silicon chip.The silicon chip is preferably the silicon chip after hydrophobic treatment.
Beneficial effects of the present invention：
1. sulfosalt unit is attached by the present invention with photoresist material of main part by chemical bond, so as to make sulfosalt list Member is realized be uniformly distributed in the photoresist.After sulfosalt unit light is according to production acid, neighbouring intramolecular acid-unstable group is acted on, Generation is dissolved in the compound of developer solution, therefore can obtain high resolution lithography figure.
2. the sulfosalt bonding benzene polyphenol type molecular glass shown in the logical formula (I) of the present invention or logical formula (II) is three-dimensional not right The amorphous micromolecular compound claimed has higher fusing point and glass transition temperature (fusing point is above 100 DEG C), Neng Gouman Sufficient lithography requirement, membrane structure is unchanged in high-temperature baking.
3. uniform film can be prepared in the photoetching compositions of the present invention, the film has good resolution Rate, light sensitivity, adhesiveness are easy to preserve, and in film-forming process, and the molecular glass as matrix composition is not precipitated.
Description of the drawings
Fig. 1 is the EUV lithography result figure of the positive photoresist prepared by embodiment 3.
Specific embodiment
Guiding theory in order to further illustrate the present invention, provides following serial specific embodiment, but the present invention not by The limitation of these specific embodiments, any understanding person skilled in art can reach similar to the few modifications of the present invention As a result, these changes are also contained among the present invention.
Embodiment 1
1. prepare chlorodimethyl -2,2- two (4- hydroxyls -3,5- two (3,4- dihydroxy phenyls) phenyl) propyl sulfosalt (1-B)
3.3g 2,2- bis- (4- hydroxyls -3,5- two (3,4- dihydroxy phenyls) phenyl) propane (III) (5mmol) is dissolved in 30mL methanol solvates are added in 100mL there-necked flasks, under the conditions of ice-water bath, are continuously passed through hydrogen chloride gas, dropwise addition is dissolved in 10mL The 0.39g dimethyl sulfoxide (DMSO)s (5mmol) of methanol continue to stir 2-3 hour under the conditions of maintaining 0 DEG C.It, will be molten after the reaction was complete Liquid is spin-dried for, and water and ethyl acetate is added to extract, and retains water phase, and repeatedly collecting water phase after extraction is spin-dried for, and is placed in 50 DEG C of vacuum drying chambers It is dried in vacuum overnight, obtains faint yellow solid powder.
MALDI-TOF(C41H37ClO10S),m/z:721.2。
2. prepare perfluoro butyl sulfonic acid dimethyl -2,2- two (4- hydroxyls -3,5- two (3,4- dihydroxy phenyls) phenyl) third Base sulfosalt (1-C)
By 3.8g chlorodimethyls -2,2- two (4- hydroxyls -3,5- two (3,4- dihydroxy phenyls) phenyl) propyl sulfosalt (1-B) (5mmol) and 3.4g perfluorobutyl potassium sulfonates (10mmol) are dissolved in deionized water respectively.The aqueous solution of (1-B) is delayed It is slow to instill in perfluorobutyl potassium sulfonate aqueous solution, and be stirred continuously, after all dripping, continue stirring 1 hour, then use The ethyl acetate extraction of amount three times, collects organic phase, first using anhydrous MgSO4Organic phase is dried, after be spin-dried for, be placed in 50 DEG C of vacuum drying chambers are dried in vacuum overnight, and obtain faint yellow solid powder.MALDI-TOF(C45H37F9O13S2),m/z:721.0。 ESI-MS(C45H37F9O13S2, ion mode), m/z:299.1.
3. prepare (two (the 3,4- tertbutyloxycarbonyls of 4- tertbutyloxycarbonyl oxygen -3,5- of perfluoro butyl sulfonic acid dimethyl -2,2- two Oxygen) phenyl) propyl sulfosalt (1)
By 13.08g di-tert-butyl dicarbonates (60mmol), 13.8g K2CO3120ml tetrahydrofurans are dissolved in, in anhydrous and oxygen-free Under the conditions of be slowly dropped into the two (4- hydroxyls -3,5- two of perfluoro butyl sulfonic acid dimethyl -2,2- that 5.1g is dissolved in 30ml tetrahydrofurans (3,4- dihydroxy phenyl) phenyl) propyl sulfosalt (1-C) (5mmol), it is stirred to react overnight.Insoluble matter is filtered out, by liquid phase It is spin-dried for, with ethyl acetate/aqueous systems extraction three times, collects organic phase, anhydrous magnesium sulfate drying, filtering is spin-dried for.With acetic acid second Ester/n-hexane system co-precipitation three times, collects white precipitate, is placed in 40 DEG C of vacuum drying chambers and is dried in vacuum overnight, obtain white solid Body powder.
MALDI-TOF(C95H117F9O33S2),m/z:1722.73872。
ESI-MS(C95H117F9O33S2, ion mode), m/z:299.1.
Embodiment 2
1. prepare chlorodimethyl -2,3,4,5- four (3,4- dihydroxy phenyls) thiophene sulfosalt (2-B)
2.6g 2,3,4,5- tetra- (3,4- dihydroxy phenyl) thiophene (IV) (5mmol) is dissolved in 30mL methanol solvates, is added in Into 100mL there-necked flasks, under the conditions of ice-water bath, hydrogen chloride gas is continuously passed through, the 0.39g dimethyl for being dissolved in 10mL methanol is added dropwise Sulfoxide (5mmol) continues to stir 2-3 hour under the conditions of maintaining 0 DEG C.After the reaction was complete, solution is spin-dried for, adds water and acetic acid Ethyl ester extracts, and retains water phase, and repeatedly collecting water phase after extraction is spin-dried for, and is placed in 50 DEG C of vacuum drying chambers and is dried in vacuum overnight, obtains light Yellow solid powder.
MALDI-TOF(C30H25ClO8S2),m/z:577.4。
2. prepare perfluoro butyl sulfonic acid dimethyl -2,3,4,5- four (3,4- dihydroxy phenyls) thiophene sulfosalt (2-C)
By 3.1g chlorodimethyls -2,3,4,5- four (3,4- dihydroxy phenyls) thiophene sulfosalt (2-B) (5mmol) and 3.4g perfluorobutyl potassium sulfonates (10mmol) are dissolved in deionized water respectively.The aqueous solution of (2-B) is slowly dropped into perfluoro butyl It in sulfonic acid aqueous solutions of potassium, and is stirred continuously, after all dripping, continues stirring 1 hour, then extracted using the ethyl acetate of equivalent It takes three times, organic phase is collected, first using anhydrous MgSO4Organic phase is dried, after be spin-dried for, be placed in 50 DEG C of vacuum drying chambers It is dried in vacuum overnight, obtains faint yellow solid powder.
MALDI-TOF(C34H25F9O11S3),m/z:577.4。
ESI-MS(C34H25F9O11S3, ion mode), m/z:299.0.
3. prepare perfluoro butyl sulfonic acid dimethyl -2,3,4,5- four (bis- tertbutyloxycarbonyl phenyl of 3,4-) thiophene sulfosalt (2)
By 10.48g di-tert-butyl dicarbonates (48mmol), 11g K2CO3120ml tetrahydrofurans are dissolved in, in anhydrous and oxygen-free item Four (the 3,4- dihydroxy benzenes of perfluoro butyl sulfonic acid dimethyl -2,3,4,5- that 4.4g is dissolved in 30ml tetrahydrofurans is slowly dropped under part Base) thiophene sulfosalt (2-C) (5mmol), it is stirred to react overnight.Insoluble matter is filtered out, liquid phase is spin-dried for, with ethyl acetate/water System extracts three times, collects organic phase, anhydrous magnesium sulfate drying, and filtering is spin-dried for.It is co-precipitated with ethyl acetate/n-hexane system Three times, white precipitate is collected, 40 DEG C of vacuum drying chambers is placed in and is dried in vacuum overnight, obtain white solid powder.
MALDI-TOF(C74H89F9O27S3),m/z:1378.2。
ESI-MS(C74H89F9O27S3, ion mode), m/z:299.0.
Embodiment 3
The preparation of positive photoresist：The compound (1) that 40mg embodiments 1 are prepared, which is dissolved in 1mLPGMEA, to be made into just Property photoresist, (spincoating conditions are for spin coating on through hydrophilic-hydrophobic treated silicon chip：500~1000rpm, 0~30s；1000~ 2000rpm, 0~30s；2000~3000rpm, 0~30s).
Fig. 1 be using the film that embodiment 3 is prepared Shanghai synchrotron radiation light source 08U1B extreme ultraviolet groove stations into The lithographic results figure of row EUV lithography.
The result shows that：The film thickness that spin coating obtains is 30~100nm, and filming performance is good, and gained film thickness is equal It is even, it can uniformly obtain the litho pattern of 70nm to 30nm line widths.
Embodiment 4
The preparation of negative photo glue composition：The compound (1) that will be prepared in 20mg embodiments 1,5mg tetramethoxies Methyl glycoluril crosslinking agent, which is dissolved in 1mL PGMEA, is re-dubbed negative photo glue composition, through hydrophilic-hydrophobic treated silicon chip (spincoating conditions are for upper spin coating：500~1000rpm, 0~30s；1000~2000rpm, 0~30s；2000~3000rpm, 0~ 30s)。
The result shows that：The film thickness that spin coating obtains is 30~100nm, and filming performance is good, and gained film thickness is equal It is even.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiments.It is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention Within the scope of shield.

Claims (9)

1. logical formula (I) or logical formula (II) compound,
In formula (I) or formula (II), X-Selected from Cl-、BF4 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、CF3CF2CF2CF2SO3 -、R is independent of each other to be selected from H ,-C1-8Alkyl, aryl (such as)；R1That This is independent to be selected from H ,-C1-8Alkyl ,-COOC1-8Alkyl (such as)、-C1-8Alkyl-O-C1-8Alkyl (such as)、-C1-8Alkyl-OCO- aryl (such as)、-C1-8Alkyl-OC1-8Alkyl- OCOC1-8Alkyl ,-C1-8Alkyl-OC1-8Alkyl-OCO- aryl (such as)、
2. compound according to claim 1, wherein, the compound is：
3. the preparation method of logical formula (I) described in claim 1 or logical formula (II) compound, which is characterized in that the logical formula (I) The preparation method of compound includes：
Wherein X-, R it is as defined in claim 1, R1As defined in claim 1, and R1It is not all H；
(1) compound (III) is reacted with R-SO-R or R-S-R generation sulfoniums, and wherein R is independent of each other to be selected from H ,-C1-8Alkane Base, aryl；It is optional later to carry out anion exchange reaction with salt, obtain compound (I-A)；Wherein, X independences be selected from Cl-、 BF4 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、CF3CF2CF2CF2SO3 -、
(2) compound (I-A) and R obtained in above-mentioned steps (1)2OR2、R3Z or CH2=CR5-OR4Reaction, wherein R2For- COOC1-8Alkyl,In one kind, R3、R4Independent optionally-C1-8Alkyl ,-COOC1-8Alkyl ,-C1-8Alkyl-O- C1-8Alkyl ,-C1-8Alkyl-OCO- aryl ,-C1-8Alkyl-OC1-8Alkyl-OCOC1-8Alkyl ,-C1-8Alkyl-OC1-8Alkyl-OCO- Aryl,R5Independent optionally H ,-C1-8Alkyl, Z are halogen；Compound (I-B) is obtained, Wherein, R1It is as defined above, and R1Be not all H, i.e., the logical formula (I) compound that hydroxyl full guard or part are protected.
Alternatively, the preparation method of the logical formula (II) compound includes：
Wherein X-, R it is as defined in claim 1, R1As defined in claim 1, and R1It is not all H；
(1 ') compound (IV) occurs sulfonium with R-SO-R or R-S-R and reacts, and wherein R is independent of each other to be selected from H, C1-8Alkyl, Aryl, it is optional later to carry out anion exchange reaction, generation compound (II-A) with salt；Wherein, X independences be selected from Cl-、 BF4 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、CF3CF2CF2CF2SO3 -、
General formula (II-A) compound and R obtained in (2 ') above-mentioned steps (1 ')2OR2、R3Z or CH2=CR5-OR4Reaction, wherein R2 For-COOC1-8Alkyl,In one kind, R3、R4Independent optionally-C1-8Alkyl ,-COOC1-8Alkyl ,-C1-8Alkyl- O-C1-8Alkyl ,-C1-8Alkyl-OCO- aryl ,-C1-8Alkyl-OC1-8Alkyl-OCOC1-8Alkyl ,-C1-8Alkyl-OC1-8Alkyl- OCO- aryl, R5Independent optionally H ,-C1-8Alkyl, Z are halogen；Obtain compound (II- B), wherein, R1It is as defined above, and R1Be not all H, i.e., the logical formula (II) compound that hydroxyl full guard or part are protected.
4. a kind of positive-tone photo glue composition, the general formula described in claims 1 or 2 including hydroxyl full guard or part protection (I) or (II) compound, the hydroxyl full guard or the logical formula (I) or (II) compound of part protection, refer to logical formula (I) or (II) R in1In it is at least one be non-H groups；
Preferably, the positive-tone photo glue composition also contains photoresist solvent.
5. positive-tone photo glue composition as claimed in claim 4, wherein, the positive-tone photo glue composition, by hydroxyl all risk insurance The logical formula (I) or (II) compound of shield or part protection and photoresist solvent composition.Preferably, the positive-tone photo glue composition Logical formula (I) containing 0.1%~10% (mass ratio) or (II) compound.
6. positive-tone photo glue composition as claimed in claim 4, wherein, the positive-tone photo glue composition is also optionally Contain photoresist, photo-acid generator or sour dispersion inhibitor etc.；Preferably, the positive-tone photo glue composition, containing 1%~ The logical formula (I) of 10% (mass ratio) or (II) compound, the photoresist of 0%~5% (mass ratio), 0%~1% (mass ratio) Photo-acid generator, the sour dispersion inhibitor of 0.001%~0.1% (mass ratio)；
The preferred photo-acid generator includes ionic or non-ionic, such as triphenylsulfonium triflate sulfonate, triphenylsulfonium Perfluoro butyl sulfosalt, two (4- tert-butyl-phenyls) iodine tosilate, N- hydroxynaphthylimide fluoroform sulphonates etc.； The photoresist solvent includes propylene glycol methyl ether acetate (PGMEA), ethyl lactate, glycol monoethyl ether, cyclohexanone etc.；It is described Sour dispersion inhibitor includes n-octyl amine, tri-n-octyl amine, two n-octyl amine of N- methyl, t-octanylamine etc..
7. a kind of negative photo glue composition, including hydroxyl is unprotected or claims 1 or 2 of part protection described in general formula (I) or (II) compound, wherein, above-mentioned hydroxyl is unprotected or the logical formula (I) or (II) compound of part protection, refers to general formula (I) R or in (II)1At least one is H.
Preferably, the negative photo glue composition also contains photoresist solvent.
Preferably, the negative photo glue composition, by hydroxyl it is unprotected or part protection logical formula (I) or (II) compound and Photoresist solvent forms；Preferably, the negative photo glue composition contain 0.1%~10% (mass ratio) logical formula (I) or (II) compound.
Preferably, the negative photo glue composition is also optionally containing photoresist, photo-acid generator, crosslinking agent.It is preferred that , the negative photo glue composition contains the logical formula (I) of 0.1%~10% (mass ratio) or (II) compound, and 0%~5% The photoresist of (mass ratio), the photo-acid generator of 0%~1% (mass ratio), the crosslinking agent of 0.01%~1% (mass ratio).
The preferred photo-acid generator includes ionic or non-ionic, such as triphenylsulfonium triflate sulfonate, triphenylsulfonium Perfluoro butyl sulfosalt, two (4- tert-butyl-phenyls) iodine tosilate, N- hydroxynaphthylimide fluoroform sulphonates etc.； The photoresist solvent includes propylene glycol methyl ether acetate (PGMEA), ethyl lactate, glycol monoethyl ether, cyclohexanone etc.；It is described Crosslinking agent includes tetramethoxymethylglycoluril, bisphenol type epoxy propyl ether etc..
8. any one of compound, the claim 4-6 described positive-tone photo glue composition or power described in claims 1 or 2 Profit requires the application of the negative photo glue composition described in 7, which is characterized in that for 365nm photoetching, 248nm photoetching, 193nm In the photoetching processes such as photoetching, extreme ultraviolet (EUV) photoetching and electron beam lithography (EBL).
9. a kind of photoresist coating, which is characterized in that by claim 4-6 any one of them positive-tone photo glue compositions or power Profit requires the negative photo glue composition described in 7 to carry out spin coating in substrate to obtain.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111302979A (en) * 2020-03-04 2020-06-19 苏州瑞红电子化学品有限公司 Single-component molecular glass and preparation method and application thereof
CN111978228A (en) * 2019-05-22 2020-11-24 中国科学院理化技术研究所 Monomolecular resin acid generator based on sulfonium salt and photoresist composition thereof
WO2022032945A1 (en) * 2020-08-11 2022-02-17 中国科学院化学研究所 Bisphenol a derivative, preparation method therefor, and application thereof in photolithography
CN115707707A (en) * 2021-08-20 2023-02-21 中国科学院理化技术研究所 Thiaxin-based sulfonium salt monomolecular resin and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603707A (en) * 2012-02-10 2012-07-25 中国科学院化学研究所 2,3,4,5,-tetra(3',4'-dihydroxyl phenyl)thiophene and application thereof as MALDI (matrix assisted laser desorption ionization) matrix in analyzing small molecules
CN103304385A (en) * 2012-03-16 2013-09-18 中国科学院化学研究所 Molecular glass photoresist containing bisphenol A skeleton structure as well as preparation method and application thereof
CN103304521A (en) * 2012-03-16 2013-09-18 中国科学院化学研究所 Molecular glass photoresist of taking tetraphenyl furan, tetraphenyl pyrrole, tetraphenylthiophene and quinary phenylpyridine as cores
CN104914672A (en) * 2015-06-11 2015-09-16 中国科学院化学研究所 Bottom anti-reflection coating composition based on molecule glass comprising multiple hydroxy structures and application thereof to photoetching

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603707A (en) * 2012-02-10 2012-07-25 中国科学院化学研究所 2,3,4,5,-tetra(3',4'-dihydroxyl phenyl)thiophene and application thereof as MALDI (matrix assisted laser desorption ionization) matrix in analyzing small molecules
CN103304385A (en) * 2012-03-16 2013-09-18 中国科学院化学研究所 Molecular glass photoresist containing bisphenol A skeleton structure as well as preparation method and application thereof
CN103304521A (en) * 2012-03-16 2013-09-18 中国科学院化学研究所 Molecular glass photoresist of taking tetraphenyl furan, tetraphenyl pyrrole, tetraphenylthiophene and quinary phenylpyridine as cores
CN104914672A (en) * 2015-06-11 2015-09-16 中国科学院化学研究所 Bottom anti-reflection coating composition based on molecule glass comprising multiple hydroxy structures and application thereof to photoetching

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王文君: "化学增幅抗蚀剂用光产酸剂—硫鎓盐的合成方法", 《中国环境管理干部学院学报》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111978228A (en) * 2019-05-22 2020-11-24 中国科学院理化技术研究所 Monomolecular resin acid generator based on sulfonium salt and photoresist composition thereof
WO2020233550A1 (en) * 2019-05-22 2020-11-26 中国科学院理化技术研究所 Sulfonium salt-based monomolecular resin acid generator and photoresist composition thereof
CN111302979A (en) * 2020-03-04 2020-06-19 苏州瑞红电子化学品有限公司 Single-component molecular glass and preparation method and application thereof
WO2022032945A1 (en) * 2020-08-11 2022-02-17 中国科学院化学研究所 Bisphenol a derivative, preparation method therefor, and application thereof in photolithography
CN115707707A (en) * 2021-08-20 2023-02-21 中国科学院理化技术研究所 Thiaxin-based sulfonium salt monomolecular resin and preparation method and application thereof

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