Polymerizable photoacid generator containing double-onium salt structure, preparation method and photoresist
阅读说明：本技术 可聚合型含双鎓盐结构的光致产酸剂、制备方法及光刻胶 (Polymerizable photoacid generator containing double-onium salt structure, preparation method and photoresist ) 是由 齐国强 顾大公 毛智彪 许从应 余绍山 许东升 于 2020-12-22 设计创作，主要内容包括：本发明适用于光刻胶领域,提供了一种可聚合型含双鎓盐结构的光致产酸剂,用于光刻胶的制备。该可聚合型含双鎓盐结构的光致产酸剂具有如下结构通式(I)：其中,n为大于等于1的整数；R-1～R-4为H、碳原子数为1～20的烷基、芳基或含硫/氧/氮杂原子的取代基中的一种或多种；阴离子M～-为磺酸阴离子。本发明的可聚合型含双鎓盐结构的光致产酸剂具有双鎓盐结构,相对于单一鎓盐结构的光致产酸剂,本发明的可聚合型含双鎓盐结构的光致产酸剂具有较高的产酸效率,可以适用于多种波长的光源。由于本发明的可聚合型含双鎓盐结构的光致产酸剂本身就是可聚合型的,所以使用该可聚合型含双鎓盐结构的光致产酸剂的光刻胶不需要再额外的添加光刻胶树脂。(The invention is applicable to the field of photoresist, and provides a polymerizable photoacid generator containing a double-onium salt structure, which is used for preparing photoresist. The polymerizable photoacid generator containing a bis-onium salt structure has the following structural general formula (I): wherein n is an integer greater than or equal to 1; r 1 ～R 4 Is H,One or more of alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom; anion M ‑ Is a sulfonic acid anion. The polymerizable photoacid generator containing the bis-onium salt structure has a bis-onium salt structure, and compared with a photoacid generator with a single onium salt structure, the polymerizable photoacid generator containing the bis-onium salt structure has high acid generation efficiency and can be applied to light sources with various wavelengths. Since the polymerizable photoacid generator containing a bis-onium salt structure of the present invention is polymerizable itself, a photoresist using the polymerizable photoacid generator containing a bis-onium salt structure does not require an additional photoresist resin.)
1. A polymerizable photoacid generator containing a bis-onium salt structure, which has the following structural general formula (I):
wherein n is an integer greater than or equal to 1; r1～R4One or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom; anion M-Is a sulfonic acid anion.
2. The polymerizable double onium salt structure-containing photoacid generator according to claim 1, wherein: the sulfonic acid anion is perfluorobutyl sulfonic acid anion, perfluorooctyl sulfonic acid anion, p-toluenesulfonic acid anion or camphorsulfonic acid anion.
3. The method for preparing the polymerizable double onium salt structure-containing photoacid generator according to any one of claims 1 to 2, comprising the steps of:
dissolving substituted diphenyl sulfoxide and substituted diphenyl sulfide in a first organic solvent according to a certain proportion, then placing the first organic solvent and the substituted diphenyl sulfoxide and the substituted diphenyl sulfide in a reaction kettle, reducing the temperature of the reaction kettle to a temperature T, then dropwise adding sulfonic anhydride, reacting for a period of time, extracting an organic phase, and desolventizing to obtain a photoacid generator monomer precursor;
dissolving a photoacid generator monomer precursor, sulfonate and 2-ethylmethacrylate in a second organic solvent, mixing, stirring, adding water, continuously stirring, performing desolventizing to obtain a turbid water phase, extracting, and performing desolventizing again to obtain a photoacid generator monomer containing a bis-onium salt structure;
adding cyclopentyl methacrylate, 1-adamantyl methacrylate and a photoacid generator monomer containing a bis-onium salt structure into a reaction kettle, adding a third organic solvent into the reaction kettle, heating the reaction kettle to a polymerization reaction temperature after stirring, dropwise adding a mixed solution of the third organic solvent and an initiator into the reaction kettle, and reacting for a period of time at the polymerization reaction temperature to obtain a polymerizable polymerization solution containing the photoacid generator containing the bis-onium salt structure;
and cleaning the polymer solution to obtain the polymerizable photoacid generator containing the bis-onium salt structure.
4. The method for producing a polymerizable photoacid generator containing a bis-onium salt structure according to claim 3, wherein: the mass ratio of the substituted diphenyl sulfoxide, the substituted diphenyl sulfide and the sulfonic anhydride is (1.5-2.5): (0.5-1.5): 1-2.
5. The method for producing a polymerizable photoacid generator containing a bis-onium salt structure according to claim 3, wherein: the structural general formula of the substituted diphenyl sulfoxide isThe substituted diphenyl sulfide has a structural general formulaWherein R is1～R4Is one or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom.
6. The method for producing a polymerizable photoacid generator containing a bis-onium salt structure according to claim 3, wherein: the sulfonic anhydride is trifluoromethanesulfonic anhydride, p-toluenesulfonic anhydride, perfluorobutylsulfonic anhydride or methylsulfonic anhydride.
7. The method for producing a polymerizable photoacid generator containing a bis-onium salt structure according to claim 3, wherein: the molar ratio of the photoacid generator monomer precursor to the sulfonate to the methacrylic acid 2-ethanesulfonate is (0.8-1.6): (0.2-1.0): (0.6-1.2).
8. The method for producing a polymerizable photoacid generator containing a bis-onium salt structure according to claim 3, wherein: the sulfonate is perfluorobutyl sulfonate, perfluorooctyl sulfonate, p-toluene sulfonate or camphor sulfonate.
9. The method for producing a polymerizable photoacid generator containing a bis-onium salt structure according to claim 3, wherein: the molar ratio of the cyclopentyl methacrylate to the 1-adamantyl methacrylate to the photoacid generator monomer having a bis-onium salt structure is (65-70): (25-29.9): (0.1-10).
10. The method for producing a polymerizable photoacid generator containing a bis-onium salt structure according to claim 3, wherein: the temperature T is in the range of-30-0 ℃, and the polymerization reaction temperature is in the range of 40-90 ℃.
11. The method for producing a polymerizable photoacid generator containing a bis-onium salt structure according to claim 3, wherein: the dosage of the initiator is 0.3-15% of the total mass of the cyclopentyl methacrylate and the 1-adamantyl methacrylate.
12. A photoresist comprising an acid diffusion inhibitor, an organic solvent and the polymerizable double onium salt structure-containing photoacid generator according to any one of claims 1 to 2.
Technical Field
The invention belongs to the field of photoresist, and particularly relates to a polymerizable photoacid generator containing a bis-onium salt structure, a preparation method of the polymerizable photoacid generator containing a bis-onium salt structure, and photoresist using the polymerizable photoacid generator containing a bis-onium salt structure.
Background
With the development of high-integration, ultra-high-speed and ultra-high-frequency integrated circuits and devices, the feature sizes of large-scale integrated circuits and ultra-large-scale integrated circuits become thinner and thinner, the further development of the integrated circuits needs the support of corresponding exposure technology, and the photoresist technology is an important component of the exposure technology. High performance exposure tools require high performance photoresists to be compatible with them to actually achieve high resolution throughput.
Photoresists are one of the key materials for fine patterning in microelectronics, and are photosensitive films for transferring images to substrates. The main components of the photoresist are a polymer resin, a Photo Acid Generator (PAG), and corresponding additives and solvents. Photoacid generators are important components of photoresist systems and decompose under light to generate acids (H +), which can act as catalysts to cause the shedding of pendant acid labile groups on the polymer during the post-exposure baking process and generate new acids, which change the polarity of the polymer, after sufficient pendant groups have been shed, the photoresist can be dissolved in the developer.
At present, photoacid generators used in photoresists are generally sulfonium salts and iodonium salts with single structures, and the photoacid generators with the single onium salt structures have strong acid generation capacity, but have low acid generation efficiency and limited absorption wavelength, and can only be applied to a single light source.
Disclosure of Invention
The embodiment of the invention provides a novel polymerizable photoacid generator monomer containing a double-onium salt structure, aiming at solving the problems of low acid generation efficiency and limited absorption wavelength of a photoacid generator with a single-onium salt structure.
The embodiment of the invention is realized by a polymerizable photoacid generator containing a bi-onium salt structure, which has the following structural general formula (I):
wherein n is an integer greater than or equal to 1; r1～R4One or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom; anion M-Is a sulfonic acid anion.
Further, the sulfonic acid anion is a perfluorobutanesulfonic acid anion, a perfluorooctylsulfonic acid anion, a p-toluenesulfonic acid anion, or a camphorsulfonic acid anion.
The embodiment of the invention also provides a preparation method of the polymerizable photoacid generator containing the bis-onium salt structure, which comprises the following steps:
dissolving substituted diphenyl sulfoxide and substituted diphenyl sulfide in a first organic solvent according to a certain proportion, then placing the first organic solvent and the substituted diphenyl sulfoxide and the substituted diphenyl sulfide in a reaction kettle, reducing the temperature of the reaction kettle to a temperature T, then dropwise adding sulfonic anhydride, reacting for a period of time, extracting an organic phase, and desolventizing to obtain a photoacid generator monomer precursor;
dissolving a photoacid generator monomer precursor, sulfonate and 2-ethylmethacrylate in a second organic solvent, mixing, stirring, adding water, continuously stirring, performing desolventizing to obtain a turbid water phase, extracting, and performing desolventizing again to obtain a photoacid generator monomer containing a bis-onium salt structure;
adding cyclopentyl methacrylate, 1-adamantyl methacrylate and a photoacid generator monomer containing a bis-onium salt structure into a reaction kettle, adding a third organic solvent into the reaction kettle, heating the reaction kettle to a polymerization reaction temperature after stirring, dropwise adding a mixed solution of the third organic solvent and an initiator into the reaction kettle, and reacting for a period of time at the polymerization reaction temperature to obtain a polymerizable polymerization solution containing the photoacid generator containing the bis-onium salt structure;
and cleaning the polymer solution to obtain the polymerizable photoacid generator containing the bis-onium salt structure.
Furthermore, the mass ratio of the substituted diphenyl sulfoxide, the substituted diphenyl sulfide and the sulfonic anhydride is (1.5-2.5): (0.5-1.5): 1-2.
Furthermore, the structural general formula of the substituted diphenyl sulfoxide is shown asThe substituted diphenyl sulfide has a structural general formulaWherein R is1～R4Is one or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom.
Still further, the sulfonic anhydride is trifluoromethanesulfonic anhydride, p-toluenesulfonic anhydride, perfluorobutylsulfonic anhydride, or methanesulfonic anhydride.
Furthermore, the molar ratio of the photoacid generator monomer precursor to the sulfonate to the methacrylic acid 2-ethanesulfonate is (0.8-1.6): (0.2-1.0): (0.6-1.2).
Still further, the sulfonate is perfluorobutylsulfonate, perfluorooctylsulfonate, p-toluenesulfonate or camphorsulfonate.
Further, the molar ratio of the cyclopentyl methacrylate, the 1-adamantyl methacrylate and the photoacid generator monomer having a bis-onium salt structure is (65-70): (25-29.9): (0.1-10).
Furthermore, the temperature T is in the range of-30 to 0 ℃, and the polymerization reaction temperature is in the range of 40 to 90 ℃.
Furthermore, the dosage of the initiator is 0.3 to 15 percent of the total mass of the cyclopentyl methacrylate and the 1-adamantyl methacrylate.
The embodiment of the invention also provides a photoresist, which comprises the polymerizable photoacid generator containing the bis-onium salt structure, an acid diffusion inhibitor and an organic solvent.
The polymerizable photoacid generator containing a bis-onium salt structure of the present invention has a bis-onium salt structure, and therefore, compared to a photoacid generator having a single onium salt structure, the polymerizable photoacid generator containing a bis-onium salt structure of the present invention has a higher acid generation efficiency, and can be applied to light sources of various wavelengths. Since the polymerizable photoacid generator containing a bis-onium salt structure of the present invention is polymerizable itself, a photoresist using the polymerizable photoacid generator containing a bis-onium salt structure does not require an additional photoresist resin. In addition, the polymerizable photoacid generator containing the bis-onium salt structure is more uniformly distributed in the photoresist, and the line width and the roughness of a circuit manufactured by using the photoresist can be effectively improved.
Drawings
FIG. 1 is a flow chart of the method for preparing a polymerizable photoacid generator containing a bis-onium salt structure according to a preferred embodiment of the present invention.
FIG. 2 is a photograph of an electron microscope after photoresist is etched according to a second embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a polymerizable photoacid generator containing a bi-onium salt structure, which is used for preparing photoresist. The photoacid generator containing the polymerizable type bi-onium salt structure has the following structural general formula (I):
wherein n is an integer greater than or equal to 1; r1～R4The alkyl group may be one or more of H, an alkyl group having 1 to 20 carbon atoms, an aryl group, or a substituent containing a sulfur/oxygen/nitrogen heteroatom.
Anion M-Is a sulfonic acid anion. The sulfonic acid anion may be a perfluorobutylsulfonic acid anion, a perfluorooctylsulfonic acid anion, a p-toluenesulfonate anion, a camphorsulfonic acid anion, or the like.
In other words, the polymerizable double onium salt structure-containing photoacid generator is a (meth) acrylic resin containing a double onium salt structure-containing photoacid generator monomer.
The polymerizable double onium salt structure-containing photoacid generator has a double onium salt structure, and the polymerizable double onium salt structure-containing photoacid generator of the present invention has a higher acid generation efficiency than a single onium salt structure-containing photoacid generator, and can be applied to light sources having various wavelengths, for example, light sources having wavelengths of 248nm (krf), 193nm (arf), 13nm (euv), and the like. Since the polymerizable photoacid generator containing a bis-onium salt structure of the present invention is polymerizable itself, a photoresist using the polymerizable photoacid generator containing a bis-onium salt structure does not require an additional photoresist resin. In addition, the polymerizable photoacid generator containing the bis-onium salt structure is more uniformly distributed in the photoresist, and the line width and the roughness of a circuit manufactured by using the photoresist can be effectively improved.
Referring to fig. 1, a method for preparing a polymerizable photoacid generator having a bis-onium salt structure according to an embodiment of the present invention includes the following steps:
step S1: the preparation method of the photoacid generator monomer containing the bis-onium salt structure comprises the following steps:
a1dissolving substituted diphenyl sulfoxide and substituted diphenyl sulfide in a certain proportion in a first organic solvent, then placing the first organic solvent in a reaction kettle filled with nitrogen, reducing the temperature of the reaction kettle to a temperature T, then dropwise adding sulfonic anhydride, and reacting for a period of time T1Adding water, stopping reaction, cooling the temperature of the reaction kettle to room temperature, separating liquid, extracting an organic phase, desolventizing to constant weight, and cleaning the organic phase to obtain a compound A, namely a photoacid generator monomer precursor, wherein the chemical reaction formula is as follows:
in the chemical reaction formulaIs a structural general formula of substituted diphenyl sulfoxide, in the chemical reaction formulaIs a structural general formula of substituted diphenyl sulfide, wherein, R1～R4Is one or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom.
The mass ratio of the substituted diphenyl sulfoxide, the substituted diphenyl sulfide and the sulfonic anhydride is (1.5-2.5): (0.5-1.5): 1-2.
In the chemical reaction formulaIs a structural general formula of sulfonic anhydride, wherein R is5、R6Including but not limited to trifluoromethyl (-CF)3) P-tolyl group, perfluorobutyl group (-C)4F9) Or methyl (-CH)3). In other words. The sulfonic anhydride includes but is not limited to trifluoromethanesulfonic acidAnhydride (Tf)2O), p-toluenesulfonic anhydride, perfluorobutylsulfonic anhydride or methanesulfonic anhydride.
The first organic solvent includes but is not limited to one or more of dichloromethane, trichloromethane and dichloroethane.
The temperature T is in the range of-30-0 ℃.
The reaction time t1The reaction time can be 3-12 h, and preferably is 5 h.
In at least one embodiment, the wash solution used to wash the organic phase is diethyl ether. It will be appreciated that in other embodiments, other precipitation solvents may be employed as the wash solution, provided that the organic phase is allowed to precipitate.
a2Dissolving a compound A, sulfonate and 2-ethylsulfonate methacrylate in a second organic solvent, mixing, stirring, adding water, continuously stirring, performing desolventizing to obtain a turbid water phase, extracting an organic phase, and performing desolventizing to obtain a compound B, wherein the compound B is a photoacid generator monomer containing a bis-onium salt structure, and has the following chemical reaction formula:
the molar ratio of the compound A to the sulfonate to the methacrylic acid 2-ethanesulfonate is (0.8-1.6): (0.2-1.0): (0.6-1.2).
M-Q in the reaction formula represents the structural general formula of sulfonate. The sulfonate includes, but is not limited to, perfluorobutylsulfonate, perfluorooctylsulfonate, p-toluenesulfonate, or camphorsulfonate, corresponding, M-Can be perfluorobutyl, perfluorooctyl, p-tolyl or camphorsulfo, and the Q can be metal ions such as Na or K. In at least one embodiment, the perfluorobutyl sulfonate is sodium perfluorobutyl sulfonate, and the corresponding Q is Na.
The 2-ethanesulfonate of methacrylic acid may be sodium 2-ethanesulfonate of methacrylic acid, potassium 2-ethanesulfonate of methacrylic acid, etc., and correspondingly, the QmIs Na or K.
The second organic solvent includes, but is not limited to, one or more of methanol, ethyl acetate, dichloromethane, ethanol, acetone, methyl ethyl ketone, and tetrahydrofuran.
In at least one embodiment, the solvent used to extract the organic phase includes, but is not limited to, one or more of dichloromethane, chloroform, ethyl acetate, dichloroethane, trichloroethane.
Step S2: the preparation method of the polymerizable photoacid generator containing the bis-onium salt structure comprises the following steps:
b1adding cyclopentyl methacrylate, 1-adamantyl methacrylate and a compound B into a reaction kettle filled with nitrogen, adding a third organic solvent into the reaction kettle, uniformly stirring, heating the reaction kettle to a polymerization reaction temperature, dropwise adding a mixed solution of the third organic solvent and an initiator into the reaction kettle, and reacting at the polymerization reaction temperature for a period of time t2The reaction was stopped, and the temperature of the reaction vessel was cooled to room temperature to obtain a polymerization solution containing a polymerizable photoacid generator having a bis-onium salt structure.
The structural formula of the cyclopentyl methacrylate is as follows:
the structural formula of the 1-adamantyl methacrylate is as follows:
the molar ratio of the cyclopentyl methacrylate to the 1-adamantyl methacrylate to the compound B is (65-70): (25-29.9): (0.1-10).
The initiator may be an azo initiator or a radical initiator of peroxide. The azo initiator includes, but is not limited to, one or two of azobisisobutyronitrile and azobisisoheptonitrile. The peroxide radical initiator includes, but is not limited to, one or more of tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoic acid hydroperoxide, benzoyl peroxide. The dosage of the initiator is 0.3 to 15 percent of the total mass of the cyclopentyl methacrylate and the 1-adamantyl methacrylate.
The third organic solvent includes, but is not limited to, one or more of methanol, ethyl acetate, dichloromethane, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane, trichloroethane.
The polymerization reaction temperature is controlled to be between 40 and 90 ℃ according to different used third organic solvents and initiators, and the polymerization reaction time t2And the time is controlled to be between 4 and 32 hours according to the difference of the third organic solvent and the initiator.
b2And washing the polymer solution by using a washing solution to generate a precipitate, then leading out the liquid, and drying the precipitate in vacuum to obtain the polymerizable photoacid generator containing the bis-onium salt structure.
It is understood that, in order to obtain a polymerizable photoacid generator having a bis-onium salt structure with a higher purity, the following may be further included:
step b3And dissolving the precipitate by using a third solvent, then washing by using a washing solution again to obtain the precipitate, then leading out the liquid, and drying the precipitate in vacuum.
As can be appreciated, said step b3Can be repeated for a plurality of times to obtain the polymerizable photoacid generator with the double onium salt structure with higher purity
The washing solution can be pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether, methyl tert-butyl ether, etc.
It is understood that in other embodiments, a method conventionally used for removing small molecule substances from polymer resins, such as drop-in cleaning, may also be used.
In the step b3, the yield of the polymerizable photoacid generator containing a bis-onium salt structure after vacuum drying is 50% to 80%.
The embodiment of the invention also provides a photoresist, which comprises the polymerizable photoacid generator containing the bis-onium salt structure, an acid diffusion inhibitor and an organic solvent. Since the polymerizable double onium salt structure-containing photoacid generator itself is polymerizable, no additional photoresist resin is required for using the photoresist.
In the photoresist, the mass percentage content of the polymerizable photoacid generator containing a bis-onium salt structure is 10-30%, the mass percentage content of the acid diffusion inhibitor is 0.1-15%, and the mass percentage content of the organic solvent is 55-89.8%.
The acid diffusion inhibitor includes, but is not limited to, one or more of N-butylamine, t-butylamine, dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-t-butylamine, trimethylamine, triethylamine, tri-N-propylamine, triisopropylamine, tri-t-butylamine, ethanolamine, diethanolamine, triethanolamine, cyclopentylamine, cyclohexylamine, morpholine, N-methylcyclopentylamine, methylaniline, ethylaniline, N-butylaniline, t-butylaniline, dimethylaniline, diethylaniline, dibutylbenzene, diphenylaniline. The acid diffusion inhibitor can inhibit acid diffusion in the photoresist.
The organic solvent includes, but is not limited to, one or more of propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone. The organic solvent can effectively dissolve other components contained in the photoresist. The content of the organic solvent is adjusted, so that the photoresist can be adjusted to a certain viscosity, and the photoresist can be uniformly coated on the surface of the base material. Preferably, the organic solvent in the photoresist is a mixed solvent of propylene glycol methyl ether acetate and propylene glycol monoethyl ether.
The photoresist comprises the polymerizable photoacid generator containing the bis-onium salt structure, so that the photoresist can be suitable for various light sources, and the polymerizable photoacid generator containing the bis-onium salt structure is uniformly distributed in the photoresist, so that the line width and the roughness of a circuit manufactured by using the photoresist can be effectively improved.
In one embodiment, the method for preparing the photoresist comprises: at room temperature, sequentially adding a polymerizable photoacid generator containing a bis-onium salt structure, an acid diffusion inhibitor and an organic solvent according to a formula ratio to obtain a mixture, shaking the mixture for 16-96 h in a dark place to fully dissolve the mixture to obtain a mixed solution, filtering the mixed solution by using a filter made of a nylon material with the particle size of 0.5 micron or less and a UPE material, and collecting filtrate to obtain the photoresist.
The present invention will now be described in detail with reference to specific examples, which are intended to be illustrative of preferred embodiments of the present invention and are not to be construed as limiting the invention thereto.
Example one
Preparation of photoacid generator monomer containing double onium salt structure
a1Dissolving 21g of diphenyl sulfoxide and 19g of diphenyl sulfide in 300ml of dichloromethane, then placing the dichloromethane into a reaction kettle filled with nitrogen, reducing the temperature of the reaction kettle to-15 ℃, then dropwise adding 29g of trifluoromethanesulfonic anhydride for 3min, reacting for 3 hours, adding 200ml of pure water, stopping the reaction, then cooling the temperature of the reaction kettle to room temperature, separating liquid, extracting an organic phase, desolventizing to constant weight, and washing twice with 50ml of diethyl ether to obtain 22g of compound A, wherein the chemical reaction formula is as follows:
a2dissolving 86g of the compound A, 33g of sodium perfluorobutylsulfonate and 20g of 2-ethylsulfonate sodium methacrylate in 50g of methanol (MeOH), mixing, stirring for 12 hours, adding 50ml of pure water, continuing stirring for 3 hours, performing desolventization to obtain a turbid aqueous phase, extracting an organic phase with 50g of dichloromethane, and performing desolventization40g of compound B is obtained, the compound B is a photoacid generator monomer containing a bis-onium salt structure, and the chemical reaction formula is as follows:
in this example, the yield of the compound a was 26% and the yield of the compound B was 38%.
Preparation of polymerizable photoacid generator containing double onium salt structure
b1Adding 45g of cyclopentyl methacrylate, 20g of 1-adamantyl methacrylate and 5g of compound B into a reaction kettle filled with nitrogen, adding 60g of ethyl acetate into the reaction kettle, uniformly stirring, heating the reaction kettle to the polymerization reaction temperature of 77 ℃, dropwise adding a mixed solution of 10g of ethyl acetate and 1g of benzoyl peroxide into the reaction kettle, reacting at the polymerization reaction temperature of 77 ℃ for 7 hours, stopping the reaction, and cooling the temperature of the reaction kettle to the room temperature;
b2adding 600g of methanol into the reaction kettle cooled to room temperature to generate a precipitate for 1 hour, and then discharging liquid in the reaction kettle;
b3adding 70g of ethyl acetate into the precipitate in the reaction kettle until the first precipitate is dissolved, adding 600g of methanol into the reaction kettle to generate precipitate, then leading out the liquid in the reaction kettle, and drying the precipitate in vacuum to obtain 37g of the polymerizable photoacid generator containing the bis-onium salt structure.
The structure formula of the polymerizable photoacid generator containing a bis-onium salt structure prepared in this example is as follows:
in this example, the yield of the polymerizable double onium salt structure-containing photoacid generator was 46%.
The polymerizable photoacid generator having a bis-onium salt structure obtained in this example was measured by GPC equipment, and its molecular weight Mw was 12000 and PDI was 1.66.
Example two
Preparation of photoresists
In a clean 100mL glass bottle, 8.5g of a polymerizable photoacid generator containing a bis-onium salt structure, 0.06g of a mixed acid diffusion inhibitor having a mass ratio of tert-butylamine to diisobutylamine of 2:8, 32g of propylene glycol monomethyl ether acetate, and 48g of propylene glycol monomethyl ether were sequentially added to obtain a mixture, and the mixture was shaken in the bottle in the dark for 24 hours to be sufficiently dissolved to obtain a mixed solution. Then, the mixed solution is filtered by using filters made of a nylon material and a UPE material of 0.22 micron and 0.02 micron in sequence, and filtrate is collected to obtain the photoresist.
A photolithography experiment was performed on the photoresist prepared in the second example. The method of the lithography experiment is as follows:
the prepared photoresist is rotated on a 12' silicon wafer at the speed of 2000-3000 r/min to form a film, then the film is baked on a hot plate at the temperature of 120 ℃ for 90 seconds, and then the film is exposed on an exposure machine at the speed of 10-50 mJ/cm2Exposing, baking on a hot plate at 110 deg.C for 90 s, developing in 2.38% TMAH developer for 60 s, oven drying, and inspecting the result under an electron microscope (see FIG. 2).
As can be seen from FIG. 2, the resolution of the photoresist after photolithography reaches the predetermined target of T81/P190, and the line width after photolithography reaches 80.72 nm. In addition, the line roughness obtained after photoetching is low in pattern view.
The polymerizable photoacid generator containing the bis-onium salt structure has a bis-onium salt structure, and compared with a photoacid generator with a single onium salt structure, the polymerizable photoacid generator containing the bis-onium salt structure has high acid generation efficiency and can be applied to light sources with various wavelengths. Since the polymerizable photoacid generator containing a bis-onium salt structure of the present invention is polymerizable itself, a photoresist using the polymerizable photoacid generator containing a bis-onium salt structure does not require an additional photoresist resin. In addition, the polymerizable photoacid generator containing the bis-onium salt structure is more uniformly distributed in the photoresist, and the line width and the roughness of a circuit manufactured by using the photoresist can be effectively improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
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