CN108997182A - Photodegradation alkali, containing its photoetching compositions and preparation method thereof - Google Patents
Photodegradation alkali, containing its photoetching compositions and preparation method thereof Download PDFInfo
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- CN108997182A CN108997182A CN201811008056.6A CN201811008056A CN108997182A CN 108997182 A CN108997182 A CN 108997182A CN 201811008056 A CN201811008056 A CN 201811008056A CN 108997182 A CN108997182 A CN 108997182A
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/40—Succinic acid esters
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- 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
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- Materials For Photolithography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application involves a kind of photodegradation alkali containing half fluorine-substituted alkyl group, have through structure shown in the following general formula (I):
Description
Technical field
This application involves photoresist (also referred to as photoresist) technical fields.Specifically, this application involves a kind of light
Decompose alkali, the photoetching compositions comprising the photodegradation alkali and the method for preparing the photodegradation alkali.More specifically, originally
Application is related to the photodegradation alkali containing half fluorine-substituted alkyl group, and comprising it and can be used for the chemistry in semiconductor machining
Scale-up version photo-corrosion-resisting agent composition.
Background technique
With the quickening of global IT application, networking process, the more and more important in the status of IC industry is in integrated electricity
In the manufacturing process of road, the support of photoetching technique plays extremely crucial effect, because photoetching technique directly determines single device
The physical size of part.Photoetching technique, which refers to, is transferred to silicon wafer or other semiconductor chips through illumination for the fine geometric figure on exposure mask
The technical process on surface.Critical material needed for photoetching technique first is that with photochemical reaction activity and have good anti-quarter
The photoresist (photoresist, also referred to as photoresist or photoresist) of corrosion energy.
Photoresist refers to through illumination, can make solubility, meltbility and adhesive force that the etch resistant of significant change occur
High molecular material is mainly used in the Micropicture processing of integrated circuit and semi-conductor discrete device.Photoresist is according to institute
With the difference of exposure light source and radiation source, and ultraviolet light induced resist, deep UV photoresist (DUV), electron beam can be divided into
Resist, x-ray resist, ion beam resist, nano impression resist etc..
Conventional chemical, which amplifies in glue, is added with antalkali (quencher), these neutralizers are evenly distributed in photoetching
In glue, neutralizer itself is insensitive to light.In the region of photoresist light, neutralizer neutralizes the acid that a part exposure generates.
In this process, the effect of neutralizer is exactly the threshold value for improving exposure intensity, influence of the scattering light to imaging is offset, to increase
The chemical imaging contrast of big photoresist, while improving the Storage period (shelf life) of photoresist.
There is a kind of special neutralizer to be referred to as photodegradation alkali (photodecomposable base or
photodecomposable quencher,PDB or PDQ).Photodegradation alkali is a kind of applied to chemical amplification photo etching glue
Photolytic activity additive, it is therefore an objective to improve photoresist performance and photolithographic characteristics, especially be used to improve the contrast of photoresist, to mention
High-resolution.Photodegradation alkali is a kind of Thermodynamically stable chemical combination compound, shows alkalinity in non-exposed area, decomposes in exposure area
Compared at neutral compound or Acidic Compounds (pKa 0 to 5), photodegradation alkali with common alkali, can be improved lithography performance,
Formulation stability and PEB (postexposure bake) delay time.Photodegradation alkali has been applied in photoetching glue formula and photoetching technique
In, especially resolution ratio is in 100nm high-end photoetching glue formula below.Photodegradation alkali is added in the formula of photoresist, with
Include improving the contrast of photoresist convenient for improving photolithographic characteristics, reduces line edge roughness, the preservation to improve photoresist
Period etc..
With the development of technology, more and more photodegradation alkali cpds have been synthesized.Since triphenylsulfonium hydrogen-oxygen in 1996
Compound be applied to the photoresist based on PHS (4-Vinyl phenol) resin of 248nm for the first time after (S.Funato et.al,
, SPIE, 1996, vol.2724,186.) the more and more more excellent photodegradation alkali cpds of people's design and synthesis,
And it is applied to amplification photo etching glue, including 248nm, 193nm, EUV and electron beam resist etc., it is that high-resolution photoresist is indispensable
Few component.
Different types of photodegradation alkali cpd is described in different patents.Such as it describes and contains in US 6492091
There is sulphur father-in-law's salt of the single-stranded carbonic acid of alkyl, symmetrical sulphur father-in-law salt, iodonium salt containing carbonate are described in US20100136477；
Asymmetrical type sulphur father-in-law salt, iodonium salt are described in United States Patent (USP) US8614047, are discussed on light acid in US7923199
It is added and achievees the purpose that reduce acid diffusion containing the alkyl that amino group is added.Pass through in patent application US20140011133A
Chemical bond links up photo-acid generator and photodegradation alkali, reduce light acid diffusion, thus reach reduction high-resolution line width by
It is influenced in diffusion bring, and most of these photodegradation alkali are described in the patent of foreign country.
These photodegradation alkali have application well in various photoresists, with the development to photoresist, these photoresists
Additive is not able to satisfy all demands.For this purpose, this field needs the superior photodegradation alkali of Persisting exploitation performance and its preparation side
Method.
Summary of the invention
The application's is designed to provide a kind of photodegradation alkali containing half fluorine-substituted alkyl group, to solve above-mentioned
In the prior art the technical issues of.The photodegradation alkali of the application not only has the advantages that general photodegradation alkali, also has them not
The some advantages having, such as there is good dissolubility and the compatibility of resin etc. in a solvent.Due to introducing half fluorin radical
Just have very low surface can, there is good distribution performance in the photoresist, due to the additive be straight chain alkyl structure,
It is good with photoresist resin compatible with very high flexibility, there is slower diffusion, the resolution of the photoresist improved
Rate, while containing half fluorine-substituted alkyl group, thus its being more evenly distributed in the photoresist, in high-end photoresist, have
Good lithography performance and application prospect.
The purpose of the application, which also resides in, provides a kind of photoetching compositions comprising above-mentioned photodegradation alkali.
The purpose of the application, which also resides in, provides a kind of method for synthesizing above-mentioned photodegradation alkali.
To achieve the goals above, the application provides following technical proposals.
In the first aspect, the application provides a kind of photodegradation alkali, has through structure shown in the following general formula (I):
Wherein, X1It indicates in symmetrical or asymmetric alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or heteroaryl
Any one or a few；
Wherein, Y1It indicates in symmetrical or asymmetric alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or heteroaryl
Any one or a few, and H atom all in Y1 structure is not all replaced by F atom；
Wherein, Z1It indicates in symmetrical or asymmetric alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or heteroaryl
Any one or a few, and H atom all in Z1 structure is all replaced by F atom；And
Wherein, M+With structure shown in the following general formula (II), logical formula (III) or logical formula (IV):
In logical formula (II), group R1、R2And R3Each independently represent alkyl, naphthenic base, aryl, miscellaneous alkyl, heterocycle alkane
Any one or a few in base or heteroaryl；Or R1And R2It can be with same R1The sulphur atom of bonding is combined together to be formed and have 2
To the Heterocyclylalkyl of 7 carbon atoms；
In logical formula (III), group R4And R5Each independently represent alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl
Or any one or a few in heteroaryl；
In logical formula (IV), group R6Indicate appointing in alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or heteroaryl
Meaning is one or more of；And L indicates C3-C20Alicyclic hydrocarbon group alicyclic hydrocarbon group.
In a kind of embodiment of first aspect, M+Including but not limited to following structures:
In a kind of embodiment of first aspect, X1Including but not limited to following structures:
In a kind of embodiment of first aspect, X1Carbon atom number be 1 to 20.
In a kind of embodiment of first aspect, Y1Carbon atom number be 1 to 20.
In a kind of embodiment of first aspect, Z1Carbon atom number be 1 to 20.
In a kind of embodiment of first aspect, Y1Including but not limited to following structures:
In a kind of embodiment of first aspect, at least one CH of alicyclic hydrocarbon group L2Group by below a kind of or
A variety of substitutions: C3-C20Naphthenic base, C3-C20Alicyclic hydrocarbon group, C6-C20Aromatic hydrocarbon group, hydroxyl, cyano, nitro or halogen family member
Element.
In a kind of embodiment of first aspect, anion part includes but is not limited to following structures:
In second aspect, the application provides a kind of photoetching compositions comprising photodegradation as described in relation to the first aspect
Alkali.
It in a kind of embodiment of second aspect, is counted on the basis of weight percent, the photoetching compositions include
Photodegradation alkali greater than 0 and less than 30%.
In a third aspect, the application provides a kind of method for preparing photodegradation alkali, and the method may include following step:
S1: under inert gas protection, reacting dicarboxylic anhydride or diacid with fluorine alcohol, obtains monoesters acid；
S2: the monoesters acid is neutralized with alkali metal hydroxide or alkali metal carbon hydride, obtains alkali metal monoesters acid
Salt；
S3: it reacts alkali metal monoesters hydrochlorate with the halogenation sulfonium that aryl replaces, obtains photodegradation alkali.
In a kind of embodiment of the third aspect, the dicarboxylic anhydride includes succinic anhydride and/or glutaric anhydride.
In a kind of embodiment of the third aspect, the diacid includes succinic acid and/or glutaric acid.
In a kind of embodiment of the third aspect, the halogenation sulfonium that the aryl replaces includes three (4- aminomethyl phenyl) brominations
Sulfonium.
Compared with prior art, the beneficial effects of the present application are as follows the photodegradation alkali of the application has very well in the photoresist
Distribution performance, and have very high flexibility, it is good with photoresist resin compatible, have very slow diffusion, improve
Photoresist resolution ratio, in high-end photoresist, have good lithography performance.
Specific embodiment
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
It is all based on weight with percentage, and test and characterizing method used is all synchronous with the submission date of the application.It is being applicable in
In the case where, any patent, patent application or disclosure involved in the application are fully incorporated in this as reference, and its
Patent families of equal value are also introduced into as reference, about the synthetic technology in this field, product disclosed by these special documents
With the definition of fabrication design, polymer, comonomer, initiator or catalyst etc..If the specific art disclosed in the prior art
Defining for language is inconsistent with any definition provided herein, then term provided herein of being subject to defines.
Digital scope in the application is approximation, therefore unless otherwise stated, it may include the number other than range
Value.Numberical range include with the increased all numerical value from lower limit value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between any high value.For example, if compositional, physics or other property (such as molecules
Amount, melt index (MI) etc.) it is 100 to 1000, it is meant that clearly list all single numbers, such as 100,101,102 etc., with
And all subranges, such as 100 to 166,155 to 170,198 to 200 etc..For comprising the numerical value less than 1 or comprising big
In the range of 1 score (such as 1.1,1.5 etc.), then suitably regard 1 unit as 0.0001,0.001,0.01 or 0.1.
For the range comprising the units less than 10 (such as 1 to 5), usually regarding 1 unit as 0.1., these are only intended to table
The specific example of the content reached, and all possible combination of the numerical value between cited minimum and peak is all recognized
In this application for clear record.Numberical range in the application particularly provides various comonomers in acrylate copolymer
In content, content of the various components in photoetching compositions, temperature and these components when acrylic ester synthesizing it is each
Kind feature and property.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, whole isomers that " hexane " either individually or collectively includes hexane).In addition, unless explicitly stated otherwise, otherwise using
"one", the noun that "an" or "the" are described also includes its plural form.
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise in the application it is all use term "comprising"s, " comprising ", or " having " composition may include appoint
What additional additive, auxiliary material or compound.On the contrary, in addition to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
Separate member listed or any combination thereof.
Term definition
As used herein, term " composition " indicates the mixture or blend of two or more components.
As used herein, term " alkyl " refers to forms after the hydrogen atom or group that alkane structure eliminates a monovalence
Substituent group.
As used herein, term " naphthenic base " refers to the alkyl including cyclic structure.
As used herein, term " C3-C20Naphthenic base " refers to that carbon atom number is 3 to 20 naphthenic base.In this application,
Indicate that group includes m to n carbon atoms by " Cm-Cn ".
There is undefined other terms such as aryl, miscellaneous alkyl, Heterocyclylalkyl and heteroaryl etc. this field usually to manage
The meaning of solution.
Embodiment
Below in conjunction with the embodiment of the present invention, clear and complete description is carried out to technical solution of the present invention.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.
Embodiment 1
Synthesis step 1:
Succinic anhydride 2.2g is weighed in the anhydrous three-necked flask of drying of 250ml, in inflated with nitrogen 10min rear substitution flask
Dry ethylene glycol dimethyl ether 80ml, pyridine 0.15ml, heating are added into reaction system for a small amount of moisture in air and reaction system
To after 75 DEG C, ten trifluoro n-octyl alcohol 7.28g and 40ml glycol dimethyl ethers are gradually added dropwise into reaction system, adition process is protected
The temperature for demonstrate,proving reaction system controls after 65-75 DEG C, addition, stops instead after keeping reaction temperature 75 DEG C of reactions 18h, 18h
It answers.
After reaction, a certain amount of saturation NaHCO is added into reaction system3, succinate monoester acid is converted to sodium salt
It is soluble in water.Then a certain amount of ethyl acetate is poured into reaction system, unreacted fluorine alcohol, succinic anhydride and reaction generate
Succinic acid dibasic acid esters is dissolved in organic phase, and monoesters acid is soluble in the aqueous phase, isolated water phase.
Obtained water phase is placed in ice-water bath, after concentrated hydrochloric acid acidification, after certain ethyl acetate extraction is added, extract liquor
After a certain amount of anhydrous magnesium sulfate drying is added, vacuum distillation obtains purer succinate monoester acid.
Synthetic route is as follows:
Synthesis step 2:
The succinate monoester acid of the above-mentioned synthesis of 4.86g is weighed in the flask of 250ml, triethylamine 1.11g is added, is added
3.85g tri- (4- aminomethyl phenyl) bromination sulfonium (CAS:3744-11-4), 40ml methylene chloride, 20ml water, (keep away under normal temperature environment
Light) be stirred to react 3h after, settle and separate obtains organic phase, to it is organic be added to a certain amount of 1% dilute hydrochloric acid neutralize after, separation
A certain amount of deionized water is added in water phase out, after stirring 30min, separates water phase, washing is three times, dense by organic phase rotary evaporation
Required product is obtained after contracting.
Synthetic route is as follows:
Synthesize example 2:
Synthesis step 1:
Glutaric anhydride 2.50g is weighed in the anhydrous three-necked flask of drying of 250ml, inflated with nitrogen 10min rear substitution flask
In a small amount of moisture of air neutralization reaction system, dry ethylene glycol dimethyl ether 80ml, pyridine are added into reaction system
0.15ml after being warming up to 75 DEG C, seven fluorine n-octyl alcohol 4.00g and 40ml glycol dimethyl ethers is gradually added dropwise into reaction system, add
Enter process and guarantee that the temperature of reaction system controls after 65-75 DEG C, addition, keeps reaction temperature 75 DEG C of reactions 18h, 18h
Stop reaction afterwards.
After reaction, a certain amount of saturation NaHCO is added into reaction system3, glutaric acid monoester acid is converted to sodium salt
It is soluble in water.Then a certain amount of ethyl acetate, unreacted fluorine alcohol, glutaric anhydride and generation penta 2 are poured into reaction system
Acid diester is dissolved in organic phase, during target product is soluble in the aqueous phase, isolated water phase.
Obtained water phase is placed in ice-water bath, after the acidification of enriching hydrochloric acid, after certain ethyl acetate extraction is added, extraction
After a certain amount of anhydrous magnesium sulfate drying is added in liquid, vacuum distillation obtains purer glutaric acid monoester acid.
The synthetic route of the step is as follows:
Synthesis step 2:
The 3.14g monoesters acid for weighing above-mentioned synthesis obtains after adding the sodium hydrate aqueous solution of 10% concentration equimolar amounts to neutralize
To monoesters acid sodium-salt.
Synthetic route is as follows:
Synthesis step 3:
Successively weigh the monoesters acid sodium-salt of 3.85g tri- (4- aminomethyl phenyl) bromination sulfonium (CAS:3744-11-4), above-mentioned synthesis
3.53g, methylene chloride 80ml, water 40ml the stirring at normal temperature 18h in the three-necked flask of 250ml, when standing one section after reaction
Between after, isolated organic phase after being washed with deionized organic phase 3 times, obtains institute in being concentrated by evaporation on Rotary Evaporators
Need product.
Synthetic route is as follows:
Embodiment 3
Synthesis step 1:
Sequentially add 13.0g (111mmol) succinic acid into the three-necked flask of 500ml, 6.78g (55.5mmol) DMAP,
10.6g (55.5mmol) EDCl, 300ml methylene chloride, stirring at normal temperature dissolved clarification；Nine fluorine n-amyl alcohol of 13.88g is dissolved in 150ml
In methylene chloride, after stirring dissolved clarification；In the solution for the succinic acid that the dissolved clarification solution of nine fluorine n-amyl alcohols is poured slowly into above-mentioned preparation,
After addition, after being mixed evenly, under room temperature, reaction is for 24 hours；After reaction, add dilute hydrochloric acid to stop reaction, isolated
After machine phase, concentration.Purification passed through chromatographic column, isolated monoesters acid.
Synthetic route is as follows:
DMAP and EDCl structure is as follows:
Synthesis step 2:
The 3.5g (10mmol) for weighing above-mentioned synthesis is added in 50g deionized water, with 10% concentration equimolar amounts
After NaOH is neutralized, it is slowly added to the AgNO of 10% concentration equimolar amounts3Solid product is obtained by filtration in solution after completion of the reaction.It will
It is spare after obtained solid drying.
Synthetic route is as follows:
Synthesis step 3:
(4- aminomethyl phenyl) the bromination sulfonium of 3.85g tri- (CAS:3744-11-4) is weighed in the three-necked flask of 250ml, is weighed
80ml methylene chloride, 40ml deionized water is added in upper in above-mentioned 250ml flask in the monoesters acid silver salt 4.57g of above-mentioned synthesis
It states after being uniformly mixed in flask, after stirring 2h is protected from light under room temperature, after filtrate is obtained by filtration, is spin-dried in Rotary Evaporators
To yellow viscous liquid, methyl tertiary butyl ether(MTBE) 30ml is added, after being washed three times with methyl tertiary butyl ether(MTBE), spin concentration obtains Huang
Color thick liquid, as product.
Synthetic route is as follows:
Embodiment 4
Synthesis step 1:
Weigh succinic anhydride (2.1g, 21m mol), tetrahydrofuran (2ml), triethylamine (0.05ml), nine fluorine n-amyl alcohols
(5.0g, 20m mol) in four mouthfuls of upper bottles of dry 50m, under nitrogen protection, stirring is warming up to 100 DEG C, after reacting 2h,
It is cooled to 30 DEG C.In the reaction solution that 20ml deionized water is added, stirring continues cooling down to 15 DEG C, and it is solid that filtering obtains white
Body (6.4g, yield 90%).
The synthetic route of the step is as follows:
Test the infrared spectroscopy, hydrogen spectrum nuclear magnetic resoance spectrum and F of products therefrom19Nuclear magnetic resoance spectrum, as a result as follows: institute
The equipment and instrument used is as follows:
Infrared (FT-IR): infrared gear model: the silent winged NICOLET IS5 membrane process test of match
Hydrogen spectrum (1H NMR):1H NMR model: test equipment Brooker DRX-400 solvent C DCl3
Fluorine spectrum (19F NMR):19F NMR model: test equipment Brooker DRX-400 solvent C DCl3
FT-IR (KBr, Vmax/cm-1): 2981,2869,1726,1698,1423,1314,1233,1196,1141,
1078,919；
1H NMR(CDCl3)(δ,ppm):4.5-4.7(-CH2-CF2-),2.5-2.8(-CO-CH2CH2-CO-)；
19F NMR(CDCl3) (δ, ppm): 118-127 (- CF2-CF2-CF2-),80.7-81.2(CF3-)。
Synthesis step 2:
Weigh 0.84g (10mmol) NaHCO3It is added in 15g water, after being uniformly dissolved, weighs 3.85g (10mmol) above-mentioned conjunction
The monoesters acid synthesized at step 1 is spare after neutralization in above-mentioned solution.
The synthetic route of the step is as follows:
Synthesis step 3:
(4- aminomethyl phenyl) the bromination sulfonium of 3.85g tri- (CAS:3744-11-4) is weighed in the three-necked flask of 250ml, is added
In and good 2 acquired solution of synthesis step in the three-necked flask of 250ml, add deionized water 25ml, 40ml dichloromethane be added
Alkane after being uniformly mixed, after stirring 2h is protected from light under room temperature, isolates organic phase, after being washed with deionized three times, Yu Xuan
Turn to be spin-dried in evaporimeter, light yellow viscous liquid (yield 65%) is obtained after being spin-dried for.
By obtained yellow viscous liquid survey infrared (IR) and nuclear-magnetism (1H NMR and19F NMR), as follows:
Infrared (FT-IR): the silent winged NICOLET IS5 membrane process test of infrared gear match
Hydrogen spectrum (1H NMR):1H NMR test equipment Brooker DRX-400 solvent C DCl3
Fluorine spectrum (19F NMR):19F NMR test equipment Brooker DRX-400 solvent C DCl3
IR (KBr, Vmax/cm-1): 3440,3081,3041,2971,2921,2887,1762,1637,1589,1491,
1447,1352,1187,1131,1072,811,505；
1H NMR(CDCl3) (δ, ppm): 7.6-7.95 ((- C6H4)3S+),4.5-4.7(-CF2-CH2-),2.5-2.8(-
CO-CH2CH2-CO-),2.4-2.5(CH3-)；
19F NMR(CDCl3)(δ,ppm):118-127(-CF2-CF2-CF2-),80.7-81.2(CF3-)。
The synthetic route of the step is as follows:
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying creative labor.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and modifies within all scope of the present application.
Claims (11)
1. a kind of photodegradation alkali has through structure shown in the following general formula (I):
Wherein, X1Indicate appointing in symmetrical or asymmetric alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or heteroaryl
Meaning is one or more of；
Wherein, Y1Indicate appointing in symmetrical or asymmetric alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or heteroaryl
Meaning is one or more of, and H atom all in Y1 structure is not all replaced by F atom；
Wherein, Z1 indicates appointing in symmetrical or asymmetric alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or heteroaryl
Meaning is one or more of, and H atom all in Z1 structure is all replaced by F atom；And
Wherein, M+ has the following general formula (II), leads to structure shown in formula (III) or logical formula (IV):
In logical formula (II), group R1、R2And R3Each independently represent alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or
Any one or a few in heteroaryl；Or R1And R2It can be with same R1The sulphur atom of bonding is combined together to be formed and have 2 to 7
The Heterocyclylalkyl of a carbon atom；
In logical formula (III), group R4And R5Each independently represent alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or miscellaneous
Any one or a few in aryl；
In logical formula (IV), group R6Indicate any one in alkyl, naphthenic base, aryl, miscellaneous alkyl, Heterocyclylalkyl or heteroaryl
Kind is several；And L indicates alicyclic hydrocarbon group.
2. photodegradation alkali as described in claim 1, which is characterized in that M+Including but not limited to following structures:
3. photodegradation alkali as described in claim 1, which is characterized in that X1Including but not limited to following structures:
4. photodegradation alkali as described in claim 1, which is characterized in that X1Carbon atom number be 1 to 20；And/or Y1Carbon it is former
Subnumber is 1 to 20；And/or Z1Carbon atom number be 1 to 20.
5. photodegradation alkali as described in claim 1, which is characterized in that Y1Including but not limited to following structures:
6. photodegradation alkali as described in claim 1, which is characterized in that at least one CH of alicyclic hydrocarbon group L2Group is by following
One or more substitutions: C3-C20Naphthenic base, C3-C20Alicyclic hydrocarbon group, C6-C20Aromatic hydrocarbon group, hydroxyl, cyano, nitro or
Halogen.
7. photodegradation alkali as described in claim 1, which is characterized in that its anion part includes but is not limited to following structures:
8. a kind of photoetching compositions comprising such as photodegradation alkali of any of claims 1-7.
9. photoetching compositions as claimed in claim 8, spy are, counted on the basis of weight percent, the photoresist
Composition includes being greater than 0 and the photodegradation alkali less than 30%.
10. a kind of method for preparing photodegradation alkali, the method includes the following steps:
S1: under an inert atmosphere, reacting dicarboxylic anhydride or diacid with fluorine alcohol, obtains monoesters acid；
S2: the monoesters acid is neutralized with alkali metal hydroxide or alkali metal carbon hydride, obtains alkali metal monoesters hydrochlorate；
S3: it reacts alkali metal monoesters hydrochlorate with the halogenation sulfonium that aryl replaces, obtains photodegradation alkali.
11. the method for preparation photodegradation alkali as claimed in claim 10, which is characterized in that the dicarboxylic anhydride includes succinic anhydride
And/or glutaric anhydride；
And/or the diacid includes succinic acid and/or valeric acid；
And/or the halogenation sulfonium that the aryl replaces includes three (4- aminomethyl phenyl) bromination sulfoniums.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811008056.6A CN108997182A (en) | 2018-08-31 | 2018-08-31 | Photodegradation alkali, containing its photoetching compositions and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811008056.6A CN108997182A (en) | 2018-08-31 | 2018-08-31 | Photodegradation alkali, containing its photoetching compositions and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
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| JP2020117490A (en) * | 2019-01-22 | 2020-08-06 | 住友化学株式会社 | Carboxylate salt, resist composition, and method for producing resist pattern |
| JP2021103233A (en) * | 2019-12-25 | 2021-07-15 | 東京応化工業株式会社 | Resist composition and resist pattern forming method |
| CN115947657A (en) * | 2022-12-26 | 2023-04-11 | 徐州博康信息化学品有限公司 | A kind of fluorine-containing photoresist resin monomer and preparation method thereof |
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| JP2020117490A (en) * | 2019-01-22 | 2020-08-06 | 住友化学株式会社 | Carboxylate salt, resist composition, and method for producing resist pattern |
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| JP2021103233A (en) * | 2019-12-25 | 2021-07-15 | 東京応化工業株式会社 | Resist composition and resist pattern forming method |
| CN115947657A (en) * | 2022-12-26 | 2023-04-11 | 徐州博康信息化学品有限公司 | A kind of fluorine-containing photoresist resin monomer and preparation method thereof |
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