CN103012227A - Sulfonium salt photo-acid generator having high photo-acid generation quantum yield, and preparation method and application thereof - Google Patents
Sulfonium salt photo-acid generator having high photo-acid generation quantum yield, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a sulfonium salt photo-acid generator having a high photo-acid generation quantum yield, and a preparation method and application thereof. The photo-acid generator compound provided by the invention is shown in the specification, wherein R1 is methyl, benzyl, pentafluorophenyl or 4-cyanobenzyl; and R2 is trifluoromethanesulfonate, hexafluorophosphate, hexafluoroantimonate or tetrafluoroborate. The PAG provided by the invention is suitable to serve as a photoactive component of photoresist for the imaging from an ultraviolet region (such as 365nm, 385nm, 405nm and 425nm) to a near visible light region. Such photo-acid generator is simple in synthesis steps, easy to purify and high in yield; and when being used for a photoresist system in the region of 365-425nm, such photo-acid generator can be prepared into photoresist having excellent property, reflects a photo-acid generation quantum yield of 0.3-0.6 and has high photoexcitation efficiency and high catalytic activity.
Description
Technical field
The present invention relates to a kind of high photogenerated acid quantum yield sulfosalt class photo-acid agent, preparation method and application thereof.
Background technology
Photoresist material is to suprabasil photosensitive film with image transfer.They form the negative or positive image.After being coated in photoresist material in the substrate, seeing through figuratum mask or light shield coating is exposed to such as UV-light, under the activation energy of near visible, in photoetching agent pattern, form sub-image.For activating radiation, light shield has opaque zone and transparent zone, has determined to transfer to the image of following substrate.By with the sub-image pattern development in the photoresist coating, obtained three-dimensional image.
Photo-acid agent is the important component in the photoresist material system, and photo-acid agent is a kind of efficient chemical amplification agent that is developed the eighties in 20th century.It can be by absorbing the photon energy generation proton that dissociates, thereby cause the variation of exposure area physicochemical property.Because the sour mechanism of this product is extraneous controlled, and this chemical amplification effect can improve photochemically reactive speed greatly, so photo-acid agent has been widely used in photoresist material in recent years, Computer To Plate is in the numerous areas such as acid polymerization and lucifuge indicator as [201010625168.3] etc.A sulfosalt type photo-acid agent conduct large class is wherein used widely by people, and various method of modifying also emerge in an endless stream.After the photoresist coating exposure that will contain photo-acid agent, select the cracking blocking group, polar functional group is provided, for example carboxyl, phenol or imines, this causes in photoresist coating exposure and the different solvability of unexposed zone formation.
Summary of the invention
The object of the invention is to a kind of high photogenerated acid quantum yield sulfosalt class photo-acid agent, preparation method and application thereof.
The isomers that contains the para-orientation in this class photo-acid agent and 201010284441 of the present invention is compared, and can provide preferably lithographic results after being made into photoresist material.Referring to following embodiment 6 for example, 7 result.
A kind of high photogenerated acid quantum yield sulfosalt class photo-acid agent that the present invention proposes, the structural formula of described photo-acid agent is as follows:
R wherein
1For in methyl, benzyl, phenyl-pentafluoride base or the 4-cyano group benzyl any; R
2 -Be gegenion.
Among the present invention, described R
2 -For in trifluoromethayl sulfonic acid root, hexafluoro-phosphate radical, hexafluoroantimonic anion or the tetrafluoroborate any.
The preparation method of the high photogenerated acid quantum yield sulfosalt class photo-acid agent that the present invention proposes, concrete steps are as follows:
(1) under protection of inert gas, with 2.67g, 10mmol N, N-pentanoic benzaldehyde is dissolved in the anhydrous tetrahydro furan, and adds 5.36g, 15mmol methyltriphenylphospbromide bromide phosphorus, 0
oDrip the 3.6g that is dissolved in tetrahydrofuran (THF) under the C, the 30mmol potassium tert.-butoxide, keeping system temperature is 0
oC ~ 10
oC; Be warming up to room temperature after dripping, stirring reaction 3 ~ 6 hours, reaction soln is poured into water, dichloromethane extraction, salt water washing, organic phase anhydrous sodium sulfate drying, column chromatography obtains liquid, after desolventizing, vacuum obtains white powder product (2.168g, 8mmol) N, N-hexichol amido vinylbenzene;
(2) under the protection of inert gas, with step (1) product 2.71g, 10mmol N; N-hexichol amido vinylbenzene adds in the 33mL trolamine, adds 2.03g, 10mmol 3-bromobenzene dimethyl sulfide and 40mg again; 0.18mmol palladium is heated with stirring to 100 ~ 120
oC, lucifuge stirs, and reacts after 10 ~ 12 hours, is poured into water to produce blackish green solid, filter, the solid that filtration is obtained is dissolved in the methylene dichloride, removes palladium through filtered through silica gel, and filtrate desolventizes rear acquisition thick liquid, purify through column chromatography, obtain faint yellow solid product 2.87g, 7mmol 3-(N, N-hexichol amido styryl) thioanisole; Wherein: the eluent that adopts in the column chromatography is the mixed solution of cyclohexane and ethyl acetate, and the volume ratio of hexanaphthene and ethyl acetate is 10/1 ~ 5/1;
(3) with step (2) product 3-(N, N-hexichol amido styryl) thioanisole is dissolved in the anhydrous methylene chloride, in dry ice acetone bath, add the trifluoro-methane sulfonic acid silver of 1.5 times of amounts and halogenated alkane or the halogenated aryl hydrocarbon of 1.5 times of amounts, lucifuge stirs after 0.5 ~ 1 hour and removes freezing plant, the desolventizing after 20 ~ 24 hours of lucifuge stirring at room, add the acetonitrile dissolving, the filtering undissolved solid, concentrated solution is added dropwise in the anhydrous diethyl ether, produce yellow mercury oxide, filter to such an extent that be dissolved in acetone after the precipitation, be added dropwise in the saturated aqueous solution of inorganic salt, produce yellow mercury oxide, obtain yellow powder after filtering, be required product.
Among the present invention, rare gas element is nitrogen described in step (1) and the step (2).
Among the present invention, halogenated alkane described in the step (3) adopts methyl iodide; Halogenated aryl hydrocarbon can adopt in benzyl bromine, 4-cyano group benzyl bromine or five fluorobenzyl bromides etc. any.
Among the present invention, the saturated aqueous solution of inorganic salt described in the step (3) be in phosphofluoric acid potassium solution, hexafluoro-antimonic acid sodium solution or the Tetrafluoroboric acid sodium solution any.
Among the present invention, the ratio of anhydrous diethyl ether and acetonitrile solution is the ether volume in the step (3): the acetonitrile solution volume is 10:1.
Among the present invention, the saturated aqueous solution of inorganic salt and the ratio of acetone soln are the saturated aqueous solution volume in the step (3): the acetone soln volume is 25:1.
The application of high photogenerated acid quantum yield sulfosalt class photo-acid agent of the present invention in photoresist material.
Among the present invention, described high photogenerated acid quantum yield sulfosalt class photo-acid agent is applied to form the photoresist material camegraph, and step is as follows:
(1) at slide glass or silicon chip coating photoetching compositions film;
(2) heating, drying is removed solvent on hot platform;
(3) with the photographic developer flash trimming;
(4) with the light source irradiation photoresist film, described optical source wavelength is 365nm～425nm;
(5) baking photoresist material after;
The film that (6) will shine with developing solution develops;
(7) cleaning and dry.
Photoresist material of the present invention is in accordance with known methods preparation generally, and except replacing existing Photoactive compounds of filling a prescription for this class photoresist material with PAG of the present invention, and PAG photogenerated acid ability of the present invention is stronger, sees embodiment 5.
Beneficial effect of the present invention is: this type of photo-acid agent synthesis step is simple, be easy to purify, productive rate is high, in 365nm～425nm zone, this type of photo-acid agent is used for the photoresist material that the photoresist material system can be prepared excellent property, embody 0.3～0.6 photogenerated acid quantum yield, optical excitation efficient is high, and catalytic activity is high.
Description of drawings
Fig. 1 SU-8 2005 rotating speeds-thickness relationship figure.
The photo-acid agent of Fig. 2 difference amount of mixing in photoresist material relative hydrogen ion content and the relation between the exposure dose.
The pattern that Fig. 3 mask plate obtains at microscopically, (a) and (b) are the image under the different amplification.
The pattern that Fig. 4 photoengraving pattern obtains under scanning electron microscope, (a) and (b), (c), (d) they are respectively the patterns under the different amplification, wherein, (a) and (b), (c) they are vertical views, (d) are sectional views.
The pattern that Fig. 5 mask plate obtains at microscopically, (a) and (b) are the image under the different amplification.
The pattern that Fig. 6 photoengraving pattern obtains under scanning electron microscope, (a) and (b), (c), (d) they are respectively the patterns under the different amplification, wherein, (a) and (b) are vertical views, (c), (d) be sectional view.
Embodiment
The preferred photo-acid agent compound of the present invention comprises following 1-4 compound.
Among these compounds 1-4, R
2 -Be trifluoromethayl sulfonic acid root, hexafluoro-phosphate radical, hexafluoroantimonic anion or tetrafluoroborate.
The concrete preparation method of photo-acid agent in the photoetching compositions of the present invention (following with specific examples as to further instruction of the present invention, but should not regard limitation of the invention as).
In the invention, parent material is N, and N-pentanoic benzaldehyde obtains intermediate N, N-hexichol amido vinylbenzene by the Wittig reaction; React intermediate N by Heck, N-hexichol amido vinylbenzene and 3-bromobenzene dimethyl sulfide carry out coupling again, and then obtain the photo-acid agent of triphen amine; Described R
1Be 4-cyano group benzyl, R
2For hexafluoro-phosphate radical is example, the used synthetic route of this preparation method is expressed as follows:
In the formula:
I: methyltriphenylphospbromide bromide phosphorus, potassium tert.-butoxide, tetrahydrofuran (THF), room temperature was reacted 4 hours;
Ii: palladium, trolamine, 3-bromobenzene dimethyl sulfide, reacted 12 hours by 120 ℃;
Iii: trifluoro-methane sulfonic acid silver, 4-cyano group benzyl bromine, methylene dichloride, room temperature, Potassium Hexafluorophosphate reacted 24 hours.
1. prepare N, N-hexichol amido vinylbenzene
Under nitrogen protection, with 10gN, N-pentanoic benzaldehyde dissolves in the anhydrous tetrahydro furan of 250mL, and drops into 17.5g methyltriphenylphospbromide bromide phosphorus, places ice bath to stir.When being cooled to 0 ℃ of left and right sides, system drips at a slow speed the tetrahydrofuran (THF) that 40mL is dissolved with 4.6 gram potassium tert.-butoxides.System maintains below 10 ℃.After dripping system is warming up to room temperature, stirred 4 hours, thin plate chromatography detection reaction finishes.Afterwards mixing solutions is toppled in the entry, use dichloromethane extraction, and use the salt water washing, column chromatography for separation obtains colourless liquid after the anhydrous sodium sulfate drying organic phase.Obtain the white powder product after the solvent removed in vacuo and be N, N-diphenyl benzene ethene, productive rate: 70%.Nuclear magnetic data is consistent with report.
2. prepare target photo-acid agent precursor
With 1.2g N, N-diphenyl benzene ethene, 1.0g 3-bromobenzene dimethyl sulfide, the 20mg palladium adds in the 25mL trolamine, and system vacuumizes logical nitrogen totally three times.Under nitrogen atmosphere, be heated to 100 ℃, lucifuge stirred 12 hours.Thin plate chromatography detection reaction finishes, system is poured into water, produce blackish green solid, collect solid and it is dissolved in the methylene dichloride, remove the insoluble substances such as palladium by filtered through silica gel, obtain the glassy yellow clear liquid, obtain yellow thick liquid after the desolventizing, remove unreacted impurity (eluent: cyclohexane/ethyl acetate=9/1), obtain faint yellow solid through column chromatography, be target photo-acid agent precursor, productive rate: 69.3%.
1H?NMR?(CDCl
3,?δ
ppm):?2.515?(s,?3H,?CH
3);?6.960?(d,?1H,?C
2H
2);?7.032~7.190?(m,?6H,?PhH)?;?7.101?(m,?6H,?PhH)?;?7.240~7.280?(m,?4H,?PhH)?;?7.365~7.86?(m,?3H,?PhH).
3. prepare the target photo-acid agent
284 mg photo-acid agent precursors are dissolved in the 15mL anhydrous methylene chloride, will be cooled to-78 ℃ in system placement and the dry ice acetone bath, add afterwards equimolar trifluoro-methane sulfonic acid silver and 4-cyano group benzyl bromine under the lucifuge condition, low temperature stirred 1 hour.Remove afterwards dry ice acetone bath, stirred 24 hours under the room temperature lucifuge condition.Thin plate chromatography detection reaction finishes, and with the methylene dichloride evaporate to dryness, with acetonitrile dissolving, elimination solid impurity, concentrated solution, the ether sedimentation with 10 times of volumes gets product, is the photo-acid agent that trifluoro-methanyl sulfonate is negatively charged ion.If directly carry out salt exchange (twice), the crude product sulfosalt is dissolved in a small amount of acetone, it is slowly splashed in the saturated phosphofluoric acid aqueous solutions of potassium of 25 times of volumes of stirring.Precipitation is arranged, filter, drying gets yellow powder 329mg, is the target product that hexafluorophosphate is negatively charged ion.Overall yield is: 69.8%.
1H?NMR(CDCl
3,?δ
ppm):?3.2462?(s,?3H,?CH
3);?4.7812?(q,?2H,?CH
2);?7.0106(q,?2H,?CH=CH);?7.0547~7.8770(m,?22H,?PhH)。
Embodiment 2
Identical with embodiment 1 preparation method, just at preparation N, in the cinnamic process of N-hexichol amido, under nitrogen protection, divide to add solid potassium tert-butoxide to system three times, and should fully stir after adding at every turn, so that system temperature is not higher than 10 ℃.
Embodiment 3
Identical with embodiment 1 preparation method, just when the preparation precursor, change solvent into DMF and triethylamine, all the other steps are constant, then synthesize identical precursor after processing.
Embodiment 4
Identical with embodiment 1 preparation method, just at the preparation target product be, 4-cyano group benzyl bromine is replaced to methyl iodide or the cylite of equivalent, all the other steps are constant, then synthesize the target photo-acid agent that methyl or benzyl replace after processing.
Embodiment 5
The various photo-acid agents of preparing are dissolved in the dry acetonitrile, be that light source adds narrow ripple pass filter and excites various photo-acid agent solution with low pressure mercury lamp, with the light intensity of light intensity instrumentation amount by spectral filter, with rhodamine B as sour indicator, as calculated, various compounds all show very high photogenerated acid quantum yield.Be that photogenerated acid quantum yield under exciting is 0.56 with the substituent target product of 4-cyano group benzyl at the 404nm visible light wherein.
Embodiment 6
Identical with embodiment 1 preparation method, just at the preparation target product be, 4-cyano group benzyl bromine is replaced to methyl iodide or the cylite of equivalent, all the other steps are constant, then synthesize the target photo-acid agent that methyl or benzyl replace after processing.
Embodiment 7 lithography process flow processs
(1) pre-treatment of substrate generally is with silicon chip or the sheet glass H at 85 ℃
2SO
4: H
2O
2Soaked one hour in the=7:3 solution, then immerse volume ratio and be that 5min removes the substrate surface zone of oxidation in 80 ℃ of aqueous solution of water 37% hydrochloric acid of 5:1:1 and hydrogen peroxide, immerse again that 5min carries out hydroxylating in 80 ℃ of aqueous solution of the water ammoniacal liquor of volume ratio 6:1:1 and hydrogen peroxide.The substrate of hydroxylating is put into silane coupling agent process, assemble 12h under the room temperature, dry after the ultrasonic cleaning, can obtain being deposited on suprabasil siloxanes organic monolayer.
(2) film.With the photoresist material for preparing, can use sol evenning machine to carry out film forming.Concerning SU-8 2005 glue, the rotating speed corresponding relation between thickness and the sol evenning machine rotating speed can be with reference to table 1.
(3) flash trimming.In the spin-coating process, photoresist material may be piled up at the edge of substrate, for better with the contacting of mask, can use cotton balls to dip a small amount of photographic developer or CH
3Cl
3The place is piled up at the edge wipe, reach the purpose of flash trimming.
(4) front oven dry.The main purpose of front oven dry is in order to remove the solvent in the SU-8 glue, and the front drying time of respective thickness can be with reference to table 1.
(5) exposure.What we adopted is that wavelength is the light source of 405nm, and exposure energy corresponding to respective thickness is referring to table 2.Long when the time shutter, may cause excessively crosslinkedly, so that the SU-8 glue of part can't be removed is clean, when exposure energy is not enough, may cause the crosslinked not thorough of film in the process of developing, be easy to cause coming off of film in the process of development.And it is also different that different photo-acid agents produces protogenic ability, the ratio of mixing of photo-acid agent has a great impact producing the acid amount too, we have studied the sour ability of life of the photo-acid agent that mixes different types of photo-acid agent and different percentage compositions in photoresist material, referring to Fig. 2, can the ratio of mixing of exposure dose and photo-acid agent be changed by Fig. 2, obtain preferably photoengraving pattern.
(6) exposure post-drying.Should immediately film be carried out heatable catalytic after the exposure, the thermocatalysis time of different thickness sees Table 3.
(7) develop.Behind the film cool to room temperature behind the thermocatalysis, be immersed in the developing solution, soak 1min, can be aided with suitable ultrasonic.
(8) cleaning-drying.Film after developing is cleaned in Virahol, remove residual photographic developer, then dry.
The corresponding front drying time of table 1 different thickness
The exposure energy that table 2 different thickness is corresponding
The thermocatalysis time of different thickness after table 3 exposure
The preparation of embodiment 8 photo-resists and lithography process
Photoresist material of the present invention is by mixing following component preparation, each amounts of components based on the photoetching compositions gross weight by weight percentage ratio represent:
Photoresist material amounts of components (wt%)
Resin binder 99%
Photo-acid agent 1%
Resin binder is that the SU-8 that does not add photo-acid agent 2005 glue that excellent company buys are thought in Nanjing hundred, and the structure of photo-acid agent compound is shown in 9.
The photoresist material for preparing is used after sol evenning machine films, heat 3min at hot platform, temperature is controlled at about 95 ± 2 ℃, is covered with after the mask, uses wavelength to be about as the light source of the 405nm 25s(light intensity of exposing: 8.7 ± 0.3mwcm
-2), heat 3min at 95 ± 2 ℃ hot platform again, then in developing solution, develop, obtain photoengraving pattern, and then it is cleaned with Virahol, drying.Lower Fig. 3 is the mask pattern of examining under a microscope, and Fig. 4 is the image of observing under the SEM Electronic Speculum after the photoetching.
The preparation of embodiment 9 photo-resists and lithography process
Photoresist material of the present invention is by mixing following component preparation, each amounts of components based on the photoetching compositions gross weight by weight percentage ratio represent:
Photoresist material amounts of components (wt%)
Resin binder 99%
Photo-acid agent 1%
Resin binder is that the SU-8 that does not add photo-acid agent 2005 glue that excellent company buys are thought in Nanjing hundred, and the structure of photo-acid agent compound is shown in 9.
The photoresist material for preparing is used after sol evenning machine films, heat 3min at hot platform, temperature is controlled at about 95 ± 2 ℃, is covered with after the mask, uses wavelength to be about as the light source of the 405nm 25s(light intensity of exposing: 8.7 ± 0.3mwcm
-2), heat 3min at 95 ± 2 ℃ hot platform again, then in developing solution, develop, obtain photoengraving pattern, and then it is cleaned with Virahol, drying.Fig. 5 is the mask pattern of examining under a microscope, and Fig. 6 is the image of observing under the SEM Electronic Speculum after the photoetching.
Claims (10)
1. one kind high photogenerated acid quantum yield sulfosalt class photo-acid agent is characterized in that the structural formula of described photo-acid agent is as follows:
R wherein
1For in methyl, benzyl, phenyl-pentafluoride base or the 4-cyano group benzyl any; R
2 -Be gegenion.
2. according to claim 1 high photogenerated acid quantum yield sulfosalt class photo-acid agent is characterized in that described R
2 -For in trifluoromethayl sulfonic acid root, hexafluoro-phosphate radical, hexafluoroantimonic anion or the tetrafluoroborate any.
3. the preparation method of a high photogenerated acid quantum yield sulfosalt class photo-acid agent as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) under protection of inert gas, with 2.67g, 10mmol N, N-pentanoic benzaldehyde is dissolved in the anhydrous tetrahydro furan, and adds 5.36g, 15mmol methyltriphenylphospbromide bromide phosphorus, 0
oDrip the 3.6g that is dissolved in tetrahydrofuran (THF) under the C, the 30mmol potassium tert.-butoxide, keeping system temperature is 0
oC ~ 10
oC; Be warming up to room temperature after dripping, stirring reaction 3 ~ 6 hours, reaction soln is poured into water, dichloromethane extraction, salt water washing, organic phase anhydrous sodium sulfate drying, column chromatography obtains liquid, after desolventizing, vacuum obtains white powder product (2.168g, 8mmol) N, N-hexichol amido vinylbenzene;
(2) under the protection of inert gas, with step (1) product 2.71g, 10mmol N; N-hexichol amido vinylbenzene adds in the 33mL trolamine, adds 2.03g, 10mmol 3-bromobenzene dimethyl sulfide and 40mg again; 0.18mmol palladium is heated with stirring to 100 ~ 120
oC, lucifuge stirs, and reacts after 10 ~ 12 hours, is poured into water to produce blackish green solid, filter, the solid that filtration is obtained is dissolved in the methylene dichloride, removes palladium through filtered through silica gel, and filtrate desolventizes rear acquisition thick liquid, purify through column chromatography, obtain faint yellow solid product 2.87g, 7mmol 3-(N, N-hexichol amido styryl) thioanisole; Wherein: the eluent that adopts in the column chromatography is the mixed solution of cyclohexane and ethyl acetate, and the volume ratio of hexanaphthene and ethyl acetate is 10/1 ~ 5/1;
(3) with step (2) product 3-(N, N-hexichol amido styryl) thioanisole is dissolved in the anhydrous methylene chloride, in dry ice acetone bath, add the trifluoro-methane sulfonic acid silver of 1.5 times of amounts and halogenated alkane or the halogenated aryl hydrocarbon of 1.5 times of amounts, lucifuge stirs after 0.5 ~ 1 hour and removes freezing plant, the desolventizing after 20 ~ 24 hours of lucifuge stirring at room, add the acetonitrile dissolving, the filtering undissolved solid, concentrated solution is added dropwise in the anhydrous diethyl ether, produce yellow mercury oxide, filter to such an extent that be dissolved in acetone after the precipitation, be added dropwise in the saturated aqueous solution of inorganic salt, produce yellow mercury oxide, obtain yellow powder after filtering, be required product.
4. preparation method according to claim 3 is characterized in that rare gas element is nitrogen described in step (1) and the step (2).
5. preparation method according to claim 3 is characterized in that halogenated alkane described in the step (3) adopts methyl iodide; Halogenated aryl hydrocarbon adopts in benzyl bromine, 4-cyano group benzyl bromine or five fluorobenzyl bromides any.
6. preparation method according to claim 3, the saturated aqueous solution that it is characterized in that inorganic salt described in the step (3) be in phosphofluoric acid potassium solution, hexafluoro-antimonic acid sodium solution or the Tetrafluoroboric acid sodium solution any.
7. preparation method according to claim 3, it is characterized in that the ratio of anhydrous diethyl ether and acetonitrile solution is the ether volume in the step (3): the acetonitrile solution volume is 10:1.
8. preparation method according to claim 3, it is characterized in that the saturated aqueous solution of inorganic salt in the step (3) and the ratio of acetone soln are the saturated aqueous solution volume: the acetone soln volume is 25:1.
9. the application of a high photogenerated acid quantum yield sulfosalt class photo-acid agent as claimed in claim 1 in photoresist material.
10. application according to claim 9 is characterized in that described high photogenerated acid quantum yield sulfosalt class photo-acid agent is applied to form the photoresist material camegraph, and step is as follows:
(1) at slide glass or silicon chip coating photoetching compositions film;
(2) heating, drying is removed solvent on hot platform;
(3) with the photographic developer flash trimming;
(4) with the light source irradiation photoresist film, described optical source wavelength is 365nm～425nm;
(5) baking photoresist material after;
The film that (6) will shine with developing solution develops;
(7) cleaning and dry.
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| CN104181772A (en) * | 2014-08-15 | 2014-12-03 | 同济大学 | Two-photon active photoacid generators taking biphenyl as conjugated structure and preparation method and application of two-photon active photoacid generators |
| CN104238268A (en) * | 2014-08-15 | 2014-12-24 | 同济大学 | Sulfonium salt photoacid generator adopting triphenylethylene as main body, preparation method of sulfonium salt photoacid generator and application of sulfonium salt photoacid generator |
| WO2015174471A1 (en) * | 2014-05-13 | 2015-11-19 | 東洋合成工業株式会社 | Onium salt, photoacid generator, photosensitive resin composition, and method for producing device |
| CN107129487A (en) * | 2017-04-10 | 2017-09-05 | 同济大学 | LED of one class using thioxanthone as conjugated structure can excite the preparation method and applications of sulfosalt |
| CN110105256A (en) * | 2019-04-30 | 2019-08-09 | 同济大学 | α-amido ketone-talan sulphur salt compounds and its preparation method and application |
| CN110824836A (en) * | 2018-08-13 | 2020-02-21 | 常州强力先端电子材料有限公司 | Cationic photocurable composition and application thereof |
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